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Title: A new system of chemical philosophy, Volume II, Part 1
Author: John Call Dalton
Release date: December 20, 2024 [eBook #74948]
Language: English
Original publication: Manchester: Executors of S. Russell for George Wilson
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*** START OF THE PROJECT GUTENBERG EBOOK A NEW SYSTEM OF CHEMICAL PHILOSOPHY, VOLUME II, PART 1 ***
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A NEW SYSTEM OF
CHEMICAL PHILOSOPHY.
PART FIRST.--VOL. II.
REPRODUCED IN FACSIMILIE
BY
WILLIAM DAWSON & SONS LTD.
102 WIGMORE STREET,
LONDON, W.1
AND PRINTED BY
HENDERSON & SPALDING
SYLVAN GROVE, OLD KENT ROAD,
LONDON, S.E.15
THIS EDITION IS LIMITED TO 1,000 COPIES
A NEW SYSTEM OF
CHEMICAL PHILOSOPHY.
_PART FIRST_
OF
VOL. II.
BY
JOHN DALTON, F.R.S.
President of the Literary and Philosophical Society, Manchester.
Corresponding Member of the Royal Academy of Sciences, Paris,
Member of the Royal Academy, Munich, and of the Cæsarean
Natural History Society, Moscow;
Honorary Member of the Royal Medical Society, Edinburgh,
and of the Philosophical Societies of Bristol, Cambridge,
Leeds, Sheffield and Yorkshire.
Manchester:
Printed by the Executors of S. Russell.
FOR
GEORGE WILSON, ESSEX STREET, STRAND
_LONDON_.
1827.
TO
JOHN SHARPE, ESQ. F. R. S.
OF STANMORE, MIDDLESEX,
(_Late of Manchester_,)
AS A TESTIMONY OF HIS FRIENDLY REGARD, AND OF HIS
LIBERAL ENCOURAGEMENT GIVEN TO THE PROMOTION
OF CHEMICAL SCIENCE:
AND TO
PETER EWART, ESQ.
_Vice-President of the Literary and Philosophical Society
of Manchester_,
ON THE SCORE OF FRIENDSHIP,
BUT MORE ESPECIALLY FOR THE ABLE EXPOSITION AND
EXCELLENT ILLUSTRATIONS OF THE FUNDAMENTAL
PRINCIPLES OF MECHANICS,
IN HIS ESSAY ON THE MEASURE OF MOVING FORCE,[1]
THIS WORK IS RESPECTFULLY INSCRIBED BY
_THE AUTHOR_.
[Footnote 1: Manchester Memoirs, Vol. II. (_second series._)]
PREFACE.
The work now submitted to the public was begun to be printed in 1817;
and the 13th and 14th sections, containing the oxides and sulphurets,
were printed off before the end of October of the same year. The
printing of the rest of the work to the appendix was finished in
September, 1821. One sheet of the appendix was printed at the end of
1823; but no addition was afterwards made till May, 1826; when the
printing was resumed, and has been continued to the present time.
It may be asked, what were the motives for such a plan of procedure.
To this it may be replied, that soon after the publication of the
first volume (in 1810), I began to prepare materials, and to institute
experiments, relating to the oxides, &c., with occasional diversions
into other departments of chemistry, as circumstances arose. As a great
portion of my time was always necessarily engaged in professional
duties, and as that part of the work I was about to commence was one
running into detail, I thought it would be best to print it as I
proceeded, whilst the train of thought and of experiments was fresh in
view. The advantage in this case was expected to be partly at least
counterbalanced by the loss of discoveries and improvements likely
to be made in the interval between the printing and publishing of
the several articles. This I was aware of; but as a principal object
I had in view was to give the results of my own experience, in the
various departments of chemical science, rather than to form the best
compilation of Chemistry at the period, this object was most likely to
be obtained by the proposed plan. It is true the time the work has been
in the press has far exceeded my expectation; notwithstanding this I am
not conscious of any very material alterations or additions, which I
should wish to make at the present moment.
It affords me great pleasure to acknowledge the assistance I have
had during the progress of this volume, from a valuable selection of
chemical apparatus, for which I am indebted to the generosity of Mr.
Sharpe; also the continued and friendly intercourse with Dr. Henry,
whose discussions on scientific subjects are always instructive, and
whose stores are always open when the promotion of science is the
object.
My present design is to add a second part to this volume, and with that
to finish the work. It will consist of the more complex compounds.
Acids, and other products of the vegetable kingdom, Salts, &c., will
form principal parts. Already I have a stock of experiments on these
subjects; but I am not satisfied without exploring this region afresh.
_August, 1827._
CONTENTS OF VOL. II.
_Part First._
Page.
CHAP. V.--COMPOUNDS OF TWO ELEMENTS.
SECTION 13. _Metallic Oxides_ 1
_Oxide of Gold_ 5
---- _Platina_ 11
---- _Silver_ 17
_Oxides of Mercury_ 19
_Oxide of Palladium_ 24
_Oxides of Rhodium, Iridium, and Osmium_ 26
---- _Copper_ 26
---- _Iron_ 28
---- _Nickel_ 34
---- _Tin_ 36
---- _Lead_ 39
_Oxide of Zinc_ 51
_Oxides of Potassium_ 53
---- _Sodium_ 56
_Oxide of Bismuth_ 57
_Oxides of Antimony_ 58
_Oxide of Tellurium_ 62
_Oxides of Arsenic_ 63
---- _Cobalt_ 68
---- _Manganese_ 71
---- _Chromium_ 80
---- _Uranium_ 86
---- _Molybdenum_ 87
---- _Tungsten_ 90
---- _Titanium_ 91
---- _Columbium_ 92
---- _Cerium_ 94
SECTION 14. _Earthy, Alkaline,
and Metallic Sulphurets_ 96
_Sulphurets of Lime_ 99
_Sulphuret of Magnesia_ 111
_Sulphurets of Barytes_ 112
---- _Strontites_ 114
---- _Alumine, Silex, Yttria,
Glucine and Zircone_ 114
---- _Potash_ 116
---- _Soda_ 119
_Sulphuret of Ammonia_ 120
_Sulphurets of Gold_ 121
_Sulphuret of Platina_ 123
_Sulphurets of Silver_ 126
---- _Mercury_ 127
_Sulphuret of Palladium_ 131
---- _Rhodium_ 132
---- _Iridium_ 132
---- _Osmium_ 132
_Sulphurets of Copper_ 133
---- _Iron_ 134
---- _Nickel_ 138
---- _Tin_ 139
---- _Lead_ 144
---- _Zinc_ 146
---- _Potassium and Sodium_ 148
---- _Bismuth_ 149
---- _Antimony_ 151
_Sulphuret of Tellurium_ 153
_Sulphurets of Arsenic_ 153
_Sulphuret of Cobalt_ 160
_Sulphurets of Manganese_ 162
_Sulphuret of Chromium_ 163
---- _Uranium_ 164
---- _Molybdenum_ 164
_Sulphuret of Tungsten_ 164
_Sulphurets of Titanium, Columbium,
and Cerium_ 165
SECTION 15. _Earthy, Alkaline,
and Metallic Phosphurets_ 166
_Phosphuret of Hydrogen_ 169
_Phosphurets of Carbon and Sulphur_ 184
_Phosphuret of Lime_ 184
---- _Barytes_ 188
---- _Strontites_ 190
---- _Gold_ 191
---- _Platina_ 194
---- _Silver_ 195
---- _Mercury_ 197
---- _Palladium_ 198
---- _Copper_ 199
---- _Iron_ 201
---- _Nickel_ 201
---- _Tin_ 202
---- _Lead_ 203
_Phosphurets of Zinc and Potassium_ 204
---- _Sodium and Bismuth_ 207
---- _Antimony and Arsenic_ 208
_Phosphuret of Cobalt_ 209
---- _Manganese_ 210
SECTION 16. _Carburets_ 211
---- of _Iron ... steel_ 212-214
SECTION 17. _Metallic Alloys_ 218
_Alloys of Gold, with other metals_ 222
---- _Platina, with other metals_ 226
---- _Silver, with other metals_ 228
---- _Mercury, and other metals:
amalgams_ 230
_Triple, Quadruple, &c. amalgams_ 236
_Alloys of Copper, with other metals_ 238
---- _Iron, with other metals_ 253
_Alloys of Nickel and Tin, with do._ 254
---- _Lead, with do._ 258
_Triple Alloys, Solders; fusible metal, &c._ 263
APPENDIX.
_Abstract of De la Roche and Berard’s essay
on the specific heat of gases_ 268
---- _Dulong and Petit’s essays,
On the expansion of air, mercury,
glass, iron, copper, and platina,
by heat_ 272
_On the capacities of certain bodies,
for heat_ 274
_On the laws of refrigeration_ 277
_On the specific heats of certain
bodies_ 280
_Remarks on the above essays_ 282
_New Table of the forces of vapours_ 298
_Table of the expansion of air, and the force
of aqueous and ætherial vapour, adapted
to atmospheric temperatures_ 299
_Applications of the above table_ 300
_Formulæ for determining the proportions of
combustible gases, in mixtures_ 305
_Heat produced by the combustion of gases_ 309
_Absorption of gases by water_ 309
_Fluoric acid--deutoxide of hydrogen_ 311
_Muriatic acid--oxymuriatic acid_ 313
_Nitric acid--compounds of azote and oxygen_ 315
_On ammonia_ 328
_Decomposition of ammonia by nitrous oxide_ 330
---- ---- ---- _by nitrous gas and oxygen_ 332
_Volume of gases from the decomposition of
ammonia_ 335
_Decomposition of ammonia by a red heat_ 335
_Decomposition of ammonia by oxymuriatic acid_335
_Sulphuret of Carbon_ 338
_Potassium, Sodium, &c._ 340
_Alum_ 341
_New table of the relative weights of atoms._ 352
ADDENDA. _Steel; mixed gases;
expansion of liquids by heat_ 354
NEW SYSTEM OF _CHEMICAL PHILOSOPHY_.
CHAP. V.
SECTION 13.
METALLIC OXIDES.
All the metals are disposed to combine with oxygen, but the combination
is effected more easily with some than with others; the compound is
usually called an _oxide_, but in some instances it is also called an
_acid_. The same metal combines with one, two, or perhaps more atoms of
oxygen, forming compounds which may be distinguished according to Dr.
Thomson, by the terms _protoxide_, _deutoxide_, _tritoxide_, &c.
Such however is the repulsion of oxygen to oxygen that we rarely
find three atoms of it retained by a single atom of any kind; and
there are not many instances of metals capable of holding two atoms
of oxygen. Various modifications of the proportions of metals and
oxygen arise from the combinations of the oxides themselves one with
another and with oxygen, so as to lead some to imagine that an atom of
metal in some instances combines with 3, 4, or more of oxygen. This
is altogether improbable: It is much more simple to suppose that one
atom of oxygen connects two or more atoms of protoxide, 1 of protoxide
unites to 1 or more of deutoxide, &c. These intermediate oxides are in
few if any instances found to combine with acids like the other two
oxides.
There is no reason that I am acquainted with for disbelieving that
oxygen combined with a metal is still repulsive of oxygen, and that by
the same law as particles of an elastic fluid; that is, the repulsion
is inversely as the distance of the centres of the atoms. Hence it
may be demonstrated that it requires twice the strength of affinity
to form a deutoxide as a protoxide, three times the strength to
form a tritoxide as a protoxide, &c. On this account it is, in all
probability, that deutoxides are not numerous, and tritoxides are
rarely if ever found.
The quantity of oxygen that combines with any metal to form an oxide
may be investigated by several methods.
1st. By combustion; a given weight of the metal may be burned and the
oxide produced may be collected and weighed; when the increase by
combustion will appear.
2. By solution in an acid and precipitation by an earth or alkali; in
this case a given weight of the metal is dissolved and precipitated;
the precipitate collected and sufficiently dried shews the increase by
oxygen.
3. By transferring the oxygen from an oxide to another metal; in this
case the metal in question is usually immersed in a saline solution of
the other metal; this latter metal gives up its oxygen to the former
and is itself reformed or _revived_ as it is termed.
4. By determining the proportion of hydrogen gas evolved during the
solution of a given weight of metal; then allowing half of that volume
for its equivalent of oxygenous gas, the weight of it shews the oxygen
united to the metal; it being now well understood that water furnishes
the two elements of hydrogen and oxygen in such case.
5. The higher oxides are conveniently determined by the application of
the solution of oxymuriate of lime to the lower oxides in solution.
6. The quantity of oxygen in several oxides may be found from the
quantity of nitrous gas evolved during the solution of a given weight
of metal in nitric acid.
The first four methods have been used by chemists for several years
past; the two last I have added from my own experience, having found
them very useful assistants in various instances. The last method by
nitrous gas, has indeed been proposed before, and labour bestowed on
it both by others and myself, but without reducing the results to any
certainty, till lately; the principal cause of this want of success
has arisen from misunderstanding the nature and constitution of nitric
acid. Most chemists seem with me to have mistaken _nitrous_ acid for
_nitric_; the former is composed of 1 atom of azote and 2 of oxygen; or
perhaps of 2 azote and 4 oxygen; the latter of 2 azote and 5 oxygen,
or 2 nitrous gas and 3 oxygen; the weight of the former is 19, or its
double 38, on my scale, and that of the latter 45. [My reasons for
adopting the above conclusion respecting nitrous acid, which is at
variance with that in VOL. 1, p. 331, will be given hereafter.] When
therefore a metal is oxidized by nitric acid, 3 atoms of oxygen (= 21)
go to the metal, and 2 atoms of nitrous gas (= 24) are disengaged.
Hence ⅞ of the weight of nitrous gas evolved is the weight of oxygen
combined. It sometimes happens however that the nitrous gas is partly
or wholly retained by the residue of nitric acid; but in this case
the oxymuriate of lime can be applied to convert the nitrous gas into
nitric acid, and from the oxygen imbibed the quantity of nitrous gas
may be inferred.
1. _Oxide of Gold._
Some difficulties have been found in ascertaining both the number and
proportions of the oxides of gold; hence the differences in the results
of authors.
Gold does not burn by exposure to heat, but gold leaf and gold wire
may be deflagrated by electricity and galvanism; a purple powder is
the product, which is considered by some as the protoxide of gold; but
others, after Macquer and Proust, conceive with greater probability
that this powder is nothing but gold reduced to its ultimate division.
Solutions of gold which are of a fine yellow, give a purple stain; and
gold deoxidized by green sulphate of iron is precipitated blue, which
precipitate gradually assumes a yellow colour as the particles become
united. The very weak affinity of gold for oxygen is shewn by the
difficulty with which it is oxidized and the ease with which the oxygen
is expelled again by heat; these facts seem to preclude the idea of
gold combining with oxygen in high temperatures.
_Protoxide._ Gold is scarcely affected by pure sulphuric, nitric
or muriatic acid; but it is easily oxidized and dissolved by
nitro-muriatic acid (that is, a mixture of nitric and muriatic acids)
when assisted by a temperature of 150 or 200°. Caustic potash being put
into the solution and heated, a brownish black precipitate is obtained;
but a part of the oxide remains in solution combined with the muriate
of potash, according to Vauquelin; and Proust has observed that the
oxide cannot be washed and dried in a moderate heat without a portion
of the gold being revived; hence the difficulty of ascertaining in this
way the weight of oxygen combining with gold.
I have succeeded, as I apprehend, in determining the relative weights
of gold and oxygen, by two methods, which mutually corroborate each
other. The first is by means of the nitrous gas generated by the
solution of gold; and the second is, by finding what quantity of green
oxide of iron is converted into red by precipitating a given weight of
gold in solution.
Ten grains of guinea gold of the sp. gr. 17.3, were repeatedly
dissolved in a small excess of nitro-muriatic acid; the quantity and
purity of the nitrous gas generated were duly observed and allowance
made for the loss occasioned by a small portion of common air
originally in the gas bottle. The volume of nitrous gas corrected as
above was always found between 1100 and 1200 grain measures, the weight
of which may be estimated at 1.6 grains, corresponding to 1.4 grains of
oxygen. The small portion of alloy (¹/₁₂) known to be in standard gold
is chiefly copper with a small part silver; now it will be seen in the
sequel that copper takes ¼ of its weight of oxygen; hence if we allow
.8 of a grain for copper and .2 for the oxygen combining with it, we
shall have 9.2 gold united to 1.2 oxygen, or 100 gold with 13 oxygen,
which is nearly the same as Berzelius has determined by precipitating
the gold by mercury.--Again, 10 grains of gold were dissolved as above
(= 9.2 pure) and precipitated by a solution of pure green sulphate of
iron of the sp. gr. 1.181 and which I had previously proved to contain
9 grains of green oxide in 100 measures. They converted 120 measures
of this green sulphate into yellow, which was carefully precipitated
afterwards by lime water, dried and weighed. The gold precipitated was
found very nearly 9 grains; and the yellow oxide of iron mixed with
oxide of copper was nearly 13 grains. Now 120 measures sulphate iron
contain 10.8 grains green oxide, and these require ¹/₉ of their weight
of oxygen (see the oxides of iron) to be changed into yellow oxide, or
1.2 oxygen. Hence it appears that the oxygen combined with the gold was
transferred to the iron unchanged in quantity. It is to be observed
however that green oxide of iron not only deoxidates the gold but it
semideoxidates the copper also; so that .1 of the transferred oxygen
above might be said to be derived from the copper, and the rest, or 1.1
from the 9 grains of gold; this would give 100 gold to 12.2 oxygen,
which is still nearer to the determination of Berzelius. Upon the whole
I am inclined to adopt the proportion of 8 to 1 or 100 to 12.5 as that
which appears the most correct approximation and at the same time a
ratio easily remembered and adapted to facilitate calculations.
We are now to consider whether the above is the protoxide. As no other
oxide has been clearly shewn to exist, and as this combines with
muriatic acid, with ammonia, with the oxide of tin, &c. and is wholly
deoxidated by green sulphate of iron and by a moderate heat, there
seems every reason to conclude it is a combination of the most simple
kind, or 1 atom of metal to 1 of oxygen. Hence the atom of oxygen being
7, that of gold must be 56, and not 140 or 200, as stated VOL. 1, p.
250.
Berzelius seems to consider the above as the tritoxide, or three atoms
of oxygen to one of gold; but it is extremely improbable that gold,
which is allowed to have a weak affinity for oxygen, should be able to
restrain the violent repulsion of three atoms of oxygen, and should on
every occasion lose them all at once, and not by degrees, as is usual
with other high oxides.
Subjoined are the results of various authors in regard to the oxide of
gold, but generally given with diffidence as to their accuracy.
gold oxygen
Bergman 100 + 10
Proust -- + 8.57 to 31.
Oberkampf -- + 10
Berzelius -- + 12 (4 suboxide)
My results -- + 12.5
Since writing the above I have had an opportunity of repeating the
experiments on the oxide of gold by an improved nitrous gas apparatus,
calculated almost entirely to exclude atmospheric air; I find less
nitrous gas produced during the solution than stated above, sometimes
by ⅓, and that it is variable according to the excess of nitric acid;
also that the solution requires a portion of oxymuriatic acid as an
equivalent for the nitrous gas retained. I prefer, however, the method
of oxidizing the green sulphate of iron; by putting a small excess of
the green sulphate and precipitating, first the red oxide and then the
green, I obtained very distinct results. On the whole I am inclined to
think my results preceding these have rather overrated the oxygen, and
that it would as nearly be stated at 11 on the hundred. This would be
nearly a mean of those in the above table, and would require the atom
of gold to be 63, and that of the oxide 70. Between the two extremes of
56 and 63 it is most probable the true weight of the atom of gold will
be found.
It may be proper to add that I have found 100 grain measures of
muriatic acid (1.16), and 25 of nitric (1.35), are sufficient to
dissolve 40 grains of standard gold; and I have reason to think the
acids are in due proportion nearly, though different from what is
usually recommended and employed.
2. _Oxide of Platina._
Platina exhibits greater difficulties than gold in the investigation
of its compounds with oxygen. It is not oxidized by heat; but by the
explosion of an electric battery it is converted into a black powder,
which is most probably the metal in extreme division, though it has
been considered by some as the protoxide. Platina is capable of being
oxidized and dissolved by nitro-muriatic acid, but less easily than
gold; it requires more acid, as high or higher temperature and long
continued digestion; nitrous gas is given out, during the solution,
but sparingly. When lime or an alkali is added to the solution with
a view to precipitate the oxide, a triple compound is usually formed
of the acid, the oxide and the alkali, which is in most instances
precipitated. This weighty compound renders the valuation of the oxygen
in it very uncertain.
Chenevix has made some observations on the oxides of platina, (see
Nichols. Journ. 7. p. 178.) He finds two oxides: the one consists of
93 platina and 7 oxygen; the other of 87 platina and 13 oxygen; but
the experiments on which these results rest are not quite satisfactory.
Mr. E. Davy in the 40th vol. of the Philos. Magazine, states his having
reduced the oxide of platina in solution by means of hydrogen; and
that he finds the oxide to consist of 84 platina and 16 oxygen nearly.
I could not succeed at all in effecting the reduction of the metal in
this way.
Berzelius has lately given us the results of his investigation on this
subject. (An. de Chimie 87--126.) According to this distinguished
chemist there are two oxides of platina; the first consists of 100
metal and 8¼ oxygen, and the second of 100 metal and 16½ oxygen,
nearly. In order to understand his process it may be proper to premise
that when nitro-muriatic acid has dissolved as much platina as it can,
there is still a great excess of one or both of the acids, which is
unnecessary for the existence of the solution, and which may, and in
general ought to be expelled by evaporation; by exposing the solution
to a heat of 100 or 150° the excess of both acids is in great part
driven off and a dry red mass is obtained, without smell, but very
deliquescent. It is equal to or rather more than twice the weight of
the platina. It consists of water, muriatic and nitric acids, oxygen
and platina; it is still an acid salt. By exposing the dry mass again
to a heat of 400 or 500°, it liquifies, exhales acid fumes having
the odour of oxymuriatic acid, and becomes again a dry mass of an
olive colour, exhaling fumes as the heat increases, and loses about
¼ of its weight. It is still soluble in water, except a few atoms of
black powder, continues acid to the tests, and may be considered as a
supermuriate of platina. If this olive powder be again heated almost to
red, it exhales a visible smoke in the open air, which has the smell
of oxymuriatic acid, and becomes a light brown powder, having lost a
little weight. It is then neither deliquescent nor soluble in water
except in a small degree so as to give the yellow colour. In this state
it has been considered as a neutral muriate. By a moderately bright red
heat this powder is decomposed and leaves a black spongy mass which is
found to be pure platina.
The insoluble muriate of platina according to Mr. E. Davy, contains
72.5 per cent. of platina, and Berzelius finds 73.3; the loss is
considered as oxymuriatic acid; hence from the known proportions of
this acid Berzelius infers the constituents of 100 muriate = 73.3
platina, 6.075 oxygen and 20.625 muriatic acid; or 100 platina take
8.3 oxygen. The near agreement of the above authors is favourable to
the accuracy of their results; but I have found some difficulty in
obtaining the insoluble muriate free from the soluble one, and at the
same time from reduced platina because the precise degree of heat
requisite to produce it is neither well known nor easily attained; and
it is desirable that a certain weight of platina should be dissolved
and the same weight reproduced as a confirmation of accuracy. From a
train of experiments on the soluble and insoluble muriates of platina,
the salts being obtained from the purified laminated metal, I am
disposed to consider the above results as good approximations to the
truth.
In order to obtain the other oxide, Berzelius digests mercury in a
solution of the supermuriate of platina; a black powder is thrown down,
which is found to be platina, and mercury is taken up, being oxidized
at the expence of the platina. It was found that 16.7 grains of mercury
had precipitated 8.5 of platina; and the mercury being calculated as
in the state of deutoxide, contained, from the known proportions of
this metal, 1.4 oxygen; hence 8.5 platina must have yielded 1.4 oxygen;
and if 8.5 ∶ 1.4 ∷ 100 ∶ 16.4; so that 100 platina must have had
16.4 oxygen in the supermuriate, or twice the quantity it had in the
insoluble muriate.
This conclusion appears to me premature; the mercurial oxide should at
least have been precipitated and a corresponding quantity have been
found and proved to be the red oxide. Even had this been the case,
it is not easy to determine what quantity of it might be due to the
residue of nitro-muriatic acid. But I have not found that the common
yellow or red oxide of mercury is precipitated by lime water in such
case; the precipitate is brown, and evidently contains both mercury and
platina. Proust had found in his excellent essay on platina (Journ. de
Physique 52--437, 1801) that mercury decomposes muriate of platina,
that an amalgam of platina with a little calomel, and much mercury
in powder, were precipitated; exposed to heat, a fine black powder
was left which had the characters of platina. Into a solution of pure
platina that had been evaporated to dryness in 150° and redissolved,
I put 9¼ grs. of mercury, and boiled it for 10 minutes in a glass
capsule, till there was apparently no further change; the liquor
filtered was as yellow as at first; the mixture of black powder and
running mercury remaining on the filter, when dried, weighed 6½ grains;
this heated to a low red in an iron spoon, left 1 grain of fine black
powder; the liquid saturated with lime water, yielded 2½ grains dry
black powder insoluble in cold nitric acid; after this, protomuriate of
tin threw down 5¾ grains of the compound oxides of platina and tin. The
solution at first contained 3.3 grains of platina.
In another experiment 2 parts of calomel were put to 1 of platina in
solution; when heated to boiling, the calomel was dissolved and a
little black powder was precipitated, which did not amount to half
the weight of the platina. Lime water threw down from the liquid,
a yellowish olive or brown precipitate, partially soluble in cold
nitro-muriatic acid; and after this, muriate of tin yielded a brown
precipitate. These experiments shew that the action between muriate of
platina and mercury or the mercurial salts, is of a complicated nature,
and is not limited to the decomposition of the oxide of platina and the
substitution of the deutoxide of mercury in its place.
The difficulties abovementioned have led me to investigate the oxygen
combining with platina by means of the nitrous gas yielded upon its
solution in nitro-muriatic acid. By three distinct experiments I found
that 10 grains of pure platina by solution yielded nearly 750 grain
measures of nitrous gas, which may be considered as 1 grain in weight;
⅞ of which = .875 for oxygen; this would give 8.75 oxygen per cent. But
from a subsequent experiment made under circumstances calculated to
preclude as much as possible every source of fallacy, I obtained 790
measures of nitrous gas from 10 grains of platina; and the solution
afterwards took 60 measures of oxymuriatic acid gas before a permanent
smell of the gas was produced. These 790 measures = 1.05 grain, ⅞
of which = .92, to which add .04 for the oxygen acquired from the
oxymuriatic acid, and we have .96 oxygen for 10 platina; or 100 platina
take 9.6 oxygen. But if 9.6 ∶ 100 ∷ 7 ∶ 73, for the weight of an atom
of platina, and 80 for that of the protoxide, as I apprehend it to be,
and the only oxide of platina we can at present form. (The atom of
platina in Vol. 1, page 248, was estimated at 100.)
3. _Oxide of Silver._
When silver wire is exploded by electricity in oxygen gas, a black
powder is produced, which is the oxide of silver. If silver be
dissolved in nitric acid and precipitated by lime water, an olive
brown powder falls which becomes black when exposed to the light. This
black powder is the only oxide of silver with which we are acquainted.
The proportion of silver and oxygen has been investigated by various
chemists; the results are as under.
silver oxygen
Wenzel 100 + 8.5
Proust + 9.5
Bucholz and Rose + 9.5[2]
Gay Lussac + 7.6[3]
Berzelius + 7.925
[Footnote 2: 7.9 when duly corrected. Annal. de Chimie, 78--114.]
[Footnote 3: Memoirs d’Arcueil 2--168.]
From the solution of 170 grains of standard silver I obtained nearly 30
oz. measures of nitrous gas = 18½ grains, corresponding to 16 oxygen.
This would give 9.4 oxygen upon 100 silver. But as ⅒ of the metal or 17
grains was copper, and this takes ¼ of its weight of oxygen, we shall
have 159 silver and 11¾ oxygen, or 100 silver and 7.7 oxygen nearly.
If we adopt 7.8 as the proper quantity of oxygen on 100 silver, we
shall have 7.8 ∶ 100 ∷ 7 ∶ 90 nearly, which represents the weight of an
atom of silver, and 97 that of the oxide.
4. _Oxides of Mercury._
Two oxides of mercury have been long known and are well distinguished
from each other. They may be obtained by exposing mercury to a heat not
exceeding 600°, in contact with oxygen gas or atmospheric air, and due
agitation; but this method is rarely adopted in practice. A high degree
of heat decomposes the oxides again.
_Protoxide._ To obtain the protoxide, mercury must be slowly dissolved
in dilute nitric acid without heat, and an excess of mercury must be
used. If to 1000 grain measures of nitric acid, 1.2 sp. gr. be put 500
grains of mercury, by occasional agitation the requisite solution will
be obtained in 24 hours. A portion of this solution must be treated
with a small excess of lime water or caustic alkali, when a black
powder will be thrown down, which is the oxide containing a minimum of
oxygen, and hence may be considered the protoxide.
_Deutoxide._ If to 1000 measures of nitric acid, 1.2 sp. gr. be put
350 grains of mercury, and the mixture be boiled till the mercury
disappear, a solution will be obtained containing the deutoxide. A
portion of this being treated as beforementioned with lime water, a
yellowish red powder is precipitated, which is the oxide of mercury
containing a maximum of oxygen; all the later authors agree that it
contains just double the quantity of oxygen to a given portion of
mercury that the former does, and may therefore be called the deutoxide.
These two oxides combine with most acids and form salts, some of which
exhibit remarkable differences occasioned by the oxides; thus, muriatic
acid with the protoxide forms protomuriate of mercury, commonly called
_calomel_, an insoluble salt; with the deutoxide it forms deutomuriate
of mercury, commonly called _corrosive sublimate_, a soluble salt.
The proportions of metal and oxygen in the two oxides may be found by
precipitating a known weight of mercury reduced by solution to either
of the oxides, then drying and weighing the oxides, when the increase
of weight by the addition of oxygen may be observed. This method is
less accurate with regard to mercury than to other metals, on account
of the very great weight of the atom, by which a small error in the
gross weight of the oxide will be a great one as it respects the
oxygen. This circumstance will partly account for the differences of
authors on this subject.
One fact has been for some time known which demonstrates the oxygen in
the red oxide to be double that in the black. Corrosive sublimate may
be reduced to calomel by adding to it as much mercury as the sublimate
contains, and triturating the mixture well, the oxygen of the red oxide
(as well as the acid) becomes equally divided amongst the mercury and
forms the black oxide, which is a constituent of calomel. Hence it
follows that if the oxygen in one oxide can be ascertained, that of the
other becomes known. Or if we can find how much oxygen must be added
to the black oxide to change it to the red, we shall know the oxygen
in both. Conformably with this last idea I have found a very accurate
and elegant method of ascertaining the oxygen required to convert the
black to the red oxide by treating protomuriate of mercury, mixed with
water and a little muriatic acid, with oxymuriate of lime in solution;
this must be gradually added till the protomuriate is dissolved, or
rather converted to the deutomuriate. The quantity of oxygen in a given
solution of oxymuriate of lime is most conveniently found by a solution
of green sulphate of iron, as will be shewn under the oxides of that
metal.
The oxides of mercury may be investigated by the nitrous gas produced
during solution. When mercury is dissolved without heat, as mentioned
above, no nitrous gas is liberated. The solution has a strong nitrous
smell and requires a great quantity of oxymuriate of lime to saturate
both the oxide and the acid. When heat is employed to accelerate the
solution, nitrous gas is liberated. I dissolved 154 grains of mercury
in nitric acid, 1.2 sp. gr., by the application of a gentle heat from
a lamp. About ⅒ excess of acid remained in the solution; the nitrous
gas obtained was 12 oz. measures = 7.5 grains, corresponding to 6.5
oxygen, which gives nearly 4 oxygen or 100 mercury. This would have
led me to suppose I had obtained the _black_ oxide in solution; it was
however entirely the _red_, as it gave no precipitate by common salt,
and exhibited the red oxide by lime water; but it required as much
oxymuriate of lime as contained 6.5 oxygen to saturate the _nitrous
gas_ in the solution before any oxymuriatic acid was liberated. It was
clear therefore that only ½ of the nitrous gas was evolved, and the
other ½ was retained in the solution, though it had been exposed to
boiling heat.
The following are the proportions assigned by the several authors for
the oxides of mercury.
Mercury. Oxygen.
+------------------+
black. red.
Bergman[4] 100 + 4 + --
Lavoisier[5] -- + -- + 7.75 to 8
Chenevix[6] -- + 12 + 18.5
Taboada[7] -- + 5.2 + 11
Fourcroy & Thenard[8] -- + 4.16 + 8.21
Sefstrom[9] -- + 3.99 + 7.99
My results give -- + 4.2 + 8.4
[Footnote 4: Kirwan’s Mineralogy.]
[Footnote 5: Annals of Philosophy, Vol. 3, p. 333.]
[Footnote 6: Philos. Trans. 1802.]
[Footnote 7: Jour. de Physique. 1805.]
[Footnote 8: Mem. d’Arcueil, Vol. 2. p. 168. 1809.]
[Footnote 9: Annals of Philosophy, Vol. 2. p. 48.]
Though the relative weights of oxygen and mercury may be investigated
as above, yet it is from the weight of mercury and the acids in the
salts of mercury, some of which are of a very definite character,
such as the muriate and the deutomuriate, that the relative weight of
the atom of mercury is best investigated. From these I first deduced
the weight of an atom of mercury to be 167 about 10 years ago, and
subsequent experience has not induced me to change the number, though
it probably may admit of some correction. If the atom of mercury be
denoted by 167, that of the protoxide will be 174, and that of the
deutoxide 181; which makes 100 mercury take 4.2 and 8.4 oxygen for the
oxides respectively, as in the above table.
5. _Oxide of Palladium._
The discoverer of this metal, Dr. Wollaston, has given us its
distinguishing chemical properties; but we are indebted to Berzelius
and Vauquelin for the proportions of oxygen and sulphur which combine
with the metal (Vid. Annal. de Chimie, 77 and 78.) Few chemists have
had an opportunity of making experiments on this metal, owing to its
great scarcity and the consequent high price of it (1 shilling per
grain). It does not seem desireable that any but those skilled in the
more delicate chemical manipulations should operate upon articles such
as the present.
Berzelius treated the muriate of palladium with mercury, which
abstracted the oxygen and left an amalgam of palladium and mercury;
from the quantity of mercury dissolved he calculates that 100 palladium
combine with 14.2 oxygen. This conclusion was corroborated by the
circumstance that 100 palladium were found to take 28 of sulphur,
or double the quantity of oxygen, which frequently happens with the
metals.
Vauquelin precipitates the oxide of palladium from the muriate by
potash; it appears of a red brown colour, and is probably a hydrate;
when washed and dried in a moderate heat, it becomes black, it loses 20
per cent. by a red heat and becomes metallic. This would give 25 oxygen
on 100 metal; but as he finds the sulphuret to be 100 metal with 24 or
30 sulphur, nearly agreeing with Berzelius, it is very probable that a
moderate heat does not free the oxide from water, and that consequently
a part of the 20 per cent. loss is water.
I dissolved 3 grains of palladium in a small excess of nitro-muriatic
acid and obtained 240 grain measures of nitrous gas; the same quantity
was obtained a second time, and to the solution (slightly acid) were
added by degrees 200 measures of oxymuriatic acid gas; after agitation
no smell was perceived, but by increasing the quantity of gas a
permanent smell of oxymuriatic acid was produced, and when 200 more
had been added the smell was sensible for some days in an open jar, a
presumption that no higher oxide is to be obtained. Now 240 nitrous gas
= .32 of a grain, corresponding to .28 of oxygen, and 200 oxymuriatic
acid = .64 of a grain, corresponding to .15 oxygen; the sum of the
two portions of oxygen = .43, which must have combined with 3 grains
of palladium; if .43 ∶ 4 ∷ 7 ∶ 50 nearly. Or 100 metal combine with
14 oxygen, as determined by Berzelius. I find the sulphuret to accord
with this determination; and by carefully saturating the excess of
acid in the nitro-muriate of palladium and then finding the quantity
of lime water necessary to precipitate a certain weight of palladium,
as well as the quantity of test muriatic acid necessary to dissolve
the precipitated oxide, I am confirmed in the opinion that the atom of
palladium must weigh 50 nearly, and its oxide 57, which there is every
reason to believe is the protoxide.
6, 7, _and_ 8. _Oxides of Rhodium, Iridium, and Osmium._
Nothing certain has yet been determined respecting the oxygenation of
these very rare metals.
9. _Oxides of Copper._
There are two oxides of copper according to the results of Proust,
Chenevix, Berzelius and others, the proportions of which are given
nearly the same by all, and so as to leave no reasonable doubt
concerning their accuracy.
1. _Protoxide._ This oxide is _orange_, and contains 12½ oxygen on
100 copper: it is obtained by precipitating a portion of copper from
the solution of any cupreous salt, by means of iron, then mixing this
copper with a rather greater portion of the deutoxide and triturating
them well. This being done, the mixture is to be dissolved in muriatic
acid, and the orange oxide may then be precipitated by an alkali.
2. _Deutoxide._ This oxide is _black_; it contains 25 oxygen on 100
copper: the _black_ oxide is obtained by dissolving copper in nitric
or sulphuric acid, then precipitating by lime water or an alkali, and
heating the dried precipitate red hot. It may also be obtained by
exposing copper to a red heat for some time in common air or oxygen
gas, removing the scales and exposing them in like manner, till at
length the black oxide is formed.
By dissolving 112 grains of copper turnings in 1000 grain measures
of 1.16 nitric acid, I obtained 48 oz. measures of nitrous gas, = 30
grains; by oxymuriate of lime I found 2 grains of nitrous gas in the
solution, making in all 32 grains = 28 grains of oxygen. If 28 ∶ 112 ∷
14 ∶ 56, for the weight of an atom of copper; hence the protoxide = 63
and the deutoxide = 70. These weights I adopted in 1806, and have not
seen any reason to modify them since.
10. _Oxides of Iron._
Two well known and well distinguished oxides of iron are now
universally admitted; the one contains 28 oxygen on 100 iron, the other
42 on 100.
1. _Protoxide._ This is always formed when iron is dissolved in dilute
sulphuric or muriatic acid; it may be precipitated from these solutions
by the pure alkalies or earths; it appears at first of a dark green,
being then a hydrate or combined with water; on a filtre it soon
becomes yellow at the surface by attracting oxygen; when dried in a
heat of 200° or upwards it becomes black. The quantity of oxygen in it
is best ascertained from the hydrogen generated during the solution
of the iron. All the authorities I have found nearly concur in their
results as under.
100 grains of iron dissolved in dilute sulphuric or muriatic acids
yield hydrogen, according to
Cavendish (1766) 155 cubic inches.
Priestley, from 147 to 162
Lavoisier 163
Vandermonde, Berthollet, } max. 176
and Monge }
Vauquelin 160 to 179
Dr. Thomson 163
My own Experiments give 160
----
Mean 164 = 82 oxygen =
27.9 grains.
By precipitating the oxide, and drying it, nearly the same result may
be obtained, as 100 iron will yield 128 oxide. This oxide is magnetic.
2. _Intermediate or red oxide._ This oxide may be obtained in various
ways. First by calcining the sulphate or nitrate of iron. Second by
precipitation from old solutions of the salts of iron; the precipitate
is _yellow_ at first, being perhaps a hydrate; but when dried and
heated it becomes brown-red. Third, by calcining iron or repeatedly
exposing iron filings to a red heat, and trituration. Fourth, by
treating a solution of the sulphate or other salt of the protoxide
with oxymuriatic acid, or oxymuriate of lime till oxymuriatic acid is
evolved; then precipitating the oxide which is thus converted into
the red. Fifth, by agitating water containing the green oxide recently
precipitated, with oxygen gas. The red oxide is not sensibly magnetic.
The quantity of oxygen in the red oxide may be investigated in various
ways, and it is generally allowed that they all concur in giving 42 on
100 iron. The one which I have used peculiarly, and prefer both for
ease and accuracy, is to find the quantity of oxymuriatic acid gas
necessary to saturate a given portion of the green sulphate. I take for
instance 100 measures of 1.149 green sulphate, which I know to contain
8 grains of black oxide; this I find absorbs nearly 13 hundred measures
of oxymuriatic acid gas before the acid smell is developed; the
oxygen corresponding to this quantity of acid is known to be near 660
measures, = .88 grain. (See VOL. 1, p. 308.) Hence, if 8 ∶ .88 ∷ 128
∶ 14; or 128 black oxide acquire 14 or become 142 when converted into
the red oxide. This fact being established, I find it very convenient
to make use of the oxymuriate of lime instead of the acid gas, adopting
the solution of green sulphate of iron as a test of the quantity of
oxymuriatic acid in a given volume of any solution of oxymuriate of
lime.
The quantity of oxygen in the red oxide of iron may be inferred,
but not so satisfactorily, from the nitrous gas obtained during the
solution of iron in nitric acid. In order to obtain the most gas from
a given quantity of the materials, they should be so proportioned
as to produce saturation nearly. If an excess of acid be used, it
absorbs the nitrous gas in part; and if an excess of iron, it is not
all dissolved. I took 50 grains of iron filings and 600 measures of
1.15 nitric acid; these were put together in a gas bottle and by the
assistance of a little heat a quantity of nitrous gas was obtained
equal to 12 grains in weight, allowing the sp. gr. of the gas to be
1.04 (air being 1); all the iron was dissolved except a few atoms, and
the solution was slightly acid; the whole of the oxide was red when
precipitated by lime water. Now 50 grains of iron take 21 of oxygen to
form the red oxide, and these correspond to 24 of nitrous gas, which
is just twice the quantity obtained; one half of the gas generated
then remains in combination with the iron, even when the constituents
of the salt are proportioned so as to produce mutual saturation. I
was in expectation that the quantity of nitrous gas retained might be
converted into nitric acid by oxymuriate of lime, and hence might be
determined; but in this I was disappointed. When oxymuriate of lime is
added to the liquid, a pungent gas is liberated, the nature of which I
have not determined. Thinking it might in part be owing to the iron,
I transferred the acid to soda, by decomposing the nitrate of iron
by the carbonate of soda; this nitrate of soda however, when treated
with oxymuriate of lime, exhibited the same phenomenon as the nitrate
of iron. When an acid is added the oxymuriatic acid itself is given
out. These results will require further consideration. At present I am
inclined to think the pungent gas is one atom of nitrous and one of
oxygen or what I formerly considered as nitric acid. (See VOL. 1, plate
4, fig. 27.)
Some authors have found as they conceive, other oxides of iron,
containing less or more of oxygen than the above; thus Darso finds by
calcination from 15 to 56 oxygen on 100, (Nicholson’s Journ. VOL. 17);
but there is great reason to believe that uncertainties must exist
in his mode of experimenting sufficient to account for the anomalies
observed. This author has suggested some doubt whether the oxygenous
gas naturally contained in water has any effect on the salts with green
oxide of iron. I have ascertained that point by repeated experiments,
and can assert that the oxygen in water immediately unites to the green
oxide of iron to convert it into red, and that the green sulphate may
be used as an accurate test of the quantity of oxygen in water. When
pure green sulphate of iron is dropped into water and then the oxide
precipitated by a gradual addition of lime water, it falls down yellow
in proportion to the oxygen in the water, which may be increased 3
or 4 times by artificial impregnation. If the oxygen of the water
be previously saturated with nitrous gas, then the oxide is wholly
precipitated green.
Gay Lussac, in the 80th VOL. of the Annal. de Chimie, asserts that an
oxide of iron containing 37.8 oxygen upon 100 iron is always obtained
when iron is burned in oxygenous gas, and still more effectually
when iron is oxydized by water or steam. If this oxide exist in the
proportions stated, it must be a compound of 1 atom of the protoxide
and 2 of the red oxide, which would give 37.3 oxygen on 100 of iron.
From the above facts and observations it is evident the atom of iron
must be considered as weighing 25, (and not 50 as already given, VOL.
1, page 258); the protoxide is 32, and the intermediate or red oxide is
2 atoms protoxide and 1 of oxygen = 71.
11. _Oxides of Nickel._
1. _Protoxide._ It appears to be ascertained from the experiments of
Proust (Journ. de Physiq. 63--442), Richter (Nichols. Jour. 12.),
Tupputi (An. de Chimie 78.), and Rolhoff (An. of Philos. 3--335.),
that the protoxide of nickel consists of 100 metal and from 25 to 28
oxygen. My experiments on the solution of nickel in nitric acid give me
14 grains nitrous gas, corresponding to 12 oxygen, in the solution of
44 grains of nickel; this gives 100 nickel to 27 oxygen, which I adopt
as agreeing with the mean of the beforementioned results. This oxide
may be obtained by precipitation from a solution of nitrate of nickel;
it is at first white, being then a hydrate; when dried in a moderate
temperature it becomes yellowish; after this, being heated to a cherry
red, it loses from 20 to 24 per cent. of water and becomes of an ash
grey colour: this is the only oxide of nickel soluble in acids, and
must therefore be deemed the protoxide: hence we have 27 ∶ 100 ∷ 7 ∶
26, nearly, for the weight of an atom of nickel; and not 25 or 50, as
estimated at page 258. VOL. 1.
_Intermediate oxide._ Thenard discovered a second oxide of nickel
by passing oxymuriatic acid through a solution of nickel and then
precipitating; it is a black powder; when treated with sulphuric
or nitric acid it gives out gas, being the excess of oxygen above
the protoxide; but with muriatic acid it gives oxymuriatic acid
gas. Rolhoff was induced to believe, but I do not know upon what
evidence, that this oxide contained 1⅓ or 1½ times the oxygen of the
protoxide. By means of oxymuriate of lime I find the protoxide recently
precipitated, takes half as much oxygen as it had previously, to form
the black oxide; and that it cannot be formed, like the red oxide of
iron, by agitation with water mixed with common air. The white oxide
treated with oxymuriate of lime becomes almost instantly blue, growing
darker till it gradually passes into brown, and finally black in about
half an hour. It contains 40 oxygen on 100 nickel, and is most probably
constituted of 1 atom of oxygen holding 2 of protoxide together, more
especially as it is not found in combination with acids. The method
I prefer to procure the black oxide is to precipitate a known weight
of oxide by lime water; then pouring off the clear liquid, I put as
much liquid oxymuriate of lime to the moist hydrate as contains ⅒ of
the weight of the oxide of oxygen, and stir frequently for half an
hour; the point of saturation is found when more oxide put to the clear
liquid is not discoloured on one hand, and when more oxymuriate of lime
does not affect the colour, but remains in the clear liquid on the
other hand.
12. _Oxides of Tin._
There are two oxides of tin, which have been carefully investigated by
several chemists, and appear to be ascertained with great precision.
The protoxide is _grey_, and contains 13½ oxygen on 100 tin; the
_deutoxide_ is _white_, and contains 27 oxygen on 100 tin.
1. _Protoxide._ There are two methods of obtaining the constitution
of this oxide. The first is by dissolving a certain weight of tin
filings in muriatic acid, precipitating by lime water or carbonated
alkalies and drying the oxide in a moderate heat; this is liable to
some uncertainty; the precipitate being a _hydrate_, requires to be
exposed to heat to expel the water; but if the heat approaches to red,
the oxide takes fire and is converted into the deutoxide. The second
method is to dissolve tin in muriatic acid and carefully collect the
hydrogen gas evolved; this was first done by Mr. Cavendish, with his
usual accuracy, and published in 1766; he found 1 oz. of tin yield 202
oz. measures of hydrogen gas. I have frequently tried this experiment
and always found a proportional quantity, or very nearly 200 measures
for each grain of tin. This mode of investigation appears to me
unexceptionable. Now 200 hydrogen unite to 100 oxygen, and 100 grain
measures of oxygen = .134 grain in weight; hence if .134 oxy. ∶ 1 tin ∷
7 oxy. ∶ 52 nearly for the weight of an atom of tin, on the presumption
this is the protoxide.
2. _Deutoxide._ This may be obtained by heating tin till it takes
fire, and the produce of the combustion is the oxide required; but
to ascertain the proportions of tin and oxygen two other methods are
preferable; the one is to treat tin with nitric acid of the sp. gr.
1.2 to 1.4; a violent effervescence and great heat ensue and the tin
is converted into a white powder. This being dried in 100° gives
about 160 grains for 100 of tin. It consists of the deutoxide united
to a little acid and water; these two may be driven off by a low red
heat, and 127 grains of the deutoxide remain in the state of a white
powder. The other method is to treat a solution of the protoxide of
tin with oxymuriate of lime till it is saturated; this will be found
when 59 grains of the protoxide have acquired 7 grains of oxygen, or
113½ grains of the deutoxide have acquired 13½ grains of oxygen, which
corroborates the result by the 1st method. This oxide containing just
twice as much oxygen as the former, may justly be considered as the
deutoxide. No higher oxide of tin has been obtained.
The two oxides, though both white when precipitated, may be
distinguished from their different appearances; the first is _curdy_,
the second, _gelatinous_.
It may be proper to subjoin authorities for these oxides:
Tin Protoxide Deutoxide
Cavendish, from the hydrogen 100 113.5 --------
Proust (Journ. de Physique 59-341) 100 115 127½.128[10]
Gay Lussac (Annal. de Chimie 80-170) 100 113.5 127.2[11]
Berzelius (Annal. de Chim. 87-55) 100 113.6 127.2[12]
My own, as above 100 113.4 127
[Footnote 10: By nitric acid, the result of 3 experiments all agreeing
for the deutoxide; the protoxide is by calculation and less certain. He
afterwards adopts 13.6 from Berzelius. Journ. de Phys. Aug. 1814.]
[Footnote 11: The protoxide from hydrogen by solution; the deutoxide by
transmitting steam over the metal at a red heat.]
[Footnote 12: The 2d. by oxydizing the sulphuret of tin by nitric acid;
the 1st. by inference only, one half of the oxygen of the 2d.]
13. _Oxides of Lead._
There are three oxides of lead now generally recognized, the _yellow_,
the _red_, and the _brown_, the proportion of oxygen in each of which
has been investigated by several chemists whose results do not well
accord with each other. I shall treat of them under the following
names, namely the _protoxide_, the _intermediate oxides_, and the
_deutoxide_, for reasons which will appear.
1. _Protoxide._ The yellow oxide of lead is the only one capable of
forming salts with acids. Lavoisier found the oxygen of this oxide
combined with 100 lead to be 4.47; Wenzel, 10; Proust, 9; Thomson,
10.5; Bucholz, 8; Berzelius, 7.7. This last accords best with my own
experience; but it is chiefly from the other combinations of lead, that
the weight of its atom as well as that of the protoxide are determined
and confirmed, as lead forms several very definite compounds with
acids, &c. The quantity of oxygen in the protoxide may be found by
several methods, as under.
1st. By dissolving a given portion of the oxide in acetic acid, and
precipitating the lead by another metal, as zinc; in this case the
oxygen of the lead goes to the zinc which becomes dissolved, and from
the loss of weight of the zinc and the proportion of oxygen in zinc
oxide being previously known, and the weight of the precipitated lead
being found, we have data for determining the oxide of lead. I took 200
measures of acetate of lead solution (1.142), which I knew contained
27 grains of oxide of lead; this being diluted with an equal volume of
water, the lead was precipitated by a rod of zinc; in 6 hours an _arbor
saturni_ was formed which was collected and well dried; it weighed
21¾ grains, and the zinc rod had lost 7 grains: care must be taken
in performing this experiment that all the lead be not precipitated,
otherwise the oxide of zinc begins to fall, and the result is
uncertain. In the residuary liquid I got 4 grains of sulphate of lead
by sulphuric acid. Here then we have the oxygen of 21¾ lead transferred
to 7 zinc; but if 7 ∶ 21¾ ∷ 29 ∶ 90 nearly. Now it is known that 29
parts of zinc take 7 of oxygen, therefore 90 lead take 7 of oxygen, and
the atom of lead = 90, and the protoxide 97.
I formerly stated the atom of lead 95. VOL. 1, page 260.
2. By dissolving 180 grains of lead in nitric acid in a small thin
capsule, and heating it till the salt was quite dry, I got 288 grains
of salt, weighed in the capsule; 36 grains of this salt yielded 24¼
yellow oxide by a low red heat = 22½ lead. This gives 90 lead to 7
oxygen.
3d. Again, 36 grains of the above salt, dissolved in water,
precipitated by ammonia, and well washed on a filter, gave 23+ grains
of oxide separated from the filter, and this had acquired 1 grain,
making 24+ grains of oxide from the 22½ lead as before; the residue of
liquid gave no signs of lead by hydrosulphuret of ammonia. The same
quantity of salt precipitated by an excess of lime water gave only 22
grains of oxide; but hydrosulphuret of ammonia precipitated 2+ grains
of sulphuret of lead from the clear liquid.
II. _Intermediate oxide or oxides._ Minium or red lead, &c. Minium
is an article of commerce used as a pigment and for various other
purposes. It is made by exposing the yellow or protoxide of lead finely
pulverized to a low red heat in a current of air, and constantly
stirring the oxide so as to expose fresh particles to the air. In
two days the yellow oxide is converted into the red. Several authors
observe that red lead usually contains 1, 2, or more grains per cent.
of impurities insoluble in nitric and acetic acids; the specimen I
used however was so pure as not to leave more than ⅓ of a grain per
cent. of insoluble matter after being heated red and treated with
dilute nitric acid.
Some of the most remarkable properties of red lead are, 1st. It is
never obtained in combination with any acid; 2d. It yields oxygen gas
when exposed to a bright red heat or when treated with concentrated
sulphuric acid, and is in both cases reduced to the protoxide; 3d. When
treated with dilute nitric acid it is dissolved in part, but constantly
leaves an insoluble brown residuum, which is the deutoxide, as will be
shewn; the weight of the deutoxide obtained is by my experiments 20 per
cent. and the part in solution is found to be the protoxide; 4th. When
treated with muriatic acid, muriate of lead is formed and oxymuriatic
acid given out; 5th. When treated with dilute acetic acid or cold
concentrated acetic acid, ½ of the oxide is dissolved and the remainder
is still red, its colour being rather improved; if concentrated acid be
used and boiling heat applied, then ⅘ of the whole oxide is dissolved
and ⅕ remains of brown oxide, the same as with nitric acid.
Some of the above facts are new, and may contribute to elucidate this
most curious oxide, which scarcely has a parallel. Proust is the only
author I know who has given a plausible conjecture concerning the
peculiar nature of this oxide. He supposes it a compound of the yellow
and brown oxides. This I believe is the fact; but it will be found I
apprehend to be a compound of 1 atom of oxygen with 6 of the yellow
oxide, as will appear from what follows.
Respecting the quantity of oxygen in the red oxide, Lavoisier finds
9 oxygen to 100 lead, Thomson 13.6, and Berzelius 11.55. This last
is partly from experience and partly from a supposed analogy, that
the successive oxides of the same metal contain oxygen as 1, 1½ and 2
respectively; and having found (I believe) correctly, that the brown
oxide contains just twice as much oxygen as the yellow, this ingenious
and generally accurate author adopts the theoretic inference in this
instance at least prematurely, and concludes the red oxide is the mean
between the yellow and the brown. But we must appeal to experience.
It has already been stated that when red lead is exposed to heat,
oxygen gas is given out, and it may be added, a small trace of water;
and yellow oxide remains.
This experiment requires considerable skill. If too great a heat is
used, a part of the lead is reduced or revived as it is termed; if
too little heat, then a part of the red lead remains unaltered. In
performing this experiment I use a small clean iron spoon to hold the
red lead, and cover it by another iron spoon; the whole is then held
by a pair of tongs in a red fire till the spoon exhibits a uniform
moderate red, and some time after.
It is then withdrawn and cooled, and the oxide weighed. The average
loss of weight is nearly 2 grains per cent. If only 1 grain or less,
a considerable portion of red oxide remains mixed with the yellow; if
3 or more grains, then the margin of the oxide exhibits particles of
lead amounting to ⅒, less or more, of the original weight; this can be
easily separated from the oxide if necessary, but it is apt to adhere
to the iron; when red oxide remains, it is so mixed with the yellow
as not easily to be separated, but its quantity may be determined by
nitric acid, which dissolves the yellow, and ⅘ of the red, leaving a
residuum of brown oxide, from which the quantity of red is inferred.
Now if the loss of weight of 100 red oxide be only 2 grains, and a
part of that be water, it is impossible that 115.55 should lose 3.85
grains of oxygen, according to Berzelius. Another experiment, equally
decisive of the question, is to determine the quantity of oxygenous gas
to be obtained by heat or acids from a given weight of red lead. In one
experiment made with great care, 500 grains of red oxide gave 6 grains
of oxygenous gas by sulphuric acid; in another, 200 yielded 2½ grains.
In order to vary the mode of determining the quantity of oxygen,
into 210 measures of test green sulphate of iron solution, (1.156) =
16.8 green oxide, put 160 grains of minium; to this was added dilute
muriatic acid more than sufficient for the minium: The oxymuriatic acid
from the oxygen of the minium was instantly seized by the oxide of the
iron, the whole of which was found by precipitation to be changed from
green to red and an excess of oxymuriatic acid appeared. Now 16.8 oxide
would require 1.86 oxygen to become red, which it must have acquired
from 160 of red lead; or 100 red lead yielded 1.2 oxygen, the same
proportion as by sulphuric acid. These experiments point out 1.2 oxygen
in 100 red lead as the excess which converts the yellow to the red
oxide. Were any doubt to remain on the subject, the experiment with
nitric acid and red oxide will remove it. If the red oxide contained
a mean of oxygen between the yellow and the brown, when it is treated
with nitric acid more than 50 per cent. of brown oxide would be
obtained instead of 20, which is contrary to all experience. It must
be observed that Berzelius informs us he extracted the yellow oxide,
mechanically mixed (as he conceives) with the red oxide, by digestion
with dilute acetic acid; but he does not inform us how much per cent.
his minium was reduced by this operation. From what is stated above, it
appears that about ½ of the whole is thus dissolved. The remaining half
would then contain double the quantity of oxygen and brown oxide per
cent. that the original did. Still these quantities are inadequate to
explain the phenomena. Besides it cannot be admitted that a _red_ and
a _yellow_ powder can be intimately mixed in equal quantities and the
mixture not be distinguishable without difficulty from the _red_ one,
and be altogether different from the _yellow_. We must then conclude
that the minium of commerce (such as I have used) is a true chemical
compound.
Grounding our reasonings upon the preceding facts, there are but
two suppositions that can be considered as plausible, respecting
the constitution of the red oxide. It may be 1 atom of oxygen and
5 of yellow oxide, or 1 atom of oxygen and 6 of yellow oxide. The
former would give 1.4 per cent. extra oxygen in 100 red oxide, and 21
brown oxide; the latter would give 1.2 per cent. extra oxygen and 18
brown oxide. I adopt the latter supposition; because it agrees with
experiment in regard to oxygen, and gives the brown oxide a little
_lower_ than experiment, as may be expected on two accounts; first, the
residue of brown oxide contains the insoluble dross of the red oxide
(which was very small however, as stated above); and, second, unless a
considerable excess of nitric acid be used, or long digestion, a small
portion of the red oxide escapes decomposition. Another and still more
important consideration, as to the question whether 5 or 6 atoms, is
the equal division of the red oxide by the operation of cold acetic
acid; it reduces the 1 oxygen and 6 yellow oxide to 1 and 3 atoms;
whereas if we adopt the other, we must conclude it reduces the 1 and 5
to 1 and 2½, a position that cannot well be reconciled to the atomic
theory.
According to this conclusion then the red oxide of lead or minium of
commerce is constituted of 1 atom of oxygen holding 6 atoms of yellow
oxide together; or it is composed of 100 lead and 9.07 oxygen. When
it is digested in cold acetic acid the residuum constitutes another
oxide consisting of 1 atom of oxygen and 3 of yellow oxide, or 100
lead and 10.4 oxygen, possessing the same colour as the former, but
distinguishable by its not being acted on by cold acetic acid, and by
its containing twice as much brown oxide and extra oxygen as minium. No
doubt the other intermediate oxides of 1 to 4 and 1 to 5 exist, and are
all alike red; but have not perhaps any remarkable distinctions besides
their containing different proportions of oxygen and brown oxide.
Whether an oxide consisting of 1 oxygen and 2 yellow oxide exists, I
have not discovered; but that 1 oxygen and 1 yellow oxide are found
united, appears below.
III. _Deutoxide._ This is the flea-brown oxide mentioned above. It may
also be obtained by treating solutions of salts containing the yellow
oxide by oxymuriate of lime, in which case the oxide is precipitated,
leaving the acid in the liquor, a proof that it is insoluble in
acids. Its more remarkable properties are: 1st. like the red oxide,
when heated to a low red, or treated with sulphuric acid, it yields
oxygenous gas, and more copiously; it is thus reduced to the yellow
oxide: 2d. with muriatic acid it yields oxymuriatic acid in great
plenty and muriate of lead: 3d. it detonates when rubbed with sulphur
in a mortar.
The quantity of oxygen in the brown oxide is stated by Thomson at 25
oxygen to 100 lead, by Berzelius at 15.6 to 100. This last is very
nearly right by my experience, and being just double of the oxygen
in the protoxide, it warrants us in denominating it the deutoxide.
Berzelius finds 100 of the brown oxide lose 6.5 by a red heat so as
to reduce it to the yellow; Dr. Thomson finds the loss 9 grains. This
difference is easily accounted for; it loses, I find, from 7 to 10
grains per cent. according to the previous degree of dryness; when
exposed to a moist atmosphere it attracts humidity; when dried in a
temperature of 200° and exposed to red heat immediately after, it does
not lose more than 6.5 or 7 per cent. This is corroborated too by the
oxygen expelled by sulphuric acid. From 100 grains of brown oxide and
sulphuric acid in a gas bottle, I obtained by the heat of a lamp 8.3
oz. of oxygenous gas = 5.3 grains; about 120 grains of grey sulphate
of lead were left in the bottle. The oxygen is rather less than was
expected; but it must be remembered that 100 grains of brown oxide,
obtained in the ordinary way, have the insoluble dross of 500 red oxide
in them, which must have some influence in diminishing the production
of oxygen.
Though the above might be deemed sufficient to demonstrate the
proportion of oxygen in the brown oxide, I was desirous to corroborate
the results by oxymuriate of lime. I found repeatedly that 100 grain
measures of acetate of lead (1.142) = 13.8 yellow oxide, required 400
measures of oxymuriate of lime = 1 oxygen, to precipitate the whole of
the oxide in a brown state. Now if 13.8 ∶ 1 ∷ 97 ∶ 7. Again, into 240
measures of test green sulphate of iron (1.156) = 19 oxide, were put
40 grains of brown oxide of lead, together with a sufficient quantity
of muriatic acid to saturate the lead, and discharge the oxygen; after
due agitation sulphate of lead was precipitated, and the whole of
the oxide of iron was found, when precipitated, to be yellow. But 19
grains oxide of iron require 2+ of oxygen to become yellow; hence the
40 grains brown oxide of lead must have furnished 2+ grains of oxygen
to form oxymuriatic acid, which transferred it to the oxide of iron.
If 40 ∶ 2+ ∷ 100 ∶ 5+ oxygen, for the excess or second dose of oxygen
in 100 brown oxide, such as is obtained by nitric acid along with its
impurities; which agrees with the results obtained by the other methods.
14. _Oxide of zinc._
When zinc is exposed to a strong heat it burns with a brilliant white
flame, and a white powder sublimes, which is the oxide of the metal.
When dilute sulphuric acid is poured on granulated zinc, hydrogen
gas is produced in great abundance and purity; the metal is oxidized
at the expence of the water and dissolved in the acid, the oxide may
be precipitated by an alkali; it is white both when precipitated
and dried, and when heated does not differ from that obtained by
combustion. By a violent heat it runs into glass.
The quantity of oxygen in zinc oxide is, I think, best estimated by
the hydrogen gas produced during the solution; it may also be obtained
by direct combustion, or by solution in nitric acid and calcination.
Dr. Thomson determines the oxygen by comparison of the weights of real
sulphuric acid and metallic zinc in a solution of sulphate of zinc,
along with the consideration that the proportion of sulphuric acid and
oxygen in the metallic sulphates is known; Mr. Cavendish obtained 356
oz. measures of hydrogen from 1 oz. of zinc by solution. I dissolved 49
grains of zinc in dilute sulphuric acid and obtained hydrogen, after
the rate of 363 grain measures for 1 grain of zinc = 182 measures of
oxygen = .24 grain of oxygen.
The following are the principal authorities for the quantity of oxygen
in zinc oxide, in the order of time.
Zinc. Oxygen.
1766. Cavendish 100 + 23.3
1785. Lavoisier -- + 19.6
1790-1800. Wenzel and Proust -- + 25
1801. Desorme and Clement -- + 21.7
Davy -- + 21.95
Berzelius -- + 24.4
Gay Lussac -- + 24.4
Thomson -- + 24.42
My own -- + 24
Now if 24 oxy. ∶ 100 zinc ∷ 7 oxy. ∶ 29 zinc, nearly, which is
therefore the weight of an atom of this metal, on the supposition that
the oxide is 1 oxygen and 1 metal; and the atom of oxide = 36.
I formerly estimated the atom of zinc at 56 (VOL. 1, page 260). This
was occasioned by taking the above as the _deutoxide_ instead of the
_protoxide_. By violently heating the oxide of zinc in a close vessel,
Desorme and Clement reduced the oxygen nearly one half, so as to
afford a presumption that an oxide with half the oxygen of the common
one subsisted. Since that time some observations of Berzelius seem to
shew that a suboxide of zinc exists. It does not appear however, that
such oxide is ever found in combination with acids; and, granting the
accuracy of the observations, it is rather to be presumed to be the
semi-oxide, or 1 atom of oxygen and 2 of metal, than the protoxide.
No higher oxidation of zinc than the above has yet been obtained, and
probably does not exist.
15. _Oxides of potassium._
Since writing the articles “potassium and sodium,” in the former
volume, a very important essay relating chiefly to these subjects has
been written by Gay Lussac and Thenard (a copy of which they were so
good as to send me), entitled “Recherches Physico-chimiques, &c.” in
2 VOL.--Many of the most interesting experiments of Davy have been
repeated on a larger scale, and a great number of original ones added;
these ingenious authors endeavour to sum up the evidences for and
against the two hypotheses concerning potassium and sodium, namely,
as to their being metals or hydrurets, and upon the whole incline to
the former, allowing however, that the facts afford great plausibility
to both. One thing they seem to have discovered and established, that
the new bodies or metals admit of various degrees of oxidation, and
of course these products have a claim to be classed amongst oxides in
general though the nature of their bases may still be an object of
dispute.
They find three oxides of potassium; the lowest degree is obtained
by exposing potassium to atmospheric air in a small bottle, with a
common cork; a gradual oxidation takes place; a blueish grey brittle
product is obtained; there does not appear however, to be any proper
limit to this oxidation besides that which they admit as characterizing
the second degree or potash, which degree of oxidation may always
be immediately obtained by placing potassium in contact with water.
This I think should be called the protoxide and considered as 1 atom
of potassium, and 1 of oxygen; before this point it is potassium and
potash mixed or perhaps combined.
Besides these there is another obtained by burning potassium in oxygen
gas at an elevated temperature; this oxide is yellow, fusible by heat,
and crystallizes in lamina on cooling; it contains three times as much
oxygen as potash; put into water it is suddenly decomposed, giving out
⅔ of the oxygen in gas and becoming potash. Very probably an oxide
containing twice as much oxygen as potash might be formed with some
mark of discrimination, by uniting 18 parts potassium with 56 of yellow
oxide, but this has not yet been done.
According to these conclusions the weights of the oxides of potassium
may be stated as under.--Potassium 35, protoxide or potash 42,
deutoxide (supposed to exist) 49, and the yellow or tritoxide 56. Hence
we have
Potassium. Oxygen.
Protoxide (potash) 100 + 20 } Gay Lussac & Thenard
19 } Davy
Deutoxide 100 + 40 (unknown)
Tritoxide 100 + 60 Gay Lussac & Thenard
One feels unwilling to admit of a _tritoxide_, (and that perhaps the
only one existing,) when the deutoxide is unknown, were it not upon
good authority. The obscurity on this subject may be removed by future
experiments.
It may be proper to add that Gay Lussac and Thenard concur with Davy
in assigning a much greater saturating power to potassium and sodium
than to the fused hydrates of potash and soda of equal weights. From
the table, Recherches, Tom. 2, p. 214, it may be deduced that 35
potassium require as much sulphuric acid to saturate them as 50 or
more of the hydrate of potash; and that 21 sodium are equivalent to 36
or 37 hydrate of sodium. If these results are accurate, the weights
of potassium and sodium, considered as hydrurets, cannot be as we
have deduced them at pages 486 and 503, VOL. 1, namely, 43 and 29
respectively, but 35 and 21, as at page 262.
16. _Oxides of sodium._
Gay Lussac and Thenard find a suboxide of sodium in the same way as
that of potassium, and it is probably a compound of soda and sodium:
the remarkable oxidation which produces soda is, I should imagine, the
protoxide or one atom to one, as obtained by placing sodium in contact
with water. A higher oxide is obtained as with potassium, by burning
sodium in oxygen gas with a vivid heat. It resembles the yellow oxide
of potassium in its appearance and properties. The degree of oxidation
varies in the different experiments from 1¼ to 1¾ times the oxygen of
soda. It is probably a combination of the protoxide and deutoxide.
Hence the oxides of sodium may be as under; reckoning the atom of
sodium 21, and soda 28.
Sodium. Oxygen.
Protoxide (Soda) 100 + 33⅓
Intermediate oxide 100 + 50
17. _Oxide of bismuth._
Only one oxide of bismuth is known, and the proportion of its parts has
been gradually approximated by Bergman, Lavoisier, Klaproth, Proust,
and others. Berzelius mentions a purple oxide obtained by exposing
bismuth to the action of the atmosphere; but as no experiments have
been made upon it, we cannot adopt it at present. According to Klaproth
and Proust, 100 bismuth unite with 12 oxygen; but by the more recent
experiments of Mr. J. Davy and Lagerhjelm 100 bismuth take 11.1 or 11.3
oxygen. If we adopt this last, which is doubtless near the truth; we
shall have 11.3 ∶ 100 ∷ 7 ∶ 62 for the weight of the atom of bismuth,
on the supposition that the compound is the protoxide or 1 atom of
metal to 1 of oxygen. My former weight of bismuth was 68 (page 263),
which is clearly too high.
Bismuth is best oxidized by nitric acid. Part of the oxide combines
with the acid and part precipitates in the state of a white powder; if
the whole be gradually heated, the acid is driven off, and at a low red
the oxide remains pure; it is fused into glass and of a red or yellow
colour, according to the heat employed. Bismuth may also be oxidized by
heat in open vessels; yellow fumes arise which may be condensed and are
found to be the oxide.
18. _Oxides of antimony._
Considerable difference of opinions exists with regard to the oxides
of antimony. Proust finds two oxides which he determines to consist,
the first, of 100 metal + 22 or 23 oxygen; the second of 100 metal +
30 oxygen. Thenard finds 6 oxides: J. Davy two oxides, namely, 100
metal + 17.7 oxygen, and 100 + 30 oxygen. Berzelius infers from his
experiments that there are 4 oxides of antimony, the first containing
4.65 oxygen, the second 18.6, the third 27.9, and the fourth 37.2 of
oxygen on 100 metal. He admits however that the oxide obtained by
boiling nitric acid on antimony and expelling the superfluous acid by
a low red heat, consists of 100 metal + 29 to 31 oxygen, as determined
by Proust and others. This is certainly the most definite of the
oxides, next to that which is obtained from the solution of antimony
in muriatic acid. This last may be had by pouring water into a solution
of muriate of antimony; a white powder precipitates, which is the oxide
with a little muriatic acid; the acid may be abstracted by boiling
the precipitate in a solution of carbonate of potash. This oxide is a
grey powder, and fusible at a low red heat. It enters exclusively into
various well known compounds, as the _golden sulphur of antimony_,
_antimoniated tartrate of potash_, &c. Its constitution, according to
Proust, is 100 metal + 23 oxygen; but J. Davy finds only 17.7 oxygen,
and Berzelius 18.6. As this oxide possesses the most distinct features,
and besides is the most important, it is desirable its constitution
should be ascertained without doubt. From several experiments I made on
the precipitation of antimony by zinc, I conclude the oxide contains
about 18 oxygen on 100 metal. I took the common muriate of antimony
with excess of acid, and immersed a rod of zinc into it, covering the
whole with a graduated bell glass. Hydrogen gas was produced by the
excess of acid, and its quantity was ascertained; the antimony was in
due time precipitated, and when the operation ceased, the loss of zinc
and the weight of antimony were found. For instance, to 50 measures
of 1.69 mur. ant. 60 water were added, no precipitation was observed;
a zinc rod was put in and the whole covered by a bell glass, over
water; in a few hours the operation had ceased, and there appeared 3480
grain measures of hydrogen gas generated; the dried antimony weighed
25½ grains, and the zinc had lost 29 grains. Now 3480 hydrogen require
1740 of oxygen = 2.3 grains in weight. But 29 zinc require 7 oxygen;
therefore the zinc must have got 4.7 oxygen from the antimony; that
is, 25.5 antimony were found united to 4.7 oxygen; this gives 100
antimony + 18.4 oxygen. I conclude then that the error is with Proust;
and this appears to be confirmed by the consideration that Proust
himself obtains only 86 oxide of antimony from 100 sulphuret, which
he allows to contain 74 antimony; now if 74 ∶ 12 ∷ 100 ∶ 17 nearly. I
am therefore inclined to adopt 18 for the oxygen which combines with
100 antimony to form the grey oxide. Whether this is the protoxide or
deutoxide may be disputed; and the facts known concerning the other
oxide or oxides will scarcely determine the case: but the proportions
of the muriate and sulphuret of antimony accord much better with the
former supposition. Now if 18 ∶ 100 ∷ 7 ∶ 39, for the weight of the
atom of antimony; I prefer the weight 40, deduced from the sulphuret,
as announced in VOL. 1, page 264.
The oxide which contains 30 on 100 must be 2 atoms of the deutoxide
and 1 of the protoxide united. What Berzelius calls the white oxide or
antimonious acid, may be 1 atom of each oxide united, containing 27
oxygen on the 100. The oxide supposed to contain 36 or 37 oxygen on
100, and which must be considered as the deutoxide, has not been proved
to exist separately. My efforts to procure it have failed as well as
those before mine: by treating muriate of antimony with oxymuriate of
lime I have obtained oxides of 30 on the 100, but never much higher.
Whenever a greater proportion of oxymuriate of lime is added, the smell
of the gas becomes permanent.
Antimony exposed to a red heat in a current of common air or oxygenous
gas takes fire, and white fumes arise formerly called _flowers of
antimony_; this oxide contains 27 or 30 oxygen on 100 metal.
Antimony thrown into red hot nitre is oxidized rapidly; the remaining
powder, washed in water, is found to be a compound of oxide of antimony
and potash. Berzelius calls the oxide the antimonic acid, and the salt
the _antimoniate of potash_. It consists, according to his experience,
of 100 acid and 26.5 potash. A similar salt formed between the
antimonious acid and potash is constituted of 100 acid and 30.5 potash.
19. _Oxide of tellurium._
We are chiefly indebted to Berzelius for the proportions in which
tellurium combines. He finds 100 tellurium unite to 24.8 oxygen. Also
that 201.5 tellurate of lead gave 157 sulphate of lead. This last
contains 116 oxide of lead, which must therefore have combined with
85.5 of the oxide of tellurium. Hence 97 oxide of lead would combine
with 71.5 oxide of tellurium = 57½ tellurium + 14 oxygen. Whether
this oxide of tellurium is the protoxide or deutoxide, is somewhat
uncertain. The atom of tellurium will weigh 57½ in the latter case,
but only 28 or 29 in the former. The analogy of the oxide to acids
favours the notion of a deutoxide; but the facility with which the
tellurium is volatilized by hydrogen is in favour of the lighter atom.
The oxide is a white powder; it is produced by dissolving the metal in
nitro-muriatic acid and precipitating by an alkali.
20. _Oxides of arsenic._
There are two distinct combinations of arsenic and oxygen; the one has
been long known as an article of commerce under the name of arsenic. It
is a white, brittle, glassy substance, obtained during the extraction
of certain metals from their ores. Its specific gravity is about 3.7.
According to Klaproth boiling water dissolves from 7 to 8 per cent.
of the oxide of arsenic; but on cooling it retains only about 3 per
cent.; and this I find is gradually deposited on the sides of the
vessel till it is reduced to 2 per cent. or less in cold weather, and
by some months standing. Water of 60° or under dissolves no more than
¼ per cent. of the oxide. At the temperature of about 400° the oxide
sublimes. This oxide combines with the alkalies, earths, and metallic
oxides somewhat as the acids do, but does not neutralize them, and in
other respects it is destitute of acid properties; as for instance, it
does not affect the colour tests. It is extremely poisonous.
The other oxide is obtained by treating either the white oxide or pure
metallic arsenic with nitric acid and heat. One hundred grains of
white oxide require two or three times their weight of nitric acid,
of 1.3, to oxidize them. The new oxide is produced in a liquid form;
from which the excess of nitric acid may be driven by a low red heat,
and the oxide is obtained pure in the form of a white opake glass,
which soon becomes liquid by attracting moisture from the atmosphere.
This oxide, discovered by Scheele, has all the properties of acids in
general, and is therefore denominated arsenic acid. When just fluid
by attracting moisture it has the sp. gravity 1.65 nearly. It is
represented as equally poisonous with the white oxide.
The proportions of the elements in these two oxides have been
investigated with considerable success. Proust finds the white oxide
constituted of 100 metal and 33 or 34 oxygen, and the second of 100
metal with 53 or 54 oxygen: with these results those of Rose and
Bucholz nearly agree. Thenard finds 100 + 34.6 for the white oxide,
and 100 + 56.25 for the acid: and Thomson 100 + 52.4 for the acid.
Berzelius however, infers from his recent experiments that the oxide
consists of 100 metal + 43.6 oxygen, and the acid of 100 + 71.3; these
last results I have little doubt are incorrect from my own experience.
It appears that when arsenic is oxidized by nitric acid, 100
parts yield from 152 to 156 of acid, dried in a low red heat. The
differences may in part be owing to the metal being partly oxidized
at the commencement of the operation. On this account I should suppose
55 or 56 to be the proper quantity of oxygen united to 100 metal to
form the acid. Proust and Thenard both found that 100 white oxide, when
converted into acid by nitric acid, gave 115 or 116. I have found the
same. Now if 116 ∶ 100 ∷ 156 ∶ 134; hence the white oxide of arsenic
must contain 100 metal to 34 oxygen, if the data be correct; or the
metal and oxygen are as 3 to 1 nearly. It is highly improbable that
any inferior oxide subsists, as no traces of such have been found, if
we disallow a conjecture of Berzelius on the subject. The white oxide
of arsenic must then be considered as the _protoxide_, and the atom of
arsenic must weigh 21 nearly, and that of the protoxide 28.
It is plain the other is not the _deutoxide_, as it does not contain
twice the oxygen of the protoxide; but as the proportion of oxygen
in it is to that of the protoxide, as 5 ∶ 3, it may be a compound
of 2 atoms of deutoxide, and 1 of protoxide; that is, it may be the
_superarseniate of arsenic_, if we consider the deutoxide as the acid,
and the protoxide as the base. According to this view, the compound
oxide, or _arsenic acid_ of Scheele, is constituted of two atoms of
the deutoxide, weighing 70, and 1 atom of the protoxide weighing 28,
together making 98, for the weight of an atom of arsenic acid, = 63
arsenic + 35 oxygen: and 100 arsenic take 55.5 oxygen to form the acid,
agreeably to the above recited experiments. Singular as this conclusion
may appear, the truth of it is put beyond doubt, I think, by the
following experiments.
I have repeatedly found that 28 parts of white oxide in solution are
sufficient to throw down 24 parts of lime, from lime water, so as to
produce 52 parts of arsenite of lime, and leave the water free from
both elements. This confirms the notion of the atom of protoxide
weighing 28.
If to 24 parts of lime dissolved in water we put 98 parts of dry
arsenic acid, the compound remains in solution, and is perfectly
neutral to the colour test, but so that the addition of a small
quantity of either ingredient disturbs the neutrality. If to this
solution 24 parts of lime dissolved in water be added, the compound
remains a limpid solution, but is very limy to the test. If to this
we put in like manner, 24 parts more of lime, the whole compound is
thrown down, and yields, when dried, 170 parts of arseniate of lime,
the liquid being now free from both elements. Here we see first, two
atoms of the deutoxide, neutralized by two atoms of base, namely, 1 of
arsenic oxide, and 1 of lime; but (second), when one atom more of lime
is added, an union of 2 deutoxide, and 3 of base is effected, which of
course is an alkaline salt; when (third) more of lime is added, the 2
deutoxide and the 1 protoxide each attach 1 of lime, and form a still
more alkaline salt, which being insoluble, is wholly thrown down, most
probably in a compound state of 98 parts arsenic acid, combined with 72
parts lime.
In like manner, I find that 42 parts of potash, 28 of soda, and 12 of
ammonia, severally neutralize 98 parts of arsenic acid.
1st. 24 lime + 32.7 arsenic acid = insoluble arseniate
2d. -- + 49 ------------ = soluble arseniate
3d. -- + 98 ------------ = neutral arseniate
It is a remarkable fact, that when neutral arseniate of potash
and nitrate of lead are mixed together to mutual saturation, the
precipitate is found to consist chiefly of arsenic acid and oxide of
lead, in proportion of 1 of acid to two of oxide, (that is, 98 ∶ 194,
or 100 ∶ 198); which does not differ much from the determination of
Berzelius.
I find however, only one fourth of the nitric acid in the residuary
liquid in a free state; which leads me to suspect that the precipitate
is a compound of subnitrate and arseniate of lead, in which the arsenic
acid and lead are in due proportion, or 98 acid, to 97 oxide. This
consideration may be properly resumed hereafter.
Hence we conclude, the atom of arsenic weighs 21 (and not 42, as at
page 264, VOL. 1), that of the protoxide of common white arsenic,
28; and that of arsenic acid = 98, being a compound of 2 atoms of
deutoxide, and 1 of protoxide. Or,
100 Arsenic + 33.3 oxygen = 133.3 protoxide
-- + 55.5 ---- = 155.5 arsenic acid
21. _Oxides of cobalt._
There are at least two oxides of cobalt, the one blue, the other black.
Authors differ as to the proportions of the elements. Proust states
the blue oxide to consist of 100 metal, and 19 or 20 oxygen, and the
black of 25 or 26 oxygen. Klaproth finds in the blue, 100 metal and 18
oxygen. But Rolhoff according to Berzelius, finds 100 metal and 27.3
oxygen in the blue oxide, and 40.9 in the black. I have taken some
pains to investigate these oxides, and have been able to satisfy myself
in a good degree, respecting their constitution. The blue or protoxide
consists of 100 metal and 19 oxygen, and the black oxide of 100 metal,
and 25 or 26, very nearly as Proust determined.
_Protoxide._ By repeated trials I have found, that if 37 parts of
metallic cobalt be treated with the due quantity of nitro-muriatic
acid, and a heat of 150°, a rapid solution takes place, and a
disengagement of pure nitrous gas; this being carefully collected, it
will be found to weigh 8 grains, and of course corresponds to 7 grains
of oxygen; hence 37 cobalt, unite to 7 oxygen, to form 44 of the blue
oxide; and as this is the only oxide that combines with acids, it must
be considered as the most simple or protoxide, being 1 atom of metal
(37), and 1 of oxygen (7). The estimation of the atom of cobalt at 50
or 60, (page 265), must therefore be corrected.
_Compound oxides._ When the blue oxide of cobalt is precipitated
from a solution, by an alkali or lime water, and oxymuriate of lime
is gradually dropped in, the precipitate changes colour rapidly; it
passes from blue to green and olive, thence to a dark bottle green,
and finally becomes black; oxygen gas is given out copiously when an
excess of oxymuriate of lime is used. I find the additional oxygen
requisite to convert the blue to the black oxide is what Proust states
it, namely, ⅓ of that necessary to form the blue; hence it must be
considered as a compound of 1 atom of oxygen and 3 of the protoxide.
Probably the other coloured oxides are 1 to 4, 1 to 5, &c. The
protoxide is blue when precipitated, but it is supposed to contain
water, or to be a hydrate; as it is dark grey when heated. The blue
oxide in a short time after precipitation being still under water,
changes to a yellowish or dead-leaf colour; which also appears to be a
hydrate of the protoxide, as it dissolves in acids without giving out
gas, and yields the blue oxide by an alkali. According to Proust, this
hydrate contains 20 or 21 per cent. water. If we suppose the blue to be
1 atom oxide, and 1 water, the yellow hydrate may be 1 water and 2 of
the proto-hydrate; or 88 oxide, and 24 water, which will be nearly 21
per cent. water.
The black oxide gives out oxygen gas by a red heat, and is reduced to
the grey oxide: it forms oxymuriatic acid, with muriatic acid, and the
protoxide remains in solution.
(See Tassaert.--An. de Chimie 28; Thenard, 42; and Proust, 60.)
22. _Oxides of manganese._
One of the oxides of manganese being a natural production, and
sometimes of great purity, and the metal not being obtainable without
skill and labour, it may be most convenient to adopt the inverse method
in our investigations; that is, to trace out the atom of metal from its
oxides.
_Native oxides of manganese._ Of late, I have met with excellent
specimens of this oxide; they are in masses of a grey, crystalline
appearance, sp. gr. 4, easily pulverizable into a greasy, shining, dark
grey powder. They are nearly pure oxide; but the more common sort is
blacker, and contains less or more of siliceous earth. Some specimens
are very harsh, require an iron mortar to pulverize them, and contain
50 or upwards per cent. of siliceous earth. Of the common sort when
pulverized, the black inclining to blue, is generally preferable to the
black inclining to brown. I have not observed any earthy carbonates
mixed with the oxide of manganese. Amongst various specimens I obtained
the following analyses.
Oxide. sand and insoluble
matter.
1. Grey, crystallized oxide 100 ----
2. Pulverized black oxide, from } 80 20
a bleacher, reputed good }
3. Another specimen, in the lump 77 23
4. A light brown oxide 47 53
5. A sparry oxide, abounding with } 27 73
flint; black brown when pulverized }
Some of the chemical characters of the native oxide of manganese are,
its giving oxygen gas by a red heat, its insolubility in nitric and
sulphuric acids, and its solubility in muriatic acid, but with the
accompanying circumstance of disengaging oxymuriatic acid.
All these facts shew that it is of the higher order of oxides, or
analogous to the brown and red oxides of lead.--The muriatic acid
solution abovementioned, contains an oxide of an inferior degree, which
is soluble in all acids, and which is the only oxide of manganese that
appears to be soluble in acids. If this be considered, (as it may with
the greatest probability), the protoxide, then it will appear from what
follows, that the common native manganese is the deutoxide, and that
there is an intermediate one, which contains a mean quantity of oxygen.
_Protoxide._ This may be obtained in solution with muriatic acid as
above, from the native oxide. Or the black oxide may be mixed with
sulphuric acid into a paste, and heated in an iron spoon to redness;
the mass being lixiviated, a solution of the protoxide in sulphuric
acid is obtained, generally with a slight excess of the acid; in this
process heat and the presence of sulphuric acid, expels the redundant
oxygen of the black oxide, and reduce it to the protoxide, which
hence becomes soluble. If in either of these solutions any oxide
of iron be present, whether from the manganese, or acquired during
the manipulation, it is easily discovered and separated, as I have
frequently found. Into any solution containing a mixture of the oxides
of manganese, the green oxide of iron, and the red oxide of iron, let
lime water be gradually poured; the red oxide of iron will be first
precipitated, next the green oxide, and lastly the oxide of manganese,
which may hence be separated from each other. Iron may also be
discovered and separated by carbonate of potash, which must be dropped
into the solution as long as any coloured precipitate appears; as soon
as it has subsided, the snow-white carbonate of manganese succeeds.
This white carbonate may be very conveniently used for obtaining
solutions of pure manganese in any of the acids.
When a solution of pure manganese is treated with lime water, or
ammonia, a light buff oxide, not much differing in appearance from the
yellow oxide of iron, is obtained. This oxide is soluble in all acids,
when recently precipitated; but, such is its avidity for oxygen, with
moderate agitation of the liquid it acquires oxygen and becomes brown,
when it ceases to be totally soluble; if dried in the air quickly, it
becomes brown and obtains considerable oxygen. The buff oxide recently
precipitated, is probably a hydrate; for, when the white carbonate of
manganese is heated gradually to red, the water and the acid are both
expelled, and a grey powder remains; this is quite black on the surface
of the mass, if exposed to the air during the process. Probably this
grey powder is the pure protoxide; it is soluble in acids, except the
black powder at the surface; perhaps but for the oxygen of the air, the
protoxide would be nearly white.
From its combinations with sulphuric and carbonic acids, I find the
weight of an atom of the protoxide to be 32, or the same as that of
iron. Dr. John, a German chemist, who seems to have investigated these
salts with more attention than any other person, has deduced nearly the
same results. (Annals of Philos. 2-172). He finds 33⅔ sulphuric acid +
31 oxide, and 34.2 carbonic acid + 55.8 oxide; that is, when reduced
to compare with my results, 34 sulphuric acid + 31.3 oxide, and 19.4
carbonic acid + 32 oxide. This near agreement may be considered as a
confirmation of the accuracy of both. Dr. John finds, as I have done,
three distinct oxides of manganese, the greyish green, the brown, and
the black. The first of these is the only one that combines with acids;
but we differ materially as to the quantity of oxygen in each. He found
manganese decompose water at the ordinary temperature; by oxidizing
the metal this way, 100 metal acquired 15 oxygen to constitute the
protoxide; according to this, 28 metal + 4 oxygen would make 32
protoxide; but this conclusion would be so contrary to all analogy,
that it cannot be admitted as satisfactory. The probability is, that
the manganese must have contained a little oxygen at the commencement
of the experiment. The general analogy of manganese to iron, lead, &c.
requires that 32 protoxide should contain 7 oxygen. If this be allowed,
we have the atom of manganese = 25, and not 40, (as at page 266, VOL.
1), the same as that of iron: and this conclusion is corroborated by
what follows.
2. _Intermediate or olive brown oxide._ This may be formed by combining
oxygen directly with the buff or protoxide recently precipitated,
and still remaining in the liquor; simple agitation in oxygenous gas
or common air for a few minutes, is all that is requisite. Or it may
be instantly formed by treating the same moist protoxide with liquid
oxymuriate of lime. Or it may be had by exposing the purest black oxide
to a bright red heat for some time, when it will lose 9 or 10 per cent.
and there will remain the olive brown oxide.
To find the proportion of oxygen absorbed, I precipitated 3.2 grains
of the protoxide by lime water; the liquid containing the oxide was
put into a well stoppered bottle of oxygen gas; on agitation the oxide
changed colour fast, from buff to brown; in a short time it absorbed
260 grain measures of gas = .35 of a grain in weight, and then ceased
to absorb. In another experiment, 3.2 grains of precipitated protoxide,
took 100 measures of a solution of oxymuriate of lime, containing .35
per cent. of oxygen, (that is, 1.45 oxymuriatic acid). Hence as 32
take 3.5, 64 must take 7; which shews the brown oxide to be a compound
of 1 atom of oxygen, and 2 of the protoxide.
The characters of this oxide are, its olive brown colour, its
insolubility in nitric and sulphuric acids, without heat or
deoxidation, and its solubility in muriatic acid after the evolution of
oxymuriatic acid. By long exposure to the air, it is gradually changed,
in all probability into the black oxide.
3. _Deutoxide._ In order to determine the quantity of oxygen deducible
from the purest native oxide of manganese, to convert it into
protoxide, I have successfully adopted the two following methods. 1st.
Let 39 or 40 grains of the oxide be mixed with 60 common salt; to this
add 80 grains of water, and 120 grains weight of strong sulphuric
acid, in a gas bottle. The heat must be gradually raised to boiling,
and the oxymuriatic acid gas may be received in a quart of lime water.
This will be found sufficient to convert 800 measures of test green
sulphate of iron (1.156) into red; that is, it will produce 29 grains
of oxymuriatic acid, which will cause 7 grains of oxygen, to unite to
the green oxide of iron. Now 100 measures of 1.156 sulphate, according
to some recent experiments of mine, contain 8 grains of green oxide,
(I estimated the sp. gr. of test sulphate, heretofore at 1.149);
hence 800 contain 64 oxide, and these require just 7 grains of oxygen
to be united to them, to form the red oxide, as has been shewn, page
34. In the above experiment, the 39 grains of oxide, will be found to
vanish or be dissolved, if pure, and to yield 32 grains of protoxide,
making up with the 7 grains of oxygen, the original weight. Hence we
have 39 grains of the oxide resolved into 32 protoxide, and 7 oxygen.
If then we allow 32 protoxide, to contain 7 oxygen, it appears that
39 grains of the native oxide, consists of 1 atom manganese (25), and
two atoms of oxygen (14); or it is the deutoxide of the metal. 2d. A
more direct and expeditious method, of transferring the oxygen from
the manganese to the iron, is as follows: Let 39 grains of pure grey
shining oxide, be mixed with 800 of test green sulphate of iron; to
this mixture let 25 or 30 grain measures of strong sulphuric acid be
added: after stirring the mixture for 5 minutes, the oxide of manganese
will be completely dissolved, and, on precipitating the oxide of iron
gradually, by lime water, it will be found to be wholly _yellow_ or
buff; shewing that 7 grains of oxygen have been transferred from the
oxide of manganese to that of iron.--If more green sulphate of iron
be used, then the surplus of the oxide will be thrown down green; the
order of precipitation being the yellow oxide of iron, the green oxide
of iron, and lastly, the yellow or buff oxide of manganese, as has been
stated. This affords an easy and elegant method of appreciating the
different oxides of manganese of commerce; and it was in this mode, the
valuations of the specimens in the above table were made.
The proportions of the three oxides are then as under:
Manganese Oxygen
Protoxide 100 + 28 -- buff; soluble in acids.
Intermediate oxide -- + 42 -- brown; insoluble.
Deutoxide -- + 56 -- black; insoluble.
It may be proper to subjoin the results of others, who have
investigated the oxides of manganese. Bergman finds 3 oxides,
containing 100 metal + 25, 35, and 66.6 oxygen; Dr. John finds 3
oxides, containing 100 metal + 15, 25, and 40 oxygen: Berzelius finds
5 oxides, containing 100 metal + 7, 14, 28, 42, and 56 oxygen; and
Davy finds 2 oxides, containing 100 metal + 26.6, and 39.9 oxygen,
respectively.
23. _Oxides of chromium._
There appear to be at least two oxides of chromium, one or other of
which is found in combination with the oxides of lead or iron, but
hitherto so very sparingly that few chemists have had an opportunity of
investigating the proportions of chrome and oxygen, in the oxides of
chromium. The chief sources for information on this subject, are essays
by Vauquelin, An. de Chimie, VOL. 25 and 70; by Tassaert, _ibid._ 31;
by Mussin Puschin, _ibid._ 32; by Godon, _ibid._ 53; by Laugier _ibid._
78, and by Berzelius, Annal. of Philosophy, 3.
The oxides of chromium, as might be supposed, are distinguished for the
colours which they possess and impart to the compounds into which they
enter. One of the oxides is green; it gives colour to the emerald. The
other is yellow, dissolved in water, but deep red when crystallized,
and possesses the characters of an acid; it unites with alkalies,
earths, and metallic oxides; it was first found in Siberia, in
combination with the oxide of lead, a salt now denominated _chromate_
of lead, of a splendid yellow colour, inclining to orange or red.
Since then, the chromate of iron, has been found in France, America,
and Siberia, with a prospect of greater abundance.
In order to investigate the weight of the atom of chromic acid, it is
necessary to attend to such of the chromates as have been carefully
examined. The chromates of potash, barytes, lead, iron, and mercury,
are those with which we are best acquainted.
Vauquelin has given us the components of the native chromate of lead
by analysis, and those of the artificial chromate by synthesis; the
results do not accord very nearly: for, according to the analysis
corrected by the modern science,
Chromate of lead = 62 acid + 97 oxide
By synth. chromate of lead = 57½ -- + 97 --
Berzelius however, has more lately given us the results of his
experience, both analytical, and synthetical; and he finds both to give
chromate of lead nearly = 44 acid + 97 oxide.
Chromate of barytes (Vauq.) = 47.8 acid + 68 barytes
Ditto (Berz.) = 44 -- + 68 --
Native chromate of iron (Vauq.) = 45 acid + 35½ oxide
Ditto (Laugier) = 55 -- + 35½ --
Having received a small portion of chromate of potash in solution,
from a chemical friend (J. Sims), I endeavoured to satisfy myself, as
far as my materials would go, as to the nature and proportions of the
chromates. The solution was of the sp. gr. 1.061, and consequently in
100 measures contained nearly 6.7 grains of chromic acid and potash,
&c.--The liquid was a beautiful yellow; it was alkaline by the colour
test. By the usual tests, I had reason to believe, that the solution
contained as under per cent.--namely,
2.2 gr. chromic acid
2. potash
.8 uncomb. potash
1.4 carb. potash
.3 sulphate of potash
---
6.7
With this liquid neutralized by nitric acid, I formed the chromates of
lead, barytes, iron, and mercury; and I am inclined to believe these
salts are nearly constituted as under:
Neutral chromate of potash 46 acid + 42 potash
-- -- of barytes 46 -- + 68 barytes
-- -- of lead 46 -- + 97 oxide
-- -- of iron 46 -- + 32 oxide (black)
-- -- of mercury 46 -- + 174 oxide (black)
According to these results, the atom of chromic acid weighs 46; it is
made 44 by the results of Berzelius, and from 45 to 62 by those of
Vauquelin; I would not be understood to place great confidence in the
above results of mine, though I am persuaded they will be found good
approximations.
Is the chromic acid the deutoxide, or the tritoxide of chromium?
The determination will evidently be affected by the question, how much
oxygen must be abstracted from the chromic acid to reduce it to the
green oxide. Vauquelin finds 46 acid to lose 6½ oxygen, and Berzelius
10½, when converted into green oxide by heat. From the former of these,
one would infer chrome to be 32, the green or protoxide of chrome to
be 39, and the acid or deutoxide 46: from the latter, chrome = 25,
protoxide = 32 (unknown), the green oxide = 1 protoxide and 1 deutoxide
united [= 71 = 50 chrome + 21 oxygen = (25 chrome + 10½ oxygen) × 2 =
35½ × 2] the deutoxide = 39, and the tritoxide or chromic acid = 46.
I have not had an opportunity to perform any experiment that appears
to me decisive as to the accuracy of one or other of these views; but
shall make a few remarks relative to them.
The green oxide being the most prominent compound next to the chromic
acid, being commonly produced from it by any deoxidizing process, being
the lowest oxide known, and combining with acids, is on these accounts
entitled to the consideration of the protoxide; indeed there does not
seem an instance where the protoxide of a metal is unknown, whilst the
deutoxide and compound oxides are known. There is however, another
oxide observed by Vauquelin and by Berzelius, which is obtained by
heating the nitrate, or combination of nitric acid and the green oxide,
to dryness and expelling the acid; this oxide is brown, and gives
oxymuriatic acid when treated with muriatic acid; on this account it
would seem to be intermediate between the green oxide and the chromic
acid; it is probably a combination of the two, or the _chromate of
chromium_. On the other view however, it must be considered as the
deutoxide. What corroborates the notion of the green oxide being 39, is
the fact which I have observed, of 46 parts of chromic acid combining
with 64 of the green oxide of iron to form 110 of chromate of iron; in
this combination the oxide of iron may be said to borrow 1 atom of
oxygen from the chromic acid, and the compound may then be considered
as the union of the green oxide of chrome, and the red oxide of iron.
When this precipitate is subjected to the action of muriatic acid, a
green solution is obtained containing the oxide of chrome, and red
oxide of iron is precipitated, as Vauquelin has observed. To form the
above chromate (or rather subchromate) of iron, let a given portion
of neutral chromate of potash be treated with green sulphate of iron,
and lime water be added, sufficient to saturate the sulphuric acid, a
brown red precipitate is obtained; more sulphate and lime water must be
gradually added to the clear liquid till the precipitate become green,
when the proportions will be found as above stated. This artificial
compound seems a subchromate; whereas the native compound seems to be a
chromate. That there is some uncertainty in decomposing a chromate by
heat with a view to obtain the green oxide, I have reason to suspect
from having decomposed 5⅓ grains of chromate of mercury by a moderate
red heat; this compound contained 1.1 chromic acid, and it yielded only
.6 of green oxide, whereas it should have been .9 or .8 at least.
Upon the whole I think the evidence is in favour of the opinion that
the atom of chrome is 32, the green or protoxide 39, and the deutoxide
or chromic acid is 46.
24. _Oxides of uranium._
There appear to be two oxides of uranium from the experiments of
Klaproth, Bucholz, and Vauquelin; but the proportions of metal and
oxygen have not been very nearly ascertained, from the great scarcity
of the minerals containing this metal. (Vid. Bucholz, An. de Chimie,
56--142. Vauquelin, ibid. 68--277; or Nicholson’s Journ. 25--69). The
oxides are obtained by precipitation from solutions of the minerals
in the nitric or muriatic acid, the foreign substances being first
separated.
The protoxide of uranium precipitates dark bottle green by caustic
alkalies, and forms crystallizable salts with acids; the other,
probably the deutoxide, precipitates orange yellow, and forms
uncrystallizable salts with acids; in these respects the oxides bear a
near resemblance to those of iron.
Bucholz estimates the yellow oxide at 100 metal + from 25 to 32 oxygen;
as it yields oxymuriatic acid when treated with muriatic, it is most
likely to be the deutoxide; now if we take 28 for the oxygen combined
with 100 metal, the protoxide must consist of 100 metal + 14 oxygen, or
of 50 metal + 7 oxygen, and the atom of uranium = 50. From his account
of the sulphate and nitrate of uranium the weight of the atom might be
inferred to be double of the above or 100. These different conclusions
can only be elucidated by future experiments.
25. _Oxides of molybdenum._
The latest and as it should seem most accurate experiments on
the oxides of molybdenum were made by Bucholz. (Vid. Nicholson’s
Journal, 20, p. 121). There appear to be 3 oxides or combinations
of molybdenum and oxygen, namely, the _brown_, the _blue_, and the
_white_ or _yellow_. The two last have the character of acids, and
none of them seem to form salts with acids, like oxides in general.
Bucholz ascertained the above gradation, and that the white oxide or
molybdic acid contains ⅓ of its weight of oxygen; (which has since
been corroborated by Berzelius); he also found that the blue was best
formed by mixing, triturating, and boiling in water 3 parts of brown
oxide, and 4 of white, or one of metal, and two of acid; and that it
has acid qualities as well as the white. Bucholz also found 3 parts
of liquid ammonia of the sp. gr. .97 dissolve 1 of molybdic acid; now
3 parts of ammonia = .186 real (VOL. 1, p. 422); and 1 ∶ .186 ∷ 64 ∶
12, the quantity of ammonia usually saturated by one atom of acid;
and Berzelius found 100 molybdic acid saturate 155 oxide of lead, or
63 acid to 97 oxide. The native sulphuret of molybdenum (the state in
which this metal is usually found) was analyzed by Bucholz and found to
consist of 60 metal and 40 sulphur.
The molybdic acid may be obtained by roasting the sulphuret in a
crucible and stirring it frequently; the sulphur in great part escapes
in the form of sulphurous acid and the metal becomes oxidated:
carbonate of soda in solution may be added to the residuum as long as
any effervescence is observed; molybdate of soda remains in solution
and the acid may be precipitated by nitric acid. The brown oxide is
best obtained by heating molybdate of ammonia to red; the ammonia and
part of the oxygen are expelled, and the brown oxide remains.
There are two views with which the preceding results may be reconciled;
namely, 1st. supposing the atom of molybdenum to weigh 21; and 2d, by
supposing it to weigh 42 or twice that number. In the first case the
brown oxide will weigh 24½ (49) being supposed 2 atoms of metal and 1
of oxygen, the blue or protoxide will weigh 28, and the white oxide
or molybdic acid will weigh 63, being a compound of the protoxide and
deutoxide, molybdena or native sulphuret will then be as usual, the
protosulphuret, consisting of 21 metal and 14 sulphur, or 60 metal
and 40 sulphur. In the 2d. case the brown or protoxide will weigh 49,
the blue or deutoxide 56, and the acid or tritoxide 63. The native
sulphuret, molybdena, must in this view be the deutosulphuret, or 42
metal and 28 sulphur.
The former of these views exhibits the oxides somewhat complicated,
but agrees well with the sulphuret; the latter shews the oxides in a
more regular train, but does not appear so probable from the sulphuret;
besides, the notion of a metallic tritoxide is rather singular,
especially in a metal that is rarely if ever found in combination
with oxygen. Upon the whole I prefer the former view; but it must be
considered as problematical only. The atom of 60 (see page 267 VOL. 1)
must doubtless be erroneous.
26. _Oxides of tungsten._
From the experiments of D’Elhuiarts, Bucholz[13] and Berzelius[14] it
seems very probable that the tungstic acid is composed of about 100
metal + 25 oxygen. It is a _yellow_ powder of the sp. gr. 6.12, and is
best obtained from the native tungstate of lime (a scarce mineral).
One part tungstate of lime and four of carbonate of potash are fused
together, dissolved in water, and then the tungstic acid may be
precipitated by nitric acid. There is an inferior oxide that is black
or dark brown; Berzelius reduced the yellow oxide to a flea-brown
colour, by sending a current of hydrogen gas through it in a glass tube
heated red hot. 100 parts of this oxide burnt be 107 yellow oxide.
Hence 100 metal must combine with about 16½ or 17 oxygen to form this
oxide, which is ⅔ of that in the yellow or tungstic acid.--Upon the
whole it does not seem improbable, considering the great sp. gravity
of this metal, that it forms three oxides and that the acid or yellow
oxide is the 3d. Hence the atom of tungsten must be 84, that of the
protoxide 91, the deutoxide 98, and the tritoxide or tungstic acid 105.
The native tungstate of lime, if pure, according to this would be 81.4
acid + 18.6 lime, which is not far from Klaproth’s analysis; he having
found 18.7 lime in one specimen; nor from that of Berzelius, he having
found 80.4 tungstic acid and 19.4 lime in 99.8 tungstate of lime.[15]
[Footnote 13: An. of Philos. 6--198]
[Footnote 14: An. of Philos. 3-244]
[Footnote 15: An. of Philos. 8--237]
There is another view however, which would accord with the experiments
and perhaps will be found preferable in other respects; that is, to
suppose the tungstic acid to be composed of 1 atom deutoxide and 1 atom
protoxide united; in this case the atom of tungsten = 42, that of the
protoxide = 49, that of the deutoxide = 56, and the tungstic acid = 105
as before.
27. _Oxides of titanium._
Nothing certain is known respecting the oxides of titanium. An
observation of Richter, quoted by Berzelius (An. of Philos. 3--251), if
it could be relied upon, furnishes an important fact, namely, that a
solution of muriate of titanium containing 84.4 oxide, gave 150 muriate
of silver. Now 150 muriate of silver contain 28 acid; hence 28 acid
must have combined with 84.4 oxide; but if 28 ∶ 84.4 ∷ 22 ∶ 66 nearly
for the weight of an atom of the oxide. This would indicate 59 for an
atom of the metal.
28. _Oxides of columbium._
The white oxide or acid of columbium is found in combination with the
oxides of iron and manganese in proportion nearly as 4 of the acid to
1 of the aggregate oxides. The two minerals, columbite and tantalite,
though yielding these substances nearly in the same proportions, are
found to differ remarkably in specific gravity, the former being
about 5.9 and the latter about 7.9. Dr. Wollaston concludes however,
from the agreement of the white oxides extracted, that they must be
the same. The white oxide of columbium is insoluble in the mineral
acids; it unites with potash by fusion, and may be precipitated by
most acids. Some of the vegetable acids, the oxalic, the tartaric, and
the citric dissolve the white oxide. When the alkaline solution of
columbium previously neutralized by an acid is treated with infusion
of galls, an orange precipitate is produced which is characteristic
of columbium. Nothing certain has been determined respecting the
proportions of metal and oxygen; but from the great proportion of the
columbic acid found with the oxides of iron and manganese, together
with the great sp. gravity of the compound, one may pretty clearly
infer the great weight of the atom of columbium. Supposing the white
oxide or acid to consist of 1 atom metal + 3 oxygen and that the
columbite is formed by 1 atom of acid to 1 of oxide, we should have
128 acid + 32 oxide. This would give 107 for the weight of an atom of
metal, and 128 for that of the tritoxide or columbic acid; but it is
unnecessary to dwell upon such conjectures.
In a recent memoir of Messrs. Gahn, Berzelius, and Eggertz (An. de
Chimie, Octo. 1816), it is maintained as probable that there is only
one oxide of columbium or tantalum, and that 100 metal take 5.485
oxygen, or 121 metal take 7 oxygen. If this be correct, the atom of
columbium must be 121 and the protoxide 128.
(See also An. de Chimie, 43--271; Philos. Trans. 1802; Nichols. Journ.
2--129; ibid. 3--251; ibid. 25--23).
29. _Oxides of cerium._
The mineral cerite is of the sp. gr. 4.53, and constituted of 50 or 60
per cent. of oxide of cerium, with silex, lime, and iron. This mineral
being calcined and dissolved in nitro-muriatic acid, the solution is
to be neutralized by caustic potash, and then treated with tartrate of
potash. The precipitate, well washed and afterwards calcined, is pure
oxide of cerium. This oxide, which is white, when calcined in the open
air becomes red and acquires more oxygen. These oxides, particularly
the white, are soluble in most acids; the red oxide with muriatic acid
gives oxymuriatic acid.
The experiments hitherto made on this subject scarcely enable us to
decide respecting the proportions of metal and oxygen, nor the relative
weights of these oxides.
Both Vauquelin[16] and Hisinger[17] agree that the protocarbonate
of cerium, when exposed to a red heat, yields 57 or 58 oxide, which
the former says is the red oxide, being changed by the calcination.
Hisinger finds the percarbonate to consist of 36.2 acid and 63.8
oxide: also that the muriate of cerium consists of 100 acid and 197.5
oxide; but Vauquelin remarks that the sulphate, nitrate, and muriate
of cerium are always more or less acid, however dried; and he found
the protoxalate of cerium to yield 45.6 red oxide by calcination, on
a mean of 3 experiments not much differing from each other. Supposing
all these facts accurate, they may be reconciled by a few suppositions
by no means improbable. Let the atom of cerium be 22, the protoxide
29, and the red oxide 32½ (that is, 1 oxy. + 2 protox. = 65); and let
the protocarbonate be 1 atom of acid, 1 of oxide, and 1 of water; the
percarbonate, 1 acid 1 oxide; the oxalate, 1 acid (40) and 1 oxide; and
the muriate, saturated with base, 3 oxide and 2 acid. Then it will be
found that,
[Footnote 16: An. de Chimie, 54--28]
[Footnote 17: An. of Philos.--4--356]
The decomposed protocarbonate will yield 57.5 red oxide;
The decomposed percarbonate will yield, 36.7 acid, 63.3 oxide;
The decomposed oxalate will yield 47 red oxide; and
The muriate will yield 100 acid (22), and 197.7 oxide.
All of which agree very nearly with the results above obtained.
Hence it appears to me very probable that the several atoms of the
metal and the oxides are as stated above; and that,
100 cerium + 31.8 oxygen = 131.8 protoxide, white.
---------- + 47.7 ------ = 147.7 intermediate, red.
Hisinsger, from some of the same data united to other hypothetical
facts than those assumed above, deduces the two oxides very different;
viz. 100 metal + 17.4 oxygen for the protoxide, and 100 + 26.1 for the
peroxide.
SECTION 14.
EARTHY, ALKALINE AND METALLIC SULPHURETS.
The sulphurets exhibit a very important class of combinations of two
elements. Many of the metals are found chiefly in the state of native
sulphurets, and are extracted by particular processes. Artificial
combinations of sulphur and the metals, and of sulphur and the earths
and alkalies are commonly practised, and are found useful in chemical
investigations. The alkaline and earthy sulphurets will scarcely be
allowed perhaps to be combinations of _two elements_ only; but their
analogy with the other compounds is such as to induce us to treat of
them under this head, especially as they are agents occasionally in
the formation of metallic sulphurets, and these cannot be so well
understood without some knowledge of the other. For like reasons
the compounds of three elements, sulphur, metal, and oxygen, called
sulphuretted oxides, and sulphuretted sulphites, and those of four
elements, sulphur, metal, oxygen and hydrogen, called hydrosulphurets,
may be considered at the same time, having an intimate relation with
the sulphurets strictly so called, or the compounds formed with sulphur
and the undecompounded bodies.
Sulphur may be combined with the earths, alkalies and metals, by heat,
of various degrees according to the nature of the subjects. The union
is attended in many cases with a glowing ignition, indicating the
evolution of heat. The metallic oxides and sulphur when heated together
commonly produce a sulphuret of the metal, whilst the oxygen escapes
with part of the redundant sulphur in the form of sulphurous acid, and
the rest of the sulphur sublimes.
In the humid way sulphur may be combined with earths, alkalies, and
metals, by means of sulphuretted hydrogen, hydrosulphurets (that is,
sulphuretted hydrogen united to other alkaline or earthy bases), and
hydroguretted sulphurets (a name given to certain earthy and alkaline
sulphurets formed mostly by boiling mixtures of the respective bases
and sulphur in water.) The sulphuretted hydrogen may be used in
this state of gas or combined with water; the hydrosulphurets and
hydroguretted sulphurets are best applied in their watery solutions.
The metals are to be used in this case in the state of salts, that is,
oxides united to acids, and in solution; or their oxides may in some
instances be precipitated previously to the addition of the sulphur
compound; the alkalies and earths are sometimes directly sulphurized in
the state of hydrates, and at other times by double affinity, in the
state of salts or combined with acids. The phenomena in the case of
sulphurets formed in the humid way, are various and often complicated,
and the true results are not always to be obtained without considerable
difficulty and uncertainty.
1. _Sulphurets of lime._
When pounded lime and sulphur are mixed together, and heated in a
crucible scarcely any union takes place; the sulphur sublimes or burns
away and leaves the lime unaltered. If for lime we substitute carbonate
of lime, it also remains unaltered. But if hydrate of lime and sulphur
are heated together in equal weights, the hydrate is decomposed, and
the lime unites to a portion of the sulphur, whilst the excess of
sulphur sublimes or burns and escapes at a low red heat. The residue,
about 60 per cent. of the original weight, is a yellowish white powder,
composed of sulphur and lime. If this be again treated with sulphur
and heated, it undergoes no material change; the last sulphur entirely
escaping, leaves the sulphuret unaltered, and hence shews that it must
be a true chemical compound.
Now if 32 parts hydrate of lime, which consist of 24 lime and 8 water,
be mixed with 32 sulphur and heated as above, they will yield 38
parts sulphuret, which must be composed of 24 lime and 14 sulphur,
or sulphur and water; but it appears from the analysis hereafter to
be given, that the whole of this last part is sulphur; therefore the
compound is formed of 1 atom of lime, and 1 of sulphur, and is the
_protosulphuret_ of lime.
When 32 parts of common hydrate of lime and 56 sulphur, are boiled
together in 1000 parts water for half an hour, or more, occasionally
adding water to supply the waste, a fine yellow liquid is obtained,
with a few grains of residuum containing both lime and sulphur nearly
in the original proportion with a few grains of alumine. This liquid
of course contains in solution, a combination of 1 atom of lime, or
perhaps hydrate of lime, and 4 atoms of sulphur; and may therefore
be called a _quadrisulphuret_ of lime. If more sulphur or lime
than the above proportion be used, the surplus will remain in the
residuum uncombined, shewing that by this process no other than a
quadrisulphuret can be formed. A similar solution may be obtained in
cold water by frequent agitation; but it is much slower in producing
the effect. The strength of liquid quadrisulphuret depends upon the
relative quantity of the ingredients. I have boiled it down till the
water was only 5 times the other materials, which appears to be its
maximum strength in the common temperature; its specific gravity was
1.146; but in general I have used it of less than 1.07 density. It
may be proper to remark here that I find the decimals multiplied by
4 express very nearly the number of grains of lime in 1000 grains
measures of the solution, and multiplied by 9 those of the sulphur;
on this account a solution of the sp. gravity 1.06 facilitates the
calculations, as 100 measures of it contain 2.4 grains of lime, and 5.4
or 5.6 of sulphur nearly.
It is rather surprising that no bisulphuret nor trisulphuret of lime
should be formed this way. One would suppose that the sulphuret of
lime in its progressive changes would have passed through the forms of
bisulphuret, &c. till it had obtained its maximum of sulphur when that
was in excess; but, as has been observed, the quadrisulphuret is the
only one formed, whatever may be the proportions of the ingredients.
I imagine the reason to be, that the sulphur has to decompose the
hydrate of lime, and that no fewer than 4 atoms of sulphur are adequate
to that effect; it is known that water adheres so strongly to lime
as to require a red heat to separate it. When therefore we mix lime
water with quadrisulphuret of lime, it must be considered as a mere
mixture of the two, and that the lime does not divide the sulphur
equally. Consistently with this reasoning, whenever the lime is in
excess in forming quadrisulphuret of lime, we ought to consider the
liquid solution as _lime water_ holding quadrisulphuret of lime. This
distinction will be of some importance when the solution is weak,
because then the lime in the lime water will be considerable, compared
with the lime combined with sulphur.
1. _Protosulphuret._ The properties of this compound are;--about 1
grain is soluble in 1000 water; this water, as well as the powder
itself, tastes like the white of an egg; salts of lead are thrown
down black by the solution; weak nitric and muriatic acids dissolve
the lime, and leave the sulphur; 100 parts of test acid require 19
of the powder, and yield 7 of sulphur; indicating the compound to be
12 lime and 7 sulphur. The same conclusion may be obtained by means
of a solution of lead; if water containing 1.9 grains of the powder
be precipitated by nitrate of lead, it will require 7 grains of the
salt = 2.2 acid and 4.8 oxide, or 4.5 lead, and about 5 or 5½ grains
of sulphuret of lead will be formed, and the liquid will contain 3.4
grains of neutral nitrate of lime.
2. _Quadrisulphuret._ This combination has been long known, and
some of its properties observed; but I have not found in authors any
determination of its proportions. It is of a beautiful yellow or orange
colour, and 1 grain imparts very sensible colour to 1000 of water; it
has a disagreeable bitter taste; when evaporated down, it crystallizes
or rather perhaps solidifies into a yellowish mass; but its properties
are affected by the process from the acquisition of oxygen. This
mass when dried, burns with a blue flame and loses 40 per cent.; the
remainder is a white powder, a mixture of sulphite and protosulphuret
of lime. Liquid quadrisulphuret exposed to the atmosphere soon becomes
covered with a white film which arises from the sulphur displaced by
oxygen gas; this film being broken subsides, and another is formed,
and so on successively till at length the acquisition of oxygen
ceases with the deposition of sulphur, and the liquid remains quite
colourless. It is intensely bitter, and contains lime, sulphur and
oxygen in proportions to be presently determined. This colourless
liquor undergoes a gradual change by being kept for years in a bottle
with a common cork; a deposition of some sulphur and sulphate of lime
takes place, but whether from a further acquisition of oxygen gas or
from some internal chemical action, I have not had an opportunity of
observing.
From the above observations it is obvious that to form _pure_
quadrisulphuret of lime the atmospheric air should be excluded, as the
agitation by ebullition would promote the oxidizement of the compound.
I mixed 168 grains of sublimed sulphur with 96 hydrate of lime, which
by previous trials I had found to consist of 70 lime including 2 or
3 grains of alumine, and 26 water; the mixture was put into a small
florence flask, which was then filled with water up to the neck and
loosely corked. This was immersed in a pan of water and boiled for 2 or
3 hours, the flask was continually turned round to agitate the mixture
and promote the solution. After the undissolved part had subsided the
clear liquor was decanted and found to be 2800 grain measures of the
sp. gr. 1.056; the residuum moderately dried weighed 34 grains; it
was found to contain 8 of lime and alumine, and 25 of sulphur. Hence
the liquid contained 62 lime and 143 sulphur, or 2.2 lime and 5.1
sulphur per cent.; that is, after the rate of 24 lime to 56 sulphur,
or 1 atom of lime to 4 of sulphur, and its weight = 80, the atom of
sulphur being supposed 14. Here then we have a synthetic proof of the
composition being a quadrisulphuret. Innumerable other experiments,
though made with less rigid accuracy, had convinced me that the liquid
is essentially the same whatever the proportions of the ingredients,
and that the residuum only varies in such cases.
I have made many experiments occasionally since 1805, on the quantities
of oxygen absorbed and sulphur deposited by quadrisulphuret of lime.
They all concur in establishing the same conclusion; namely, that each
atom of the compound takes 2 of oxygen and deposits 2 of sulphur,
in its transformation from the yellow to the colourless state. For
instance, 100 measures of the above 1.056 took 900 of oxygen gas = 1.22
grains, and let fall 2 grains of sulphur, besides a small portion which
adhered to the bottle, which was estimated at a few tenths of a grain.
The method is to put 100 measures into a graduated and well stoppered
bottle filled with oxygen; to agitate briskly for half an hour,
occasionally opening the stopper a little under water to admit its
entrance into the place of the oxygen absorbed. Whenever the agitation
has been continued for five minutes without any sensible increase in
absorption, and the liquor, after standing to let the sulphur subside,
appears colourless, the experiment is finished. This new combination
then consists of 1 atom lime, 2 sulphur, and 2 oxygen = 66; it will be
necessary to give it a name: I propose calling it sulphuretted sulphite
of lime, as it is an atom of sulphur united to sulphite of lime; and
the rather, as it will appear in the sequel that other neutral salts
do combine occasionally with an atom of sulphur. This sulphuretted
sulphite may be boiled down to the sp. gr. 1.1 before it precipitates:
the liquid then contains about 12 per cent. of the salt, or 5 sulphur,
2½ oxygen, and 4½ lime. The salt precipitates from the liquid by
evaporation in the form of a white powder; it burns with a feeble blue
flame, and loses about 20 per cent.; the remainder is sulphite of lime.
When 100 grain measures of the liquid sulphuretted sulphite (1.1) are
saturated with oxymuriate of lime, they acquire 5 grains of oxygen, and
then yield 12½ grains of sulphuric acid (containing 5 sulphur and 7½
oxygen), as may be found by the barytic tests. The point of saturation
is known by the smell of oxymuriatic acid being given out permanently.
If however we oxidize the quadrisulphuret of lime by oxymuriate of
lime, the results are somewhat different. As soon as an atom of the
quadrisulphuret has received two atoms of oxygen it becomes colourless
as before, but ¾ of the sulphur is thrown down instead of ½; and
when more oxymuriate is added, so as to impart 3 atoms of oxygen to
one of the salt, a complete sulphate of lime is formed. The point of
saturation is determined by adding a small portion of muriatic acid to
the liquid, which develops the oxymuriatic acid as soon as it becomes
in excess. This method excels in the analysis of the alkaline and
earthy sulphurets in general.
When quadrisulphuret of lime is treated with an alkaline carbonate, a
reciprocal change takes place; the carbonic acid takes the lime, and
the alkali the sulphur, leaving however 1 atom of sulphur with the
carbonate which precipitates. Hence a sulphuretted carbonate of lime is
obtained and a trisulphuret of the alkali. The sulphur burns off from
the carbonate below a red heat and leaves 75 per cent. of carbonate of
lime; this affords an excellent analysis of quadrisulphuret of lime as
far as lime is the object. Thus 540 of the above 1.056 quadrisulphuret
took 100 test carbonate of potash (1.25), and gave a precipitate of
29 grains, which burned blue and left 22 grains = 12 lime, and 10
acid; but if 540 ∶ 12 ∷ 100 ∶ 2.2, as above determined synthetically:
moreover, 12 lime, 10 acid, and 7 sulphur, are as 24 lime, 20 acid,
and 14 sulphur; the composition of an atom of sulphuretted carbonate
of lime, which is analogous to the sulphuretted sulphite of lime, as
found above.
When quadrisulphuret of lime is treated with as much sulphuric acid
as is sufficient for the lime, the sulphur is in part precipitated,
but it is in union with the sulphate of lime, or at least they are
not separable by mechanical means. This compound is sold in the shops
under the name of precipitated sulphur. It is about one half sulphate
of lime, and the other half sulphur. The nitric and muriatic acids
precipitate the sulphur partially from quadrisulphuret, but the sulphur
assumes a viscid form and exhales sulphuretted hydrogen, and the
proportion of the elements of quadrisulphuret are not easily obtained
by any of these acids.
The mutual action of quadrisulphuret of lime, and the metallic salts
is curious and interesting; for instance, with nitrate of lead. Let
a solution of nitrate of lead, containing 97 oxide, be treated with
a solution of quadrisulphuret of lime by degrees, as long as a black
precipitate appears, marking the exact point of saturation; this will
be found when 36 parts of lime have entered, and 84 of sulphur; the
sulphuret of lead will fall, and when dried will weigh 145 parts,
and contain 90 lead, and 55 sulphur; that is, 1 atom of lead, and 4
of sulphur, and is consequently a quadrisulphuret of lead. The liquid
remains clear and colourless, and contains the nitric acid, lime,
oxygen of the lead, and ⅓ of the sulphur; each atom of nitric acid
combines with one of lime, which retains one of the 4 atoms of sulphur,
forming a sulphuretted nitrate of lime, consisting of 45 acid, 24 lime,
and 14 sulphur; the 7 parts of oxygen unite with 7 of sulphur to form
sulphurous acid, which require 12 parts of lime to saturate them and
7 of sulphur, forming a sulphuretted sulphite of lime: hence we see
that 28 parts of sulphur remain in the liquor, and the rest (56) unite
with the lead. If now we add gradually more nitrate of lead, a silvery
white precipitate appears, increasing till half the original quantity
is added, and then the liquid is saturated. This white precipitate is
sulphuretted sulphite of lead; when heated it soon grows black and
loses 15 or 20 per cent., being then a protosulphuret of lead. The
liquid now contains sulphuretted nitrate and simple nitrate of lime;
nitrate of lead has no effect, but nitrate of mercury precipitates a
black sulphuret.
Quadrisulphuret of lime saturated with oxygen, as has been observed,
contains sulphuretted sulphite of lime in solution, and deposits
sulphur: the liquid treated with nitrate of lead, gives as above the
white, silvery sulphuretted sulphite of lead as a precipitate, and
holds nitrate of lime in solution.
_Hydrosulphuret of lime._ This compound may be formed by passing
sulphuretted hydrogen into lime water; the water assumes a brownish
colour, but the point of saturation is not easily found, as the lime
water is not neutralized so as to shew by the colour test, and water
of itself absorbs above twice its volume of the gas. By means of a
neutral solution of nitrate of lead it may be found that 1000 lime
water in volume, require about 600 sulphuretted hydrogen, because then
a mutual saturation is observed by double affinity; that is, sulphuret
of lead and neutral nitrate of lime are formed; but otherwise the
liquid remaining is either acid or alkaline. Hydrosulphuret of lime,
as well as the other hydrosulphurets, has a peculiar bitter taste. It
forms a useful reagent in regard to metals, but is apt to be spoiled by
keeping, owing to the acquisition of oxygen.
2. _Sulphuret of magnesia._
I have not succeeded in endeavouring to combine sulphur and magnesia in
the dry way; but a liquid sulphuret is easily formed by the action of
double affinity.
Let a quantity of the liquid quadrisulphuret of lime be treated with
a solution of sulphate of magnesia, so that the sulphuric acid may be
sufficient for the lime; by digesting in a moderate heat, the sulphate
of lime is precipitated, carrying with it one fourth of the sulphur,
and a trisulphuret of magnesia remains in solution. I have not observed
any remarkable feature of distinction between this sulphuret and that
of lime, except as above noticed in the proportions of their compounds.
_Hydrosulphuret of magnesia._ This compound may be formed by pouring
sulphuretted hydrogen water into recently precipitated magnesia; it
does not differ much from that of lime. One atom of sulphuretted
hydrogen (15), combines with one of magnesia (17), and the compound is
soluble in water.
3. _Sulphuret of barytes._
_Protosulphuret._ The protosulphuret of barytes may be procured the
same way as that of lime, by heating hydrate of barytes and sulphur
till the mixture becomes red. It is very little soluble in water, and
accords in other respects with the like compound of lime. It consists
of 68 barytes and 14 sulphur, or 100 barytes and 20½ sulphur.
_Quadrisulphuret._ The quadrisulphuret of barytes may be formed the
same way as quadrisulphuret of lime, by boiling the hydrate of barytes
and sulphur together. A yellow solution of the compound is formed, not
distinguishable in appearance from that of lime; and it appears to
be analogous to it in most of its properties. By acquiring oxygen it
becomes colourless sulphuretted sulphite of barytes, and crystalizes in
needles; in this last respect it differs from that of lime. The maximum
density of liquid quadrisulphuret I have not had an opportunity of
ascertaining; it is 1.07 or upwards; that of the liquid sulphuretted
sulphite is much less than that of lime; the crystals are found in a
liquid so low as 1.004 sp. gr. They have a fine silky lustre when dry,
and a yellowish colour; heated they burn with a blue flame and leave
a white mass of sulphate preserving the same crystalline appearance
as before, and lose about 20 per cent. of weight. Ten grains of the
crystals of sulphuretted sulphite, when treated with liquid oxymuriate
of lime to saturation, require 2+ grains of oxygen and yield 8 grains
of sulphate of barytes, together with an excess of sulphuric acid which
with muriate of barytes gives 8 grains more of sulphate. From these
facts it may be concluded that the sulphuretted sulphite consists of
one atom barytes, 2 sulphur, 2 oxygen, and 2 water, and that 4 more of
oxygen are derived from the oxymuriatic acid to convert the sulphurous
oxide into sulphuric acid. The sulphuretted sulphite of barytes seems
to pass into sulphate by length of time. The weight of the atom of
quadrisulphuret of barytes is 124; the compound in mass consists of 100
barytes and 82 sulphur.
_Hydrosulphuret of barytes._ This compound may be formed in the same
manner as that of lime, and is found to have similar properties. The
proportions for mutual saturation are, I find, as in the case of lime,
15 sulphuretted hydrogen to 68 barytes by weight, or one atom of each.
4. _Sulphurets of strontites._
The protosulphuret and quadrisulphuret of strontites may be formed
in the same way as those of lime and barytes. From a few experiments
made on these compounds I have not observed any remarkable feature of
distinction between them and the corresponding ones of the other earths.
_Hydrosulphuret of strontites._ This compound may be formed in the same
way as that of lime; the proportions to produce mutual saturation will
be 1 atom of each, or 15 parts sulphuretted hydrogen, to 46 strontites
by weight.
5, 6, 7, 8, _and_ 9. _Sulphurets of alumine, silex, yttria, glucine_,
and _zircone_.
I made several unsuccessful attempts to combine alumine and sulphur.
When alumine and sulphur mixed together are heated, the sulphur
sublimes chiefly, and leaves the alumine with traces of sulphate of
alumine.
In the humid way, recently precipitated and moist alumine mixed
with sulphur and boiled in water, give a liquid with some traces of
sulphuric acid, but no sulphuret of alumine; the sulphur and alumine
both subside, and when the sulphur is either sublimed or burnt, the
alumine remains much the same as at first. When a solution of alum
is treated with sulphuret of lime, sulphate of lime is precipitated
along with the greatest part of the sulphur in a kind of feeble union
rather than mechanical mixture, it should seem; the alumine is at the
same time precipitated probably in mechanical mixture; there remain in
solution a little sulphuret of potash and sulphate of lime.
_Sulphuret of silex_ is not known, I apprehend, to exist. When
silicated potash in solution is treated with quadrisulphuret of lime, a
copious dark brown or black precipitate instantly appears; the liquid
when filtered is of a pale yellow colour, and seems to contain about
one half of the sulphur and potash, whilst the other half is thrown
down in union with the lime and silex. This black compound is probably
1 atom of lime, 2 of sulphur, 2 of potash, and 2 of silex; it cannot
therefore be accounted a sulphuret of silex.
_Sulphurets of yttria_, _glucine_, and _zircone_, are as yet, I
presume, unknown.
10. _Sulphurets of potash._
Potash has a strong affinity for sulphur and unites with it in various
ways and proportions.
1st. _In the dry way by heat._ When either pure potash or the carbonate
(salt of tartar) is heated in a covered crucible with sulphur, a
chemical union of the two principles takes place. Eight parts of dried
hydrate of potash unite to six or seven of sulphur: a heat of 4 or
500° of Fahrenheit is convenient for the purpose. If the carbonate of
potash be used, then 12 parts dried in a low red heat will require
8 of sulphur for their complete saturation: in this case a higher
degree of heat is requisite in order to expel the carbonic acid; a
low red heat seems sufficient from my trials. When the heat does not
exceed 3 or 400° a partial union takes place; the carbonate of potash,
without losing any acid, unites to ⅓ of the sulphur, and the rest of
the sulphur remains uncombined; when intermediate degrees of heat are
used, I have found the result a mixture of the pure sulphuret and the
carbonated sulphuret, with more or less of sulphate of potash. A high
degree of heat and exposure to the atmosphere produces a sulphate
instead of a sulphuret. The sulphurets obtained this way are in fusion
till poured out and cooled; they are of a _liver_ colour, and hence
were formerly called _livers_ of sulphur. They are largely soluble in
water, and give a brownish yellow solution.
2d. _In the humid way by solution._ Pure caustic potash in solution
when boiled with sulphur dissolves it largely, 42 parts of real potash
being saturated with about 56 of sulphur. If we boil a solution
of carbonate of potash with sulphur, for an hour or more, a brown
liquor is obtained, which consists of 60 parts carbonate of potash
and 14 sulphur in chemical union.--It has already been observed
that a trisulphuret of potash may be obtained by double affinity
from quadrisulphuret of lime and carbonate of potash, together with
sulphuretted carbonate of lime.
From what has been stated we may infer at least three varieties in the
compounds of sulphur and potash, viz.
1st. _Sulphuretted carbonate of potash._ This consists of 1 atom
carbonate of potash (61) with 1 atom of sulphur (14). Its analysis
may be effected as follows: the quantity of carbonic acid may be
found by the lime water necessary to saturate it; the potash may be
known from the quantity previously entering into the mixture; and
the sulphur in the same manner, or from the quantity of sulphuretted
carbonate of lead that it forms.--The sulphur may also be known, from
the quantity of oxygen it requires by means of oxymuriate of lime to
produce saturation; this I find to take place when the oxygen is half
the weight of the sulphur, or one atom to one of sulphur; it soon
happens, that one atom of sulphur deprives two others of their oxygen,
and sulphuric acid is formed whilst the other two atoms of sulphur join
the carbonate of lime and are precipitated along with it. As it may
frequently happen, that the sulphuretted carbonate is mixed with common
carbonate of potash, the proportions may be found by means of nitrate
of lead, which being cautiously dropped into the solution, lets fall
first the brown sulphuretted carbonate of lead, and then the common
white carbonate of lead.
The sulphuretted carbonate of potash absorbs oxygen and precipitates
metals much the same in appearance as the other sulphurets; but
essential distinctions are observable, some of which are noticed above,
and others will appear in the sequel.
2 and 3. The _trisulphuret_ and _quadrisulphuret_ of potash so nearly
resemble the quadrisulphuret of lime in their properties, as not to
require any additional remarks.
_Hydrosulphuret of potash._ This combination, when duly proportioned,
consists of 15 parts sulphuretted hydrogen, and 42 potash by weight,
or one atom of each. It may be formed by directly uniting the two
elements, or by decomposing hydrosulphuret of lime by carbonate of
potash. Its properties agree with those of the other hydrosulphurets.
11. _Sulphurets of soda._
I have repeated most of the experiments on the sulphurization of potash
with soda, and have not found anyone remarkable feature of distinction,
besides those which arise from the weights of the atoms.
1. _Sulphuretted carbonate of soda_ consists of 1 atom of carbonate of
soda united to 1 of sulphur; or of 47 parts of the former and 14 of the
latter.
2. _Trisulphuret of soda_ consists of 1 atom soda (28) and 3 of sulphur
(42).
3. _Quadrisulphuret of soda_ consists of 1 atom soda (28) and 4 atoms
of sulphur (56).
_Hydrosulphuret of soda._ This compound consists of one atom of each
of the elements, or 15 sulphuretted hydrogen, and 28 soda. In other
respects it agrees with hydrosulphuret of potash.
12. _Sulphuret of ammonia._
The best way which I have found of procuring sulphuret of ammonia,
is to treat quadrisulphuret of lime with the carbonate of ammonia as
long as any precipitate takes place; the precipitate is sulphuretted
carbonate of lime, 3 atoms of sulphur to 1 of carbonate of lime. The
liquid is of a pale yellow, and contains ammonia and sulphur united
in the ratio of 1 atom (of 6) to 1 of sulphur: it may therefore be
denominated the protosulphuret of ammonia.
The carbonate of ammonia is best procured by heating the common
subcarbonate of ammonia, first pulverized, in a temperature of 100°
for half an hour, or exposing it for a few days to the atmosphere.
What remains of the salt is almost without smell; it should consist of
19 parts acid, 6 ammonia, and 8 water nearly: the ammonia is usually
however a small degree in excess.
_Hydrosulphuret of ammonia._ This compound may be formed in the
dry state by combining the two gases of sulphuretted hydrogen and
ammonia over mercury; it is of a white crystalline appearance, and
very soluble in water, and forms a fuming liquor of a very pungent
smell. It may also be obtained by passing sulphuretted hydrogen into a
vessel containing liquid ammonia. I find about 110 or 120 measures of
sulphuretted hydrogen require 100 of ammoniacal gas. Hence it is 1 atom
of sulphuretted hydrogen (15), that unites to 1 of ammonia (6).
13. _Sulphurets of gold._
There exist at least two sulphurets of gold, the nature and proportions
of which are easily ascertained; though several authors assert that
no combinations of gold and sulphur are known; amongst these it is
surprizing to find Proust: indeed most of the others have probably been
led by his authority to adopt the opinion without examination. It is
not very easy to account for his deception.
Obercampf, in the Annal. de Chimie, tom. 80. 1811, is the first author
I have seen who distinctly maintains the existence of one or more
sulphurets of gold, though it seems to have been admitted previously
by Bucholz. The last author finds 82 gold unite to 18 sulphur, and the
former 80 to 20 nearly.
_Protosulphuret of gold._ This compound is formed whenever a solution
of muriate of gold is agitated with sulphuretted hydrogen gas, or with
the same united to a base, as lime or alkali. A black or deep brown
powder falls down by the addition of more gas, till the whole of the
gold is precipitated. The oxide of gold loses one atom of oxygen, and
receives one of sulphur in its place, whilst the hydrogen of the gas
is carried off along with the oxygen of the oxide. The sulphuret dried
and heated, burns with a blue flame, leaving the gold nearly pure. This
compound consists, I find, of 81 gold and 19 sulphur per cent.; or 100
gold unite to 23 sulphur.
_Trisulphuret of gold._ This compound is obtained whenever
quadrisulphuret of lime is gradually dropped into a solution of muriate
of gold; it is a black powder, not quite so deep as the former. Care
must be taken to saturate the excess of acid previously by lime water,
to prevent any uncombined sulphur precipitating. Trisulphuret of gold
being heated, burns with a blue flame, and leaves the gold nearly pure;
it loses from 10 to 45 per cent. by the process. It is constituted of
1 atom gold and 3 sulphur, or 60 gold and 42 sulphur, nearly; or 100
gold combine with 70 sulphur.
From several experiments I am led to conclude that each atom of oxide
of gold takes 3 of sulphur, and parts with 1 of oxygen to the remaining
sulphur; thus a trisulphuret of gold is formed, and an oxide of
sulphur; the liquid, being afterwards treated with oxymuriate of lime,
is found to require twice the oxygen of the gold for its saturation,
when a corresponding portion of sulphuric acid may be precipitated by
muriate of barytes.
14. _Sulphuret of platina._
Sulphur may be combined with platina in several ways, and probably
in different proportions; but the combination is not so easily
and elegantly effected as with many other metals, and hence some
uncertainty still remains on the subject.
When a salt of platina is treated with sulphuret or hydrosulphuret of
lime, or sulphuretted hydrogen water, the liquid slowly and gradually
grows dark brown and finally black; after agitation and standing a
few hours, the liquid is semitransparent, and a black flocculent
precipitate appears at the bottom. Sometimes after violent agitation,
the liquid on standing a few minutes becomes a transparent brown,
but soon grows turbid again. In the course of a few days, and by
occasional agitation, the liquid finally becomes clear and nearly free
from platina, and the precipitate may be collected on a filter and
dried. This circumstance of slow and indolent precipitation cannot be
prevented by any means I have found, such as saturating the excess of
acid, &c.
Mr. Edmund Davy, in the 40th VOL. of the Philos. Magazine, has given us
the results of his experiments and observations on the sulphurets of
platina, containing some useful and original information. He combines
platina with sulphur by heating the ammonia-muriate of platina with
sulphur; also by heating platina and sulphur in an exhausted tube;
and by sending sulphuretted hydrogen gas or water into a solution of
muriate of platina; this precipitate he calls hydrosulphuret of platina.
He has just noticed the precipitate formed by sulphuret of potash with
muriate of platina, but gives no opinion as to the compound obtained
this way. He determines three sulphurets, namely,
Subsulphuret, 100 platina + 19 sulphur
Sulphuret, 100 ---- + 28.2 ----
Supersulphuret, 100 ---- + 38.8 ----
I have obtained the sulphuret of platina in five ways: 1st. By pouring
sulphuret of lime solution by degrees into muriate of platina, and
agitating the mixture well or till it grew black each time; after
digesting for some days, repeated filtering, and drying, a black
powder is obtained: 2. Instead of sulphuret, hydrosulphuret of lime
was used; the precipitate was obtained under like circumstances: 3d.
Sulphuretted hydrogen water was used, and the precipitate obtained
in like manner: 4th. Ten grains of ammonia-muriate of platina were
treated with sulphuretted hydrogen water; by continued agitation the
yellow powder disappeared, the liquid looked uniformly black, and at
length a precipitate was formed; by repeated filtration and addition of
sulphuretted hydrogen water, the whole of the platina was thrown down,
and the liquid remained colourless; but it is difficult to discover the
exact quantity of sulphuretted hydrogen requisite for any weight of the
ammonia-muriate from the tediousness of the operation; 6 grains of well
dried black powder were obtained, besides perhaps 1 grain of loss on
the filters: 5th. Ammonia-muriate of platina was heated in a covered
crucible along with sulphur till it was judged that all the uncombined
sulphur was sublimed or dissipated.
All these sulphurets appear to me to be the same when dried in a
moderate heat. When exposed to a low red heat they yield water and
sulphurous acid, and lose about ⅖ of their weight.
The subject however, requires further investigation. The sulphurets
of platina appear of a complex nature, and the proportions of their
elements are not yet determined with precision.
15. _Sulphurets of silver._
Silver combines with sulphur in two different proportions, and forms
two sulphurets, both of them black or dark brown.
1. _Protosulphuret of silver._ This may be formed either by the dry
or humid way: if thin lamina of silver be heated with sulphur, they
combine and form this sulphuret; a higher degree of heat expels the
sulphur again. It is formed too by passing sulphuretted hydrogen or a
hydrosulphuret through a solution of silver in nitric or other acids.
The atom of silver unites with that of sulphur, whilst the hydrogen
unites with the oxygen. Of course this compound is composed of 90
silver, and 14 sulphur, and the atom weighs 104; or 100 silver unite
with 15.5 sulphur. Klaproth finds 100 silver and 17.6 sulphur; Wenzel
100 silver, and 14.7 sulphur; Berzelius 100 silver, and 14.9 sulphur;
and Vauquelin 100 silver, and 14 sulphur.
_Trisulphuret of silver._ This compound is formed whenever neutral
nitrate of silver is dropped into a solution of quadrisulphuret of lime
or alkali. Mutual saturation seems to take place when eight atoms of
nitrate meet with seven of quadrisulphuret. Trisulphuret of silver is
constituted of 90 silver, and 42 sulphur; or of 100 silver, and 46.5
sulphur. Its colour is not so dark as that of the protosulphuret. The
residuary liquid contains sulphurous acid, which is easily converted
into sulphuric by the addition of a portion of lime; and the quantity
of acid may then be determined by muriate of barytes.
16. _Sulphurets of mercury._
Mercury combines readily with sulphur both in the dry and humid way,
and that in several proportions, as under: namely,
1. _Protosulphuret of mercury._ This is most conveniently formed
by passing sulphuretted hydrogen gas through a solution of the
protonitrate of mercury, or by pouring hydrosulphuret of lime, &c.
into the same solution. The protosulphuret falls down in the state of
a black powder. It consists of 167 mercury, and 14 sulphur; or of 100
mercury, and 8.4 sulphur. The theory of its formation is the same as
that of silver.
2. _Deutosulphuret of mercury._ This is formed in the humid way
whenever sulphuretted hydrogen or a hydrosulphuret in excess is mixed
with the deutonitrate or deutomuriate of mercury (corrosive sublimate);
a brown powder is precipitated which is the deutosulphuret. If the
sulphuretted hydrogen be only one half what is sufficient to form
the deutosulphuret, then we obtain no sulphuret, but instead of it a
protonitrate or protomuriate, as was first intimated by Proust; I find
however, the atom of sulphur adheres to the atom of salt, and that it
is therefore a sulphuretted protonitrate or muriate, whilst 1 atom of
oxygen unites with the hydrogen. The brown precipitate does not change
to yellow, orange, and red, when left undisturbed for a few days, in
my experience; though this is stated to have been observed by Mr.
Accum. Notwithstanding the difference in colour, this deutosulphuret
must be the same nearly as the cinnabar and vermillion of commerce, if
Proust and others are right in their analysis of these articles. The
combination of the elements of sulphur and mercury when intended to
form cinnabar is made in the dry way by trituration, and a moderate
heat: the compound, at first black, is afterwards sublimed by a duly
regulated heat and becomes red. This compound must consist of 100
mercury and 17 sulphur nearly.
3. _Quadrisulphuret of mercury._ This compound is formed when a
solution of protonitrate of mercury is treated with quadrisulphuret of
lime, added by degrees till the clear liquid no longer gives a dark
coloured precipitate. The oxygen of the mercurial salt unites, it
should seem, to part of the sulphur, and forms sulphuric acid, whilst
the rest of the sulphur unites to the mercury. This sulphuret is a
black or dark brown powder, and when heated burns with a blue flame. It
consists of 100 mercury, and 33 or 34 sulphur, as appears to me from
the synthesis.
When the insoluble muriate of mercury (calomel), is triturated in
liquid quadrisulphuret of lime, it is soon decomposed; quadrisulphuret
of mercury is formed, with muriate of lime and sulphuric or sulphurous
acid.
When the soluble muriate (corrosive sublimate), has quadrisulphuret of
lime dropped into it by degrees; at first a yellowish white precipitate
is obtained, which increases till it is one half saturated; after
this, by continually adding more sulphuret, the precipitate grows
darker, and ends in being quite black. It is at least as high as
quadrisulphuret. Much sulphurous acid is found in the liquid.
The deutonitrate of mercury, produces a copious yellow precipitate with
quadrisulphuret of lime. Exposed to the sun, it grows black in a few
minutes on the light side, but continues yellow on the opposite side
of the jar; at the same time, an effervescence and disengagement of
oxygen gas are observed. Finally, the precipitate becomes the common
quadrisulphuret, and the liquid contains sulphurous and sulphuric acids.
The recently precipitated and washed oxides of mercury act upon
quadrisulphuret of lime. The black oxide seems to take 4 atoms of
sulphur and part with its oxygen to another portion of sulphur; but
the red oxide becomes light brown and retains the colour when dried.
It seems to take the same sulphur as the black, but whether it retains
any of the oxygen, I have not ascertained. The action is more slow
than when the nitrates are used, and more quadrisulphuret of lime is
expedient.
Mercury and sulphur combine in the dry way by trituration and by heat,
forming a black powder; but the species of compounds and quantities of
the ingredients combining in this mode, have not been ascertained.
17. _Sulphuret of palladium._
Berzelius exposed 15 grains of palladium filings mixed with as much
sulphur to a heat sufficient to expel the uncombined sulphur. The
increase of weight was 28 per cent. upon the palladium: when exposed
afresh with sulphur to heat, no addition was made to the weight.
Vauquelin heated 100 parts of the triple salt of palladium with an
equal weight of sulphur, and obtained 52 parts of a blueish white
sulphuret, very hard, and when broken exhibiting brilliant plates in
its fracture. He had previously found that 100 salt contained 40 to 42
of metal: hence 100 metal combined with from 24 to 30 of sulphur. This
agrees nearly with the above results of Berzelius. A very high degree
of heat expels the sulphur and oxidizes the metal; but a more moderate
heat leaves the palladium of a silver white colour and nearly pure.
According to this the atom of protosulphuret of palladium must consist
of 50 palladium, and 14 sulphur.
18. _Sulphuret of rhodium._
Vauquelin found that 4 parts of the ammonia-muriate of rhodium
(containing 28 or 29 per cent. of metal) being mixed with an equal
weight of sulphur, and heated, a blueish white button was obtained,
weighing 1.4. Hence 100 metal seem to take 25 of sulphur; and allowing
this to be the protosulphuret of rhodium, the atom must consist of one
rhodium 56, and one sulphur 14, making the whole weight 70.
19. _Sulphuret of iridium._
According to Vauquelin, 100 parts of the ammonia-muriate of iridium
heated with as much sulphur, yield 60 parts of black powder resembling
the other metallic sulphurets; but 100 parts of the salt were found to
yield from 42 to 45 of metal. Now supposing the last number the most
correct, it should seem that 3 parts iridium take 1 sulphur, or 100
take 33⅓. This being supposed the protosulphuret, the atom of iridium
must be 42, and that of the sulphuret 56.
20. _Sulphuret of osmium._
It is as yet unknown whether any combination of sulphur and osmium
exists.
21. _Sulphurets of copper._
Copper readily unites with sulphur both in the dry and humid way. When
3 parts of copper filings are mixed with 1 part of sulphur, and heat
applied, a brilliant combustion ensues, which indicates the union of
the two bodies. Copper leaf burns in the fumes of sulphur, as Berzelius
has observed, with great brilliancy.
The protosulphuret of copper obtained by these similar methods, when
pulverized, is black or dark coloured; it has been analyzed by various
authors, who nearly agree in their results. Proust finds 100 copper
unite with 28 sulphur; Wenzel, 100 copper and 25 sulphur; Vauquelin,
100 copper and 27 sulphur; and Berzelius 100 copper and 25 sulphur.
If the atom of copper be 56, and that of sulphur 14, the atom of
protosulphuret of copper will be 70; which gives just 100 copper and 25
sulphur.
The protosulphuret may also be formed in the humid way, by sending
sulphuretted hydrogen gas or a hydrosulphuret into a solution of
protomuriate of copper, or amongst the recently precipitated protoxide
of copper.
_Deutosulphuret of copper._ This compound is formed whenever
sulphuretted hydrogen gas or a hydrosulphuret is sent into a solution
of salt containing the deutoxide, or into the deutoxide just
precipitated from any acid. It is a dark brown powder not differing
much in appearance from the protosulphuret. It consists of 100 copper
and 50 sulphur; the weight of the atom is 84.
_Quadrisulphuret of copper._ This compound is formed by mixing
quadrisulphuret of lime with a salt of the deutoxide of copper, and
diluting the solution. A light brown precipitate falls immediately,
which is the quadrisulphuret of copper. It burns with a blue flame,
and leaves the protosulphuret. The atom consists of 56 copper and 56
sulphur, or weighs 112; and hence the sulphuret consists of equal parts
copper and sulphur.
The blue hydrate of copper recently precipitated from a salt of copper
and washed, acts upon quadrisulphuret of lime; the results, according
to my experience, is quadrisulphuret of copper, and the oxygen unites
with the sulphur remaining in the liquor.
22. _Sulphurets of iron._
Sulphur may be united to iron either by the dry or humid way, and that
in various proportions.
_Protosulphuret of iron._ This compound may be formed by passing a
hydrosulphuret into a solution of the green oxide in any acid. It
is a black powder. It may also be formed by rubbing a highly heated
bar of iron with a roll of sulphur; the two unite in a fluid form
and soon congeal into a brownish black mass. It is too a natural
production, though not very common; excellent analyses of it, as well
as of the common pyrites, were some time ago given by Mr. Hatchett.
(See Nicholson’s Journ. VOL. 10.) The protosulphuret is magnetic in a
considerable degree; it is soluble in acids, and yields sulphuretted
hydrogen. It is proper to notice that the sulphuret of iron is not
precipitated from solutions by sulphuretted hydrogen simply or without
a base. According to Mr. Hatchett this sulphuret consists of 100
iron, and 57 sulphur, which corresponds with 1 atom iron 25, and 1 of
sulphur, 14, nearly.
_Deutosulphuret of iron._ This is a natural production frequently met
with, and in various forms; it is called pyrites, or iron pyrites; it
is a yellowish mineral and often appears when broken, of a radiated
texture, but sometimes it is crystallized in cubes or dodecahedrons.
Acids have little effect upon it, except the nitric, which when
diluted attacks both the sulphur and iron; much nitrous gas is
produced, the iron is dissolved, and the sulphur chiefly converted into
sulphuric acid. This sulphuret consists, according to Proust, of 100
iron, and 90 sulphur, and with this Bucholz recently agrees (Nichols.
27--356); but Hatchett makes it 100 iron, and 112 sulphur. From an
experiment of my own on the radiated pyrites, I found nearly equal
parts of iron and sulphur. One atom of iron (25,) and two of sulphur
(28,) would give 100 to 112; but if the atom of sulphur be only 13, it
gives 100 iron to 104 sulphur. Mr. Hatchett unfortunately calculating
the proportions of the ingredients _in_ 100 sulphuret, instead of _on_
100 iron, did not notice that the sulphur in the common pyrites is just
double of that in the magnetic pyrites.
_Quinsulphuret of iron._ This combination consisting of 5 atoms of
sulphur with 1 of iron, is formed by mixing a solution of green
sulphate of iron with quadrisulphuret of lime in due proportion. I
found 50 measures sulphate 1.168 saturate 310 of 1.05 sulphuret diluted
so as to become 6 oz.; this yielded 14 grs. dried sulphuret of iron =
3.6 iron, known to be in the sulphate, and 10.4 sulphur; the liquid
contained 2+ sulphur combined with the lime and oxygen of the oxide;
for it took 2.3 oxygen by means of oxymuriate of lime to convert the
sulphur into sulphuric acid together with 1+ from the oxide, making 3+
oxygen, which unites to 2+ sulphur to constitute 5+ sulphuric acid; and
this quantity of acid was found to exist by muriate of barytes together
with five more brought in by the sulphate of iron. This sulphuret is
a yellowish brown powder; it readily exhales sulphur by heat and is
reduced to the protosulphuret; but in the open air it burns with a
blue flame and leaves the protosulphuret partially, as I apprehend,
oxidized. The theory of the formation of quinsulphuret seems to be
this: 3 atoms of quadrisulphuret of lime are requisite to saturate 2
of sulphate of iron; the 2 atoms of sulphuric acid seize 2 of lime,
three fourths of the sulphur unite to the iron, and one fourth to its
oxygen, forming 2 atoms of oxide of sulphur, which attack the 3d atom
of sulphuret and decompose it, giving its sulphur to the iron, and
neutralizing the lime (for the liquid is found neutral). In this way
10 atoms of sulphur are united to 2 of iron, and 2 of sulphur to 2 of
oxygen, with one of lime, which last compound remains in solution, and
the oxide of sulphur may be converted into sulphuric acid immediately
by the application of oxymuriate of lime.
It is remarkable that neither the green nor the yellow oxides of
iron, even when recently precipitated and not dried, seems capable of
decomposing quadrisulphuret of lime.
It is probable that trisulphuret and quadrisulphuret of iron may be
formed; but I have not ascertained the truth of this opinion.
23. _Sulphurets of nickel._
_Protosulphuret._ According to Proust, nickel unites to sulphur by
heat, so that 100 take 46 or 48; the sulphuret is of the colour of
common pyrites. (Journ. de Physique, 63 and 80). According to Mr. Ed.
Davy 100 nickel take 54 sulphur. By saturating a solution of nitrate
of nickel with hydrosulphuret of lime I obtained 40 grains from 33
protoxide or 26 metal. This was evidently the protosulphuret; it was a
fine black powder, and consists of 100 metal and 54 sulphur.
_Quinsulphuret._ This compound may be obtained from nitrate of nickel
and quadrisulphuret of lime, in the same manner as that of iron. It is
a deep black powder, and consists of 100 nickel, and 215 sulphur. By
exposure to heat, the greatest part of the sulphur burns off, and the
rest may be expelled by an increase of temperature.
Probably intermediate sulphurets may be formed; but I have not pursued
the investigation.
24. _Sulphurets of tin._
Sulphur and tin unite both in the dry and humid way, and in various
proportions.
_Protosulphuret._ This may be readily formed in the dry way as follows;
let 100 grains of tin be fused in a small iron ladle and heated to 6 or
8 hundred degrees Fahrenheit; let then small pieces of sulphur of 10
or 20 grains be successively dropped into the fused metal: a copious
blue flame will instantly arise each time, and a glowing heat will take
place, when the sulphur and tin are in contact; as soon as this ceases,
another fragment of sulphur must be dropped in, and this two or three
times repeated, heating it at last to a perfect red; the mass may then
be taken out and pounded in a mortar; a great part of it will be a
pulverulent powder, but some portions of malleable metal will still be
mixed with it, which may be separated by a sieve. This must be again
heated and treated with sulphur as before, and the whole mass will be
converted to a sulphuret. I find that 100 parts of tin become in this
way 127 grains; which is the due proportion of 52 tin and 14 sulphur,
so that no loss of tin is sustained by the process when duly managed.
According to Wenzel, 100 tin take 18 sulphur; Bergman, 25; Pelletier,
15 to 20; Proust, 20; but Dr. John Davy and Berzelius find nearly 27 as
above stated, and I have no doubt it is near the truth.
The protosulphuret of tin is a dark grey shining powder, with a streak
like molybdena or plumbago; it is not much different in colour and
appearance from native sulphuret of antimony, only less blue. It is
soluble in muriatic acid by heat, and yields sulphuretted hydrogen and
protomuriate of tin.
_Deutosulphuret._ This compound is better known than the former: it may
be formed in various ways; one is by heating a mixture of deutoxide
of tin and sulphur in a retort almost to a red heat; sulphur sublimes
and sulphurous acid is disengaged, and there remains a yellow, light
shining, flaky mass at the bottom of the retort which is the sulphuret.
It was formerly called _aurum musivum_ or mosaic gold. Pelletier and
Proust were of opinion that this product is a sulphuretted oxide of
tin; but Dr. John Davy and Berzelius have rendered it more probable
that it is a true deutosulphuret, consisting of 100 tin and 54 sulphur.
It is insoluble in muriatic or nitric acid, but slowly soluble by the
compound of the two acids; it is also soluble in potash by heat.
By exposing it to a bright red heat, it burns with a blue flame and
leaves a yellowish powder which dues not seem to differ much from
protosulphuret.
Berzelius distilled a mixture of protosulphuret and sulphur at a low
red heat, and obtained a mass of a yellow grey colour and metallic
lustre, which consisted of 100 tin, and 14 sulphur, which is just the
mean sulphur between the other two. This would seem to indicate that a
compound of the two sulphurets, 1 atom to 1, is capable of being formed.
_Hydrosulphuret of tin_ minor. This compound is formed according
to Proust, when sulphuretted hydrogen, or an alkaline or earthy
hydrosulphuret is passed into a solution of protomuriate of tin. It
is of a brown or dark coffee colour when precipitated, and black
when dried. By heat it yields water and protosulphuret. From some
experiments I am inclined to believe, that it is formed of 1 atom
protosulphuret and 1 of water: or, which is the same, 1 atom protoxide
of tin and 1 of sulphuretted hydrogen. If this be right it may be said
to be a compound of 100 tin, 27 sulphur and 15 water.
_Hydrosulphuret of tin_ major. This name is given by Proust to
the yellow compound thrown down by sulphuretted hydrogen or by
hydrosulphurets from solutions of the deutoxide of tin. When dried
moderately, the precipitate is of a dull yellow colour, and vitreous
fracture, but I find it is almost black, dried in a heat of 150° or
upwards. By moderate heat it yields water, sulphurous acid, sulphur,
and the residue is deutosulphuret of tin according to Proust. I heated
4 parts of the above previously dried so as to become a black vitreous
powder; it burned feebly with a blue flame, and after being made
moderately red, left nearly 3 parts exactly resembling the artificial
protosulphuret. I believe the dried precipitate will be found to be
constituted of 1 atom tin, 2 sulphur and 1 water; that is, 100 tin, 54
sulphur and 15 water = 169 by weight; and that it loses 27 sulphur and
15 water by a red heat, which reduces the weight just one fourth.
_Quinsulphuret of tin._ This is obtained in the humid way, by first
precipitating the oxide, and then putting quadrisulphuret of lime or
potash to the liquid containing the precipitate, till the liquid after
agitation and subsidence of the precipitate continues of a yellowish
colour. I found that 31 measures of protomuriate of tin of 1.377
= 7 grains acid, 7.5 tin and 1 oxygen, precipitated by 10 oz. lime
water, required 450 measures of 1.40 sulphuret of lime, containing 16
sulphur and 7.2 lime, for their saturation. The residuary liquid was
nearly colourless, and the precipitate dried in an oven of 100° or
more, for 10 hours, weighed 17 grains besides loss in the operation.
It was a yellow, vitreous mass, and when pulverized and heated, burned
with a blue flame, and lost 40 per cent. in weight; the residue was a
yellow grey colour, and seemed to be like the intermediate sulphuret
of Berzelius; it would not give sulphuretted hydrogen by hot muriatic
acid. Now if 52 (1 atom tin) ∶ 70 (5 atoms sulphur) ∷ 7.5 tin ∶ 10+
sulphur; hence the sulphuret should have weighed 17.5 grains, which was
the observed weight, allowing ½ grain for loss. According to this, 100
tin combine with 135 sulphur, and when burnt, the 235 are reduced to
140, the weight observed by Berzelius in the instance alluded to. The
liquid required 5 grains of oxygen from oxymuriate of lime, to convert
the sulphur into sulphuric acid, and the weight of this acid, found by
muriate of barytes, was 11 grains, indicating 4.4 sulphur. It may be
observed that the 4.4 grains, and 10 grains, do not make up the whole
(16) of the sulphuret of lime; but the reason I apprehend was, that the
quadrisulphuret was old, and did not contain the full share of sulphur,
it being usual for a small part to fall by time.
The deutomuriate of tin, precipitating the oxide in like manner,
yielded a sulphuret rather lighter yellow than the above; about 10
tin gave 25 grains of sulphuret dried in a temperature of 80 to 100°.
This compound still contained water, and I suspect it will be found
constituted of 1 atom tin, 5 sulphur, and 2 water.
25. _Sulphurets of lead._
Lead combines with sulphur in various proportions, some of which are
natural productions of great purity.
_Protosulphuret._ This is a natural production which is called galena;
it is of lead grey colour and metallic appearance, and is found both
in masses and crystallized; its sp. gr. is about 7.5. It may be
formed artificially by heating lead or its oxide with sulphur; also
by treating a solution of lead with sulphuretted hydrogen or with a
hydrosulphuret. Authors are well agreed as to the proportions of the
ingredients; 100 lead combine with from 15 to 16 sulphur. That is, 90
lead with 14 sulphur; or 1 atom of lead with 1 of sulphur.
_Deutosulphuret._ Dr. Thomson mentions a natural production or species
of galena which contains twice the quantity of sulphur of that above.
I have reason to believe that this compound is easily formed in the
humid way, by treating the precipitated oxide with the due quantity of
quadrisulphuret of lime.
_Trisulphuret_ and _quadrisulphuret_. These compounds, I find, may
be formed by means of quadrisulphuret of lime or potash. When a
solution of any salt of lead or the recently precipitated and moist
oxide, is treated with the requisite quantity of quadrisulphuret of
lime, a combination consisting of 1 atom of lead and 3 of sulphur is
formed. It is a black powder not differing much in appearance from the
protosulphuret; it is lighter and more spongy. It consists of 100 lead
and 46 or 47 sulphur. The due proportions of the elements to form the
above compound are, lead 100 parts in solution, and sulphur, 62 parts;
¼ of the sulphur is retained by the lime, and may be converted into
sulphuric acid instantly by the addition of as much oxymuriate of lime
as contains oxygen equal in weight to the sulphur, as it has already
as much oxygen as converts it into sulphurous oxide, derived from the
oxide of lead.
Quadrisulphuret of lead is to be obtained in the same way; only we must
have an excess of the sulphuret of lime, or more than 80 sulphur for
100 lead in solution, as ⅕ part of the sulphur at least is retained
by the lime. The quadrisulphuret is a black powder like the others;
it burns with a blue flame and loses nearly 40 per cent., the residue
being still black. It consists of 100 lead and 62 sulphur.
I have not ascertained whether any higher sulphuret of lead is capable
of being formed this way.
It has been already noticed (page 109), that a beautiful white, silvery
sulphuretted sulphite of lead is formed and gradually precipitated,
when nitrate of lead is dropped into a solution where as much black
quadrisulphuret of lead has been just thrown down as the sulphuret of
lime can form.
26. _Sulphurets of zinc._
Zinc and sulphur are scarcely to be united directly by heat; but by
heating the oxide of zinc and sulphur together, a combination is
effected; part of the sulphur carries off the oxygen in sulphurous
acid, and part combines with the zinc. Mineralogists give the name of
_blende_ to a mineral which is chiefly the protosulphuret of zinc: its
colour is yellowish, brown, or black almost like galena: its specific
gravity is usually 3.9 or 4.
_Protosulphuret._ The above artificial compound, or the mineral, may
be taken as examples of the union of 1 atom zinc and 1 sulphur. But
the most correct and convenient way of forming it for the purpose of
chemical investigation is, to drop a given portion of some salt of zinc
into a dilute hydrosulphuret. A white precipitate falls, which when
dried becomes a dark cream colour. It is found to consist of 2 parts
zinc and 1 of sulphur nearly; that is, of 29 parts zinc and 14 sulphur.
_Deutosulphuret_, _trisulphuret_, &c. of zinc. These combinations
may be made, up to the 5th or _quinsulphuret_, in the humid way by
quadrisulphuret of lime, &c. The oxide may be first precipitated by
lime water, or not, as we please, and then treated with quadrisulphuret
according to the degree of sulphuration required. I found 100 measures
of 1.29 nitrate of zinc with 2500 of 1.026 sulphuret of lime yield 40
grs. dry sulphuret zinc, of a yellowish white colour; the liquid was
found to retain 13 or 14 grains of sulphur, by converting it into
sulphuric acid by means of oxymuriate of lime. The nitrate contained
11½ zinc and 2.8 oxygen; so that about 28 sulphur had combined with
the zinc, and about 14 remained in solution, or ⅓ of the whole, as has
been already explained. By proportion, if 11½ ∶ 28 ∷ 29 ∶ 70; or 1 atom
of zinc (29) combines with 5 atoms of sulphur (70). The intermediate
combinations I have not particularly examined; they do not differ
much in appearance from the one just described; they burn blue and
are reduced by it to the protosulphuret; and they give sulphuretted
hydrogen by muriatic acid.
27 _and_ 28. _Sulphurets of potassium and sodium._
According to Davy and Gay Lussac, potassium and sodium unite with
sulphur by heat with vivid combustion. The compounds appear to be
protosulphurets, that of potash being nearly as 35 potassium to 14
sulphur, and that of sodium as 21 sodium to 14 sulphur. When potassium
and sodium are heated along with sulphuretted hydrogen, an union
likewise takes place; two atoms of gas unite to one of the metals,
except that 1 atom of hydrogen is liberated, corresponding of course
in quantity to that liberated by treating them with water. When the
compound thus formed is treated with muriatic or sulphuric acid,
the same quantity of sulphuretted hydrogen nearly is liberated that
was originally combined. So that the compound may be regarded as
sulphuretted hydrogen united to the protosulphurets. The colour of
these sulphurets varies from grey to yellow or reddish.
29. _Sulphurets of bismuth._
_Protosulphuret._ Bismuth combines with sulphur by heat, in the manner
already described in the account of tin sulphurets. I found 100 parts
bismuth in this way combine with 22 sulphur after 4 operations: this is
therefore the protosulphuret or 1 atom bismuth (62) with 1 of sulphur
(14). It may also be formed by substituting the oxide of bismuth for
the metal. It has a dark brown or black metallic appearance, much like
that of tin. It yields sulphuretted hydrogen in heated muriatic acid.
_Hydrosulphuret of bismuth._ When a solution of bismuth in
nitro-muriatic acid is dropped into hydrosulphuret of lime, a black
powder precipitates, which, when dried in the common temperature,
appears to be hydrosulphuret of bismuth, or one atom sulphuretted
hydrogen and one oxide of bismuth. It yields sulphuretted hydrogen by
cold muriatic acid. But if the precipitate be dried in a heat of about
200°, the atom of water seems to be expelled, and there remains only
the protosulphuret. Thus I found 69 parts oxide of bismuth unite to 15
sulphuretted hydrogen to form 84 hydrosulphuret of bismuth, when dried
in the air; but upon being heated a little, it lost 8 parts of water
and was reduced to the protosulphuret, retaining in great part the same
appearance as before.
_Deutosulphuret and trisulphuret of bismuth with oxygen._ When
nitro-muriate of bismuth is thrown into water the oxide is
precipitated; if the acid water be decanted, quadrisulphuret of lime be
put to the moist oxide and due agitation be used, the oxide abstracts
sulphur from the lime so as to obtain 2 or 3 atoms for each one, if
the sulphur be sufficient in quantity. To 6 oz. water I put 100 grain
measures of 1.286 nitro-muriate, which I knew from its formation
contained 20 oxide; after the precipitate had subsided I poured off 5
oz. of acid water, and to the remaining precipitate diluted with water
I put 300 of 1.056 sulphuret of lime and agitated for 10 minutes.
There were obtained 33 grains of brownish black sulphuret of bismuth
dried for some hours in a temperature of 120°. I put the above 33
grains into a gas bottle with 100 muriatic acid and boiled it; there
were obtained only 2 or 3 cubic inches of sulphuretted hydrogen, the
oxide was dissolved and sulphur liberated; the sulphur collected and
dried weighed 9 grains, and the oxide precipitated again from the
muriatic acid by water and dried, weighed 17 grains, besides loss.
From this it is evident the oxygen of the oxide must have been chiefly
retained in the compound, and must have united to 2, and in great part
to 3, atoms of sulphur. For 20 oxide would require 12 sulphur to form
trisulphuretted oxide; and there was evidence of its having nearly, if
not wholly, that quantity.
30. _Sulphurets of antimony._
_Protosulphuret._ This is a natural production, and found in the state
of a dark grey mineral of metallic appearance, and of the sp. gr. 4.2.
It may also be formed artificially by uniting metallic antimony and
sulphur by heat. Most authors nearly concur in assigning to it 74 parts
antimony and 26 sulphur, per cent. That is, 1 atom antimony (40) and 1
of sulphur (14). It yields sulphuretted hydrogen by muriatic acid and
heat, and a solution of the metallic oxide is obtained.
_Hydrosulphuret._ When antimony is precipitated from a solution, by
sulphuretted hydrogen or a hydrosulphuret, or from an alkaline solution
of the sulphuret by an acid, it appears in the form of an orange yellow
powder, denominated golden sulphuret. It is constituted of 1 atom
sulphuretted hydrogen and 1 of protoxide of antimony; it readily yields
sulphuretted hydrogen by muriatic acid, and the oxide combines with
this acid. Exposed to heat, water is expelled and protosulphuret left.
It is constituted of 40 antimony, 7 oxygen, 14 sulphur and 1 hydrogen;
or of 54 protosulphuret and 8 water.
_Bisulphuretted_, _trisulphuretted_ and _quadrisulphuretted oxide of
antimony_. When crystallized muriate of antimony is agitated along with
dilute quadrisulphuret of lime, an orange yellow compound is formed,
consisting of the oxide and sulphur. To 350 quadrisulphuret of lime,
diluted with lime water, I put 22 grains moist crystals of muriate, and
agitated well for some time. Got 26 grains dry yellow sulphuret, which
heated burned blue, and left from 13 to 14 black grey sulphuret, equal
to 10 antimony nearly; hence it must have been a quadrisulphuret, or
rather sulphuretted oxide; for, by heating this compound in muriatic
acid, a solution is obtained and sulphur liberated without the
extrication of gas. Less of the sulphuret of lime would have produced a
sulphuret of the same colour, but containing less of sulphur; so that
it is evident various proportions may exist in combination. Instead of
the crystallized muriate, the recently precipitated oxide, nearly free
from acid, may be used to produce these compounds.
31. _Sulphuret of tellurium._
Tellurium unites with nearly its weight of sulphur, by heat, according
to Davy. It is probable that as usual in such cases, a protosulphuret
is formed. This would lead to the conclusion that the atom of tellurium
is only equal in weight to that of sulphur; which does not accord with
results from the other combinations of tellurium, and hence the above
fact may not perhaps be sufficiently ascertained.
32. _Sulphurets of arsenic._
Arsenic may be combined with sulphur by exposing a mixture of the
metal and sulphur or of the white oxide and sulphur, to a heat
approaching to redness. In the latter case more sulphur is required,
because the oxygen is carried off in the shape of sulphurous acid.
Three parts of arsenic with two, three or more of sulphur may be used;
the heat should be less if a greater proportion of sulphur is intended
to be united. As both the elements are volatile in a moderate heat, and
that in unequal degrees, considerable difficulty occurs in ascertaining
by the synthetic mode, the proportions of the elements combined; if
too little heat be used, only a mechanical mixture is obtained, of any
proportions we please; if too much heat be used, part of the arsenic as
well as part of the sulphur sublimes, and the sulphuret itself sublimes
at a heat not much exceeding that required for their union. Hence in a
great measure we have the discordant results of those who have taken
the synthetic method. The analytic method is to be preferred, and those
who have taken it have succeeded the best; but even this is attended
with greater difficulties than with most of the other sulphurets.
The artificial sulphurets of arsenic constitute two varieties chiefly,
and these are also found native in various parts of the earth.
_Protosulphuret._ Native sulphuret of arsenic, called orpiment, is
found in Turkey and elsewhere in considerable masses; when broken it
exhibits a foliated structure, somewhat flexible, and of a brilliant
golden yellow colour. Its specific gravity is usually about 3.2; at
least that was the case with the specimen I used. When heated so as
to be near melting, its surface reddens, probably by the loss of
sulphur. The same sulphuret is procured artificially in the humid way
whenever a solution of the oxide of arsenic in water, &c. is treated
with sulphuretted hydrogen, or a hydrosulphuret, and afterwards with
an acid; or when this or any other species of sulphuret of arsenic is
dissolved in an alkali and the solution treated with an acid. Kirwan
in 1796 states, that it is generally thought to consist of 100 arsenic
and 11 sulphur, but that Westrumb says it contains 100 arsenic and
400 sulphur, which Kirwan thinks more probable; they are both however
very wide of the truth. Thenard, in the 59 VOL. of the An. de Chimie,
1806, asserts that it consists of 100 arsenic and 75 sulphur; but he
does not point out the experiments on which this result rests; and it
is not very near the truth. Laugier in the same An. VOL. 85, for 1813,
in a paper of great merit, finds the native orpiment to contain 38
per cent. of sulphur; his method is to dissolve the orpiment in warm
dilute nitric acid; to precipitate the sulphuric acid by nitrate of
barytes, and from the sulphate of barytes infer the sulphur; the rest
he considers as arsenic, not knowing how to detach the arsenic acid
from the nitric acid so as to determine the arsenic by experiment. I
have pursued this method with the advantage of being able to determine
the arsenic as well as the sulphur: Ten grains of orpiment in fine
powder were dissolved in 100 measures of 1.346 nitric acid diluted with
as much water, by digesting in a heat so as to keep a constant moderate
effervescence for about 2 hours. The liquid obtained, being diluted,
yielded 536 measures of 1.061. By carefully and gradually dropping
in muriate of barytes I found 150 measures of 1.162 just sufficient
to saturate the sulphuric acid, and the sulphate of barytes produced
dry was 28 grains, the loss I estimated 1 grain: now one third part
being sulphuric acid, and ⅖ of the acid being sulphur, we have ²/₁₅ of
29 = 3.87, or 3.9 for sulphur. The residuary liquid was then treated
with lime water till an excess was manifest, and produced no farther
precipitate; the arseniate of lime was collected and dried, and gave 16
grains. Now I had determined by experiments hereafter to be related,
that ⁴/₇ of arseniate of lime are acid and ⅔ of the acid are arsenic;
hence ⁸/₂₁ of 16 = 6.1 for the arsenic, which added to 3.9 sulphur,
make up the 10 grains of orpiment.
When this orpiment is treated with caustic alkali, it is completely
dissolved; it is thrown down by acids I find unaltered. If 61 arsenic
combine with 39 sulphur, 100 must take 64 nearly; which corresponds
with 1 atom of each, or 21 arsenic + 13 or 14 sulphur.
_Subprotosulphuret._ Sulphur and arsenic are found native in certain
places, combined in masses of a brownish red or orange colour and
glassy fracture: this combination is called _realgar_, and is also
manufactured in large quantities in Saxony, chiefly for the use
of calico-printers. Its constitution and specific gravity vary
considerably, owing chiefly I imagine to the greater or less heat
to which it is exposed, and to the proportions of the elements in
the first mixture. I have specimens of 3.3 and 3.7 sp. gr.; and it
is probable these are not the extremes; the heaviest is the darkest
colour. Of course the heaviest contains the most arsenic, and I
have reason to believe that the sp. gr. is nearly as good a test
of the proportions of the elements as chemical analysis. Realga
when pulverized is of an orange colour: it is much sooner dissolved
in dilute nitric acid and requires less, than the same weight of
orpiment. Caustic alkali dissolves it partially, taking up the
protosulphuret and leaving the excess of arsenic, the quantity of which
may hence be ascertained. Ten grains of realgar took 80 measures of
1.347 nitric acid, diluted with as much water; digested in a heat of
about 150° it was all dissolved in 1½ hour, and yielded 536 liquid of
1.05 sp. gravity. This treated as before gave 24 sulphate of barytes =
3.2 sulphur, and 18 arseniate of lime = 6.9 arsenic. This result agrees
nearly with Laugier’s in regard to the sulphur in native realgar: but
the artificial realgar, which he made by combining arsenic and sulphur,
yielded him 40 per cent. sulphur by my estimation and 42 by his own:
the sp. gravity of his artificial realgar is not given. Westrumb
estimates realgar at 100 arsenic and 25 sulphur, and Thenard at 100
arsenic and 33 sulphur. But from the above it must be concluded to
contain 100 arsenic and 45 to 50 of sulphur. One hundred parts of the
same realgar heated in caustic potash were resolved into 78 orpiment
taken up by the liquid and 22 arsenic precipitated.
It appears to me most probable that a true subsulphuret would be most
convenient for the printers’ use, or one containing 100 arsenic and 32
sulphur, that is, 2 atoms arsenic and 1 sulphur. The object being to
deoxidize indigo and obtain it in solution in a green state, we may
suppose that 1 atom arsenic takes the oxygen from the indigo and then
forms arseniate of lime which precipitates, whilst the other atom in
union with the sulphur, takes the green indigo and unites it to the
potash, making a quadruple compound of arsenic, sulphur, green indigo
and potash in solution. If this view be right the heaviest and darkest
coloured realgar of commerce must be the most advantageous for this
purpose. Some printers however prefer the protosulphuret.
_Deutosulphuret._ Proust, by heating 100 arsenic with 300 sulphur in
one instance got 222 parts, and in another 234 parts of a transparent
deep greenish yellow sulphuret, (Jour. de Phys. 59--p. 406. 1804). Now
it is very remarkable that if we take the atom of sulphur at 13 and
that of arsenic 21, one of this and two of the former will be found as
100 to 124, together 224; but if sulphur be 14, then the proportion
will be 100 to 133, together 233. It seems more than probable that
Proust had accidentally used that degree of heat in the combination
which is requisite for forming the deutosulphuret. It is probable too
that Laugier always used a higher heat, as he uniformly obtained the
same (lower) sulphuret whatever were the proportions, the excess of
either being sublimed or separated by the heat.
_Trisulphuret_, _quadrisulphuret_, &c. When a solution of the oxide of
arsenic is treated with quadrisulphuret of lime, little precipitate
appears; but if muriatic acid be dropped in, a fine yellow precipitate
is formed. This I have reason to think is sometimes a trisulphuret,
and at other times a quadrisulphuret or higher; but it is difficult
to investigate these compounds, and on that account I speak with some
uncertainty.
33. _Sulphuret of cobalt._
Sulphuretted hydrogen does not precipitate cobalt from solutions
containing that metal; but hydrosulphurets precipitate it.
_Protosulphuret._ This compound is obtained whenever a neutral solution
of cobalt is treated with hydrosulphuret of lime, &c. or it may be
obtained from any acid solution by first precipitating the blue oxide
by an alkali, and then introducing sulphuretted hydrogen into the
mixture. By this last method I found a solution previously known
to contain 44 parts by weight of protoxide to absorb 15 parts of
sulphuretted hydrogen; when filtered and dried in a heat of 100° it
yielded 51 parts of protosulphuret. In appearance it resembles many of
the other black sulphurets. It consists of 100 cobalt and 38 sulphur;
Proust finds 40 sulphur, but he considers it only an approximation.
The same sulphuret may be formed by heating the oxides of cobalt and
sulphur together to a red heat; at least a combination is effected as
Proust observed, but I have not investigated the proportions. Sulphur
does not seem to combine with the metal in this way.
_Deutosulphuret_ ... _dodecasulphuret_. When the recently precipitated
and moist oxide of cobalt, the neutral muriate, or acid muriate of
cobalt, as well as other salts of the same, are treated with dilute
quadrisulphuret of lime, sulphurets of cobalt are formed in various
proportions according to the ingredients, from the deutosulphuret to
the dodecasulphuret: these precipitates are all black and not easily
distinguished in appearance; but there is reason to believe they are
true chemical compounds.
34. _Sulphurets of manganese._
Though sulphur and manganese do not unite directly, they can be brought
into union by intermediate bodies, both in the dry and humid way.
_Protosulphuret._ This compound may be formed by heating to a low
red, a mixture of the oxide of manganese and sulphur, or of the white
carbonate of manganese and sulphur; or it may be formed by treating a
solution of manganese by a hydrosulphuret, (sulphuretted hydrogen not
producing any precipitate); this last method seems to produce a dry
hydrosulphuret of manganese, which being heated to red nearly, parts
with water and a little sulphur and there remains the protosulphuret.
The protosulphuret is of a snuff brown colour; but the hydrosulphuret,
when recently precipitated is of a light drab colour, which grows
deeper when exposed to the air, and when dried becomes brown like
the protosulphuret; when heated, the colour is not much changed.
The hydrosulphuret of manganese gives sulphuretted hydrogen by cold
muriatic acid, and the protosulphuret gives the same by the acid
heated.
The proportion of the elements in the protosulphuret may be inferred
from the fact that the black oxide yields its own weight of
protosulphuret; that is, 156 grains, composed of 100 metal and 56
oxygen give 156 of sulphuret; hence the atom of metal, 25, unites with
one of sulphur, 14. I found 32 of the protoxide in solution unite to 15
of sulphuretted hydrogen to form 47 hydrosulphuret dried in 100°. This
lost about 8 parts or rather upwards by heat.
_Deutosulphuret_, _trisulphuret_ and _quadrisulphuret_. These may be
formed by treating neutral solutions of manganese, or the recently
precipitated oxide, by quadrisulphuret of lime. They are formed
somewhat slowly and by considerable agitation with a smaller or greater
proportion of the lime sulphuret. They are all light drab, and are
reduced to the protosulphuret by heat.
35. _Sulphuret of chromium._
I have not had an opportunity of ascertaining whether chromium or its
oxides combine with sulphur or not, though several attempts were made
for that purpose.
36. _Sulphuret of uranium_.
From the experiments of Bucholz it would seem that uranium may be
combined with sulphur, but the proportions have not been ascertained.
(An. de Chimie. 56--142.)
37. _Sulphuret of molybdenum._
From Bucholz and Klaproth’s analyses of molybdena it would seem that
the native sulphuret consists of 60 metal and 40 sulphur; but it does
not appear whether this should be considered as the protosulphuret or
the deutosulphuret. If it is the protosulphuret the atom of molybdenum
weighs 21, but if the deutosulphuret, the atom of metal weighs 42; and
the atom of the sulphuret or molybdena must weigh either 35 or 70.
38. _Sulphuret of tungsten._
According to Berzelius, a sulphuret of tungsten may be obtained, by
heating a mixture of tungstic acid and sulphuret of mercury in the
proportion of 1 to 4, in a crucible. The mixture in his experiment was
covered with charcoal and the crucible inclosed in another containing
charcoal; the whole was then exposed to the heat of a furnace for half
an hour. The sulphuret obtained was a greyish black powder; it was
found to consist of 100 metal and 33¼ sulphur, or about 3 metal to 1
sulphur. Hence this must be the deutosulphuret if we consider the atom
of tungsten to be 84; but considering the high degree of heat to which
it was exposed, it would seem more likely to be the protosulphuret; if
so, the atom of tungsten must be considered as 42 only, or half of the
other number.
39. _Sulphuret of titanium._
No compound of titanium and sulphur has been formed.
40. _Sulphuret of columbium._
This combination is unknown.
41. _Sulphuret of cerium._
This combination is also unknown.
SECTION 15.
EARTHY, ALKALINE, METALLIC AND OTHER PHOSPHURETS.
Phosphorus like sulphur is capable of being combined with several of
the earths and metals as well as with other bodies; but the combination
is not so easily effected, and the products are less interesting
than those of sulphur: from considerations of these circumstances
together with those of the expence and danger in making experiments
on phosphorus we may account for, this class of bodies being as yet
imperfectly known.
Margraf in 1740 attempted to combine phosphorus with many of the
metals; but his experiments were mostly unsuccessful.
Gengembre in 1783 endeavoured to unite phosphorus with the alkalies; in
this he failed of success, but discovered the phosphuret of hydrogen,
or the spontaneously inflammable gas now denominated phosphuretted
hydrogen. (Journal de Physique, 1785.)
In 1786 Mr. Kirwan published some experiments on phosphuretted
hydrogen, (Philos. Trans.); he ascertained that water impregnated with
this gas had the property of precipitating various metals from their
solutions.
The ingenious and indefatigable Pelletier has more merit than any other
person in his investigations of the phosphurets. An important memoir
of his on the manufacture of phosphorus in the large, is given in
the Journal de Physique for 1785; in this he states that 4 or 5 lbs.
sulphuric acid are commonly requisite for 6 lbs. calcined bones; and
that from 18 lbs. calcined bones he obtained by the usual process, 12
oz. of phosphorus. In 1788 he read an essay on the phosphurets of gold,
platina, silver, copper, iron, lead and tin. (An. de Chimie, 1--106).
In 1790 he published an essay on the combinations of phosphorus with
sulphur. (_Ibid._ 4--1). An additional memoir was published in 1792
on the same metallic phosphurets; and another on the phosphurets of
mercury, zinc, bismuth, antimony, cobalt, nickel, manganese, arsenic
and the other metals.
M. Raymond in the An. de Chimie, 1791, recommends, instead of potash,
moist hydrate of lime and phosphorus in order to obtain phosphuretted
hydrogen with greater facility; and in the same Annals for 1800 he
asserts that water absorbs a considerable portion of phosphuretted
hydrogen, and becomes capable of precipitating metals from their
solutions in acids, and of forming phosphurets, in this respect
resembling sulphuretted hydrogen.
Mr. Tennant discovered in 1791 that carbonic acid combined with the
earths and alkalies is capable of decomposition by phosphorus, in a
red heat; and Dr. Pearson, following up the discovery, found that pure
or caustic lime may be united to phosphorus by heat so as to form
phosphuret of lime; and that this dry compound when put into water is
decomposed and gives out bubbles of phosphuretted hydrogen gas, which
as usual explode spontaneously on reaching the surface of the water and
coming into contact with the air.
In 1810 I published the method of analysing phosphuretted hydrogen by
Volta’s eudiometer; having found that this gas and oxygen may be mixed
together in a narrow tube without explosion and afterwards exploded as
other similar mixtures by an electric spark.
Dr. Thomson published an essay on phosphuretted hydrogen in the Annals
of Philosophy for August, 1816. He agrees with me very nearly as to the
constitution and properties of this gas, as far as I have gone; but he
has ascertained several additional properties of the gas, which I shall
advert to in the sequel.
Sir H. Davy and Gay Lussac have investigated several compounds of
phosphorus, particularly with muriatic and oxymuriatic acids, and with
the new metals potassium and sodium, which I shall have to notice in
their proper places.
Other authors have written on phosphurets besides those I have
mentioned, but they do not require to be particularly distinguished
in this enumeration. We shall therefore proceed to describe the
phosphurets more particularly.
1. _Phosphuret of hydrogen._
From recent experiments which I have made on phosphuretted hydrogen
gas, I find the account already given (VOL. 1. page 456) is deficient,
and in several respects inaccurate; I shall therefore substitute the
following, as more perfect and correct.
Phosphuretted hydrogen may be obtained nearly pure, by the methods
recommended by Dr. Thomson. Phosphuret of lime that has been carefully
secluded from the atmosphere, may be put into a small phial filled
with water, acidulated by muriatic acid; into this a cork with a bent
tube must be immediately put under water, so that the phial and tube
are both full of water; gas soon begins to appear, which rising to
the top of the phial, expels a corresponding portion of water, and in
due time the gas itself comes over and may be received as usual: if
the phial in which the gas is generated be warmed to 140 or 150°, the
gas is given out more readily. A half ounce phial with 20 grains of
phosphuret in small lumps, will produce 3 or 4 cubic inches of gas.
If the phosphuret of lime has been previously exposed for a few hours
to the atmosphere, the gas is more abundant, but consists chiefly of
hydrogen, mixed with a little phosphuretted hydrogen.
Pure phosphuretted hydrogen is distinguished by the following
properties: 1. It explodes when coming into the atmosphere in bubbles,
and a white ring of smoke subsequently ascends: 2. It is unfit for
respiration, and for supporting combustion: 3. Its specific gravity
is 1.1 nearly, that of atmospheric air being unity: 4. Water absorbs
fully ⅛ of its bulk of this gas, which is expelled again by ebullition
or by agitation with other gases, but not without some loss: 5. A
small portion being electrified for some time, deposits abundance of
phosphorus, and expands from one volume to 1⅓ nearly, which is found to
be pure hydrogen: 6. Liquid oxymuriate of lime absorbs phosphuretted
hydrogen, converting it into phosphoric acid and water, and leaves any
free hydrogen that may be present; hence we are enabled to ascertain
the proportion of free hydrogen in any such mixture, an important
point as far as regards this gas: 7. One volume of pure phosphuretted
hydrogen, requires two volumes of oxygen for its complete combustion by
an electric spark, in Volta’s eudiometer; (the gases must be previously
mixed in a tube not more than ³/₁₀ of an inch in diameter, to prevent
an explosion in the act of mixing, after which they may safely be
transferred into any other vessel); the result of the combustion is
phosphoric acid and water: 8. One volume of phosphuretted hydrogen,
mixed with from 2 to 6 volumes of nitrous gas, may be exploded by
electricity in Volta’s eudiometer; or it may be exploded by sending
up a bubble of oxygen, without electricity; in like manner, may the
mixtures of phosphuretted hydrogen and oxygen be exploded by a bubble
of nitrous gas: 9. One volume of phosphuretted hydrogen, mixed with
4, less or more, of nitrous oxide, is also explosive by electricity,
but the mixture undergoes no change without electricity, at least in
a day: 10. Mixtures of phosphuretted hydrogen and nitrous gas have a
slow chemical action, by which in from 1 to 12 hours, the phosphuretted
hydrogen is burnt and the nitrous gas decomposed into nitrous oxide and
azotic gas: 11. According to Sir H. Davy and Dr. Thomson, phosphuretted
hydrogen gas being heated along with sulphur in a dry tube, the gas is
decomposed and a new gas, sulphuretted hydrogen, is formed, and the
phosphorus unites with the sulphur. Davy says the gas is doubled in
volume by this operation; but Thomson says it remains the same; some
doubt therefore exists respecting this fact: 12. When phosphuretted
hydrogen gas is let up to oxymuriatic acid gas, a quick combustion with
a yellow flame is observed, and the result varies according to the
proportions: when one volume phosphuretted hydrogen is put to 3 or 4
of acid gas, both of the gases disappear, and muriatic and phosphoric
acids are produced.
As these properties differ in many respects from those hitherto
assigned to this gas, it will be necessary to enlarge upon them. The
sp. gr. of this gas has already been adverted to, (VOL. 1.), and its
great variation from .3 to .85; more recently Dr. Thomson finds it
about .9. In all these instances it was, I have no doubt, contaminated
with less or more of hydrogen; at least it was so in my own instance;
for, I have the proportion of oxygen which it required for its complete
combustion, both before and after it was weighed. It was what I then
thought pure gas: that is, 100 volumes required nearly 150 of oxygen;
but I am now convinced that gas of this description contains ⅓ of its
volume of free hydrogen; hence the correction of the sp. gravity. Davy
estimates the sp. gr. of the gas which he denominates _hydrophosphoric_
at .87 or 12 times that of hydrogen; this gas, as will appear from this
and other properties, is in all probability phosphuretted hydrogen gas,
nearly pure.
The absorption of this gas by water, has been stated variously. In 1799
M. Raymond found that water absorbs rather less than ¼ of its volume of
this gas: in 1802, Dr. Henry rates its absorption at ¹/₄₇ only; in 1810
I found it ¹/₂₇; in 1812, Davy found it (hydrophosphoric gas) to be ⅛;
in 1816, Dr. Thomson found it to be ¹/₄₇; I now estimate it as stated
above at ⅛. These enormous differences may be partly accounted for by
varieties in the gas; and partly from the theory of the absorption
not being understood; but these are scarcely sufficient excuses in
all the cases. I find that my early experiments on the absorption of
phosphuretted hydrogen by water, were made prior to the discovery of
the method of analysing the gas by electric combustion; consequently
they were deficient in regard to the quality of the gas, both before
and after agitation; the best gas that ever I had, was such as took
150 oxygen per cent. for its combustion, exclusive of any common air;
and it was often such as to require considerably less. The bottle
which I used for the purpose in 1810 contains 2700 grains of water; at
first I charged water with hydrogen: into this 120 grain measures of
phosphuretted hydrogen were put, and the whole well agitated: there
were left 98 measures;--this proved that the gas was more absorbable
than hydrogen: into the same water were put 98 more phosphuretted
hydrogen and agitated; out, 80; this confirmed the proof: Into the same
water were put 97 hydrogen and agitated well; out 105: This shewed
that the hydrogen had expelled a part of the gas again, and was less
absorbable of the two. As the phenomena were much the same as if oxygen
had been used instead of phosphuretted hydrogen, it was concluded to
have the same absorbability.
In the present instance, however, I have been more circumstantial;
after repeatedly agitating water with pure azotic gas, so as to
saturate it and expel the oxygen, I then put in 110 grain measures
of phosphuretted hydrogen composed of 100 pure gas, 5 hydrogen, and
5 azotic gas or rather atmospheric air. After due agitation, all was
absorbed but 35; this was mixed with a known portion of oxygen and
exploded; the diminution was 19 measures; the oxygen remaining was
determined by hydrogen; from which it appeared that 10 combustible
gas had taken 9 oxygen. Now 10 being ²/₇ of 35, we may consider the
water as ²/₇ impregnated with the phosphuretted hydrogen, and ⁵/₇ with
azote; but as there were 105 combustible gas and only 10 left, 95 must
have entered the water and caused it to be ²/⁷ charged with the gas;
whence we may infer that 332 gas would have been a full charge for 2700
water, which is almost exactly ⅛, as stated above. Other experiments
gave corresponding results. On admitting 51 azotic gas to the water,
and agitating it a good deal for 4 or 5 minutes, there came out 51
measures or the same volume: this was found in the same way to consist
of 43 azote and 8 combustible, which took 10 oxygen. Again 51 azote
was agitated in the water, and there came out 51, of which 5 + were
combustible and took 9 oxygen. After this the bottle of water was put
into a pan of water which was raised to the boiling heat, a bent tube
filled with water being adapted to the water bottle, and having its end
immersed in water: by this operation gas was expelled from the water,
and caught in the neck of the bottle; when it amounted to 22 grain
measures it was transferred and was found to consist of 17 azote + 5 +
combustible, which took 10 oxygen. By these experiments we see that the
gas is expelled again from the water, both by ebullition and by other
gases, nearly the same in quality, but much diminished in quantity,
the reason of which is not very obvious. The liquid now required 30
measures of oxymuriate of lime, equivalent to 100 measures of oxygen,
before it was saturated; that is, there appeared to be 50 phosphuretted
hydrogen remaining in the water. Adding a little lime water threw down
a very sensible quantity of phosphate of lime.
The expansion of phosphuretted hydrogen by electricity is a subject on
which there has been as much diversity as on its absorption. In 1797,
Dr. Henry found that it expanded “equally with carbonated hydrogen.”
(Philos. Trans.). In 1800, Davy states that phosphuretted hydrogen was
not altered in volume by electricity. (Researches, page 303.) In 1810,
my experiments led me to adopt the same conclusion. In 1811, Gay Lussac
found (Recherches, page 214), that potassium heated in phosphuretted
hydrogen gas, expanded 100 volumes to 146; he infers that the true
expansion ought to have been to 150. In 1812, Davy observes, that when
electric sparks are passed through gases of this kind, “usually there
is no change of volume.” (Elements of Chem. Philos. p. 294.) But he
adds that when a gas (sp. gr. 6, hyd. being 1) was heated with zinc
filings over mercury, there was an expansion of volume of more than ⅓.
Also potassium heated in it, made 2 parts become 3 or 3, parts rather
more than 4, (1810); the residual gas in these cases was pure hydrogen.
Hydrophosphoric gas (sp. gr. 12) yielded 2 volumes of hydrogen, by
heating potassium in it. In 1816, Dr. Thomson found that by electric
sparks phosphorus was deposited, and hydrogen remained “exactly equal
to the original bulk of the phosphuretted hydrogen.” Lastly, in 1817,
I found by two experiments, that by electrifying 30 grain measures
of phosphuretted hydrogen in a tube over water, uninterruptedly for
nearly 2 hours, I produced an expansion of ⅕, or the gas became 36
measures; originally the gas contained 2½ common air, and the rest was
combustible so that 100 measures took 190 oxygen. By exploding the
residue with oxygen, I found that ¹/₁₅ or ¹/₂₀ of the phosphuretted
hydrogen still remained undecomposed. Taking these observations into
consideration along with the fact, that 1 volume of the purest gas
requires 2 of oxygen for its combustion, I conclude that the true
expansion should be ⅓, or 3 volumes of gas should become 4, and then it
will be found that ⅓ of the oxygen is joined to the hydrogen and ⅔ to
the phosphorus, which accords with what appears to me the only correct
view of the constitution of phosphoric acid, namely, 2 atoms of oxygen
to 1 of phosphorus.
The action of oxymuriatic acid, whether free or combined, on
phosphuretted hydrogen, is curious and interesting; in both cases it
effects a complete and instantaneous combustion of both phosphorus
and hydrogen; when the acid is put to in the state of gas, it not
only burns the phosphuretted hydrogen, but any free hydrogen that may
be present; but this has a limit: if the phosphuretted hydrogen be
largely diluted (90 per cent.) with hydrogen, this last is wholly left;
the reason seems to be, the phosphuretted hydrogen burns at a lower
temperature; and hence probably it is, that liquid oxymuriate of lime
burns the phosphuretted hydrogen, but not the hydrogen gas.
The quantity of oxygen necessary to saturate a given volume of
phosphuretted hydrogen is easily found. Oxygen gas containing a known
per centage of azotic gas, must be used in some excess, mixed with a
due portion of the gas. After exploding the mixture, the loss must be
observed, and then the remaining oxygen must be found by exploding
it with hydrogen. Hence the true volume of oxygen spent by the first
explosion, and that of the combustible gas are both determined. The
due proportion of oxygen is so nearly 2 to 1, that I have not been
able to determine on which side the truth lies. Dr. Thomson says that
when phosphuretted hydrogen and oxygen are mixed, two volumes to one,
a white smoke takes place, the volume of oxygen gradually disappears,
and there remains behind a quantity of hydrogen exactly equal to the
original volume of the phosphuretted hydrogen. I have observed nothing
at all like this. A mixture of phosphuretted hydrogen and oxygen stood
24 hours without sensible diminution, and afterwards being exploded, 2
volumes of oxygen disappeared for 1 of phosphuretted hydrogen, the same
as would have done at the moment of mixing. Perhaps the _temperature_
may have some influence; mine was about 55°.
I have tried the minimum of oxygen that will consume or dissipate
phosphuretted hydrogen gas. It may be exploded with about ¼ of its
volume of oxygen, with the same phenomena as Davy observed of the
hydrophosphoric gas. Phosphorus is thrown down and a volume of
combustible gas is left about 10 per cent. greater than the original
volume of phosphuretted hydrogen. This gas is nearly pure hydrogen.
Hence the whole gas may be dissipated at 2 successive explosions, by
rather less than an equal volume of oxygen. If phosphuretted hydrogen
be exploded with an equal volume of oxygen, phosphorous acid, water and
a little phosphoric acid are formed, and some hydrogen remains.
One of the most remarkable properties of phosphuretted hydrogen, is
that announced by Dr. Thomson, namely, its combustion with nitrous
gas by electricity; and the _slow_ combustion by the same gas, which
I have mentioned above is a fact still more difficult to explain. I
tried the combustion of phosphuretted hydrogen by nitrous gas and
electricity in 1810, but did not succeed. The reason was, the gas was
not sufficiently pure. No phosphuretted hydrogen that is not 70 or
80 per cent. pure, can, I imagine, be exploded by nitrous gas; even
the purest requires sometimes more than one spark, when mixed in the
most favourable proportions; and I have known instances in which the
mixture has exploded after electrification for a few minutes. An excess
or defect of nitrous gas, occasions oxygen or hydrogen to be found in
the residual gas, just as when we explode with oxygen. One volume of
phosphuretted hydrogen requires, as nearly as I can find, 3½ of nitrous
gas for mutual saturation. The azote developed amounts to 1¾ volumes
or rather less, (due allowances in all such cases being made for that
already existing in the two gases.)
The mutual action of nitrous gas and phosphuretted hydrogen without
electricity exhibits one of the most singular phenomena we have in
chemistry. Nitrous gas seems constantly to be decomposed, one part
producing nitrous oxide and another part azote, even though an excess
of nitrous gas remain undecomposed in the mixture, and both the
phosphorus and hydrogen are completely burnt; but if the nitrous gas be
deficient, then nitrous oxide, azote, and some of the phosphuretted
hydrogen are found in the residue, and the rest of the phosphuretted
hydrogen is completely burnt or converted into phosphoric acid and
water; here appears no preference of phosphorus to hydrogen in this
case, nor any partial combustion. From an attentive consideration
of the results of several experiments, I am inclined to offer the
following solution of this remarkable case: One atom of phosphuretted
hydrogen attacks 5 of nitrous gas at the same instant; the atom of
phosphorus takes 2 of oxygen, and gives the corresponding 2 of azote
to the two of nitrous gas, and thus makes two atoms of nitrous oxide,
while the hydrogen takes 1 of oxygen from the fifth atom and liberates
the azote; thus 2 measures of nitrous oxide are formed along with 1 of
azote; and they are generally found in the residue in that ratio. The
azote does not seem to pass through the intermediate state of nitrous
oxide; for, as soon as the nitrous gas ceases to exist, there is an end
of the combustion.
It may be proper to advert more particularly to the hydrophosphoric gas
of Davy. That this gas is the same as that we have been describing,
can hardly admit of a doubt. Their near agreement in sp. gr., in
their absorbability by water, in the quantity of oxygen requisite
for their combustion, in their moderate expansion by burning with a
minimum of oxygen and in their combustibility by oxymuriatic acid, are
circumstances sufficient to warrant their identity. It is said that
by heating potassium in this gas, one volume yields two of hydrogen;
but it has not been found to yield two volumes by electricity, the
more accurate criterion. Besides, both Davy and Gay Lussac find that
potassium heated in the more common phosphuretted hydrogen expands
it from 1 to 1⅓ or 1½ volume, which common electricity will not do;
it is presumed therefore that the potassium in some way conduces to
the production of a portion of the hydrogen. Spontaneous ignition
or explosion is, I believe, no distinctive mark of variety in
phosphuretted hydrogen; when this gas is _produced_, it is usually
explosive from the uncombined phosphorus which it elevates; but the
best and purest phosphuretted hydrogen loses the property wholly or
partially by standing a while over water, though it loses no sensible
part of its phosphorus.
It is commonly stated that phosphuretted hydrogen deposits phosphorus
by long standing. This seems to be true; but the deposition is slower
than I imagined. Seven years ago I set aside a bottle of impure
phosphuretted hydrogen which I then labeled, 10 combustible take
14.6 oxygen; this bottle has not been preserved with special care to
seclude the atmosphere; notwithstanding that, it is now such, that 10
combustible take 6.7 oxygen, and hence it still contains some genuine
phosphuretted hydrogen.
2 _and_ 3. _Phosphurets of carbone and sulphur._
See VOL. 1. page 464.
_4. Phosphuret of lime._
This compound may be formed by subliming phosphorus in a glass tube
containing small fragments of recently calcined lime, heated to a low
red. The sublimed phosphorus coming into contact with the hot lime,
the two unite with a vivid glow, and in due time mutual saturation is
produced. The result is a dry, hard compound of a deep brown or reddish
colour, which on cooling must be put into a bottle and well corked, if
not intended for immediate use, as it soon changes by the action of
atmospheric air and moisture. With this precaution, I have reason to
think it may be kept unimpaired for years.
As far as I know, no experiments have been published relating to the
proportion in which phosphorus and lime unite. M. Dulong, in a valuable
paper on the combinations of phosphorus and oxygen, in the _Memoires de
la Société d’Arcueil_, VOL. 3. (1817,) has given some account of his
experiments on the earthy phosphurets; but it is to be regretted that
he has given none on the proportions of their elements.
In order to ascertain the phosphorus, I put 10 grains of well preserved
phosphuret of lime, into 1000 grains of liquid oxymuriate of lime, such
that by previous trials I knew would impart 3.5 grains of oxygen; to
this mixture a quantity of muriatic acid was put, sufficient to engage
the lime; the phosphuretted hydrogen disengaged, was of course made
to pass through the liquid as it was generated, and became oxidized,
so as to lose its gaseous form; the surplus gas was prevented from
escaping by an inclination of the bottle; it was 45 grain measures
only, and of this 30 were found to be pure hydrogen, and the rest
atmospheric air detached from the water; these 30 measures were the
_free_ hydrogen, which would have been mixed with the phosphuretted
hydrogen, in the ordinary way. In due time, the whole of the phosphuret
of lime was dissolved. The liquid was strongly acid, and manifested
no smell of oxymuriatic acid, a proof that it was all decomposed. To
this were added 70 more of the oxymuriate of lime before the smell of
it was permanently developed. The liquid was next saturated with lime
water, and the phosphate of lime carefully collected and dried; when
heated to a low red it weighed 12 grains, and consisted, according to
my estimate of this compound, of 6-- grains of phosphoric acid and
6 + grains of lime. The 6-- grains of acid contained 2.4 phosphorus
and 3.5 of oxygen. It must be remembered that 10 grains of phosphuret
yield about 500 measures of phosphuretted hydrogen, and these contain
650 measures of hydrogen, which last is also oxidized at the expence
of the oxymuriatic acid; but then there is an equivalent of oxygen
from the water, so that this does not influence the calculation for
oxygen. There appears then to be only an excess of .24 grains of oxygen
unaccounted for, (arising from the additional 70 of oxymuriate of
lime), which is as little as can be expected in such an experiment. If
the phosphorus amount to 24 per cent. we may reasonably infer that the
remainder (76) is mostly lime, though I have not been able to detect
above 60. Now if an atom of phosphorus weigh 9⅓ and one of lime 24, the
due proportion of the protophosphuret of lime would be 28 phosphorus
and 72 lime; but when the article is made for sale, it is more likely
to find a defect than an excess of phosphorus.
According to Dulong, when the earthy phosphurets are decomposed by
water, phosphuretted hydrogen and subphosphorous acid are formed. I
believe this determination is right; for I find at most only ⅓ of the
above proportion of phosphorus in the phosphuretted hydrogen yielded
by 10 grains of the phosphuret of lime; the remaining ⅔ seem to rest
in the liquid in combination with the oxygen and lime; that is, 1 atom
of hydrogen combines with 1 of phosphorus, and 1 of oxygen with 2 of
phosphorus. Notwithstanding this, the phosphoric acid produced from the
residue by means of oxymuriate of lime, does not in general correspond
to the above quantity. Perhaps this loss may be owing to the phosphorus
carried over in mechanical suspension by the gas.
M. Dulong observes, that even the earthy subphosphites are very
soluble; this did not appear to me to be the case with that of lime: 10
grains of phosphate of lime, that had been exposed for 20 minutes to
the air, were put into a gas bottle filled with 400 grains of water;
this was kept at nearly the boiling heat for an hour, when 725 grain
measures of gas were produced, and some phosphorus was carried over
with it into the receiving bottle and bason of water. The gas being
analysed, was found to consist of 62 per cent. phosphuretted hydrogen,
33 hydrogen and 5 common air. The 400 grains of water in the gas bottle
treated with oxymuriate of lime, and then with lime water, scarcely
gave any appreciable quantity of phosphate of lime. The insoluble
residue when dried yielded 9 grains. This dissolved in muriatic acid
left a fraction of a grain of dirty yellow powder, which indicated some
phosphorus; and the muriate of lime indicated about 6 grains of lime.
_5. Phosphuret of barytes._
The combination of phosphorus and barytes may be effected in the
same way as the foregoing, and the compound has the same appearance.
According to Dulong, who has examined this phosphuret with particular
attention, it gives out phosphuretted hydrogen when dropped into
water, the same as that of lime. When the gas ceases to be given out,
a powder remains completely insoluble in water, of a variable colour,
yellow, grey or brown. It is not altered by the air; but it gives out
a slight phosphoric flame when heated. Dilute nitric or muriatic acid,
dissolves nearly the whole with a trace of phosphuretted hydrogen,
and leaves only a few atoms of greenish yellow powder, soluble in
oxymuriatic acid. The part dissolved by the acids being precipitated
by ammonia, gives phosphate of barytes. From these facts he infers
that the residue insoluble in water, consists of a small portion of
phosphuret of barytes with excess of base, and phosphate of barytes.
The water in which the phosphuret was decomposed, contains most of the
barytes; carbonic acid produces a slight precipitate, and then leaves
a neutral liquid containing the subphosphate of barytes, which appears
to be a very soluble salt. Sulphuric acid throws down the barytes and
leaves the subphosphorous acid in the liquid.
Nothing certain is determined from experiment respecting the proportion
of phosphorus and barytes which combine; but from analogy it is
probable that they combine atom to atom, or 68 parts barytes with 9 of
phosphorus; or 100 parts of the compound contain 88 of barytes and 12
of phosphorus.
_6. Phosphuret of strontites._
Phosphuret of strontites may be formed as the two preceding articles.
It is in all respects similar to the phosphuret of barytes according to
Dulong, and its properties therefore need not be particularized.
From analogy, I should apprehend, it must be constituted of 46
strontites and 9 phosphorus, or one atom of strontites to one of
phosphorus; that is, 100 parts of phosphuret should contain 83
strontites and 17 phosphorus.
Combinations of the other earths and phosphorus have not yet been
effected. Neither have the alkalies been combined with phosphorus; the
hydrates of these as well as those of the earths, yield phosphuretted
hydrogen when heated with phosphorus, and probably a phosphate or
subphosphate of the base. M. Sementini of Rome is said to have
succeeded in combining potash and phosphorus by means of alcohol.
His experiments, however, appear to me too indefinite to warrant
the conclusion. (See An. of Philos.--7. p. 280). The compounds of
phosphorus with potassium and sodium are described in the sequel,
amongst the metallic phosphurets.
_7. Phosphuret of gold._
M. Pelletier heated together in a crucible, half an ounce of pure gold,
one ounce of phosphoric glass and ⅛ of an ounce of powdered charcoal,
the heat was raised sufficiently to fuse the gold. Phosphoric fumes
arose, but the whole of the phosphorus was not dissipated. The gold
remaining was whiter than natural, and brittle under the hammer.
Exposed to a very high heat it lost ¹/₂₄ of its weight, and resumed the
ordinary characters of gold.
The same chemist heated 100 grains of pure gold in filings to a bright
red; he then projected small fragments of phosphorus amongst the gold
successively till after it had entered into fusion. The gold preserved
its colour, but became brittle under the hammer and granular in the
fracture; it had increased 4 in weight.
Mr. Edmund Davy, by heating in a tube deprived of air, finely divided
gold and phosphorus, effected a combination of them. It had a grey
colour and metallic lustre. The heat of a spirit lamp was sufficient
to decompose it. It contained about 14 per cent. of phosphorus.
(Davy’s Chemistry, page 448--An. 1812).
Oberkampf and Thomson have successively observed the precipitation
occasioned by water impregnated with phosphuretted hydrogen, in
solutions of muriate of gold. The former of these has some interesting
remarks on the phenomena. When a current of this gas is passed through
a dilute solution of muriate of gold for a time, and then suddenly
discontinued, the solution becomes brown and passes soon to a fine deep
purple. A yellowish brown precipitate is obtained, which is metallic
gold, and the liquid, now become yellow again, contains muriate of gold
and phosphoric acid. The experiment may be continued with the like
results. But if the liquid be saturated with gas before any precipitate
is suffered to subside, a black powder is obtained which does not
seem to contain any metallic gold, and the liquor ceases to have any
colour. This black powder is the phosphuret of gold; exposed to heat it
inflames and leaves metallic gold, but its elements are not separable
by mechanical means. (An. de Chimie, 80--146, for 1811).
Water impregnated with the gas was found to have like effects as the
gas itself. Whence Oberkampf concludes that as long as an excess of
gold remains in solution, the phosphuretted hydrogen precipitates the
metal only; but when the gas is in excess, the phosphorus leaves the
hydrogen and unites with the precipitated gold.
I should rather suppose that the precipitation of the gold may be,
in part at least, owing to the _free_ hydrogen which we now know
accompanies the phosphuretted hydrogen largely, in the manner in which
this gas was formerly procured; however that may be, I find that water,
impregnated with the purest phosphuretted hydrogen, has the property
of precipitating the black phosphuret of gold from the muriate of
that metal, in such manner as to effect complete mutual saturation,
leaving nothing in the liquid but the muriatic acid. Let a solution
containing a known quantity of gold be gradually dropped into water,
containing a known quantity of phosphuretted hydrogen, as long as any
black precipitate is formed. The point of saturation will be found when
60 parts by weight of gold have united to 9 of phosphorus, nearly; or
when one atom of gold has united to one of phosphorus. Hence it may be
concluded that 100 grains of the phosphuret of gold contain 13 or 14
of phosphorus, which agrees very nearly with the results of Mr. Edmund
Davy abovementioned.
8. _Phosphuret of platina._
M. Pelletier succeeded in combining platina with phosphorus by the same
methods as with gold. By projecting phosphorus on grains of platina
heated to a strong red, the latter acquired an increase of weight of
18 on the hundred; but this was probably an excess, as some vitreous
phosphoric acid was found mixed with the mass.
In the Philos. Magazine, VOL. 40, Mr. E. Davy has related some
experiments made with a view to combine platina and phosphorus; he
effected it by heating platina and phosphorus together in an exhausted
tube; the union commenced below a red heat and was attended with vivid
ignition and flame. The compound was of a blueish grey colour and
consisted of 82½ platina and 17½ phosphorus according to his estimate.
Also by heating the ammonia-muriate of platina with ⅔ of its weight of
phosphorus in a retort over mercury, muriatic gas was liberated, and
muriate of ammonia and phosphorus were sublimed, but there remained at
dull red heat an iron black or dark grey mass at the bottom, of the sp.
gr. 5.28. It was estimated to consist of 70 platina and 30 phosphorus;
but I doubt whether it could consist of these two elements only.
Phosphuretted hydrogen water scarcely has any effect on muriate of
platina. After some time a very light flocculent matter appears, as
Dr. Thomson has observed; but this seems to me to be nothing but a
slight precipitation of phosphorus alone; I apprehend the gas unites
with the platina, but the compound remains in solution somewhat in the
same manner as platina and sulphuretted hydrogen. The platina may be
precipitated from the clear liquid by muriate of tin, much the same in
appearance as if no phosphuretted hydrogen were present.
9. _Phosphuret of silver._
When pieces of phosphorus are dropped amongst silver heated to red in a
crucible, the two unite and enter into fusion, according to Pelletier;
when the metal is saturated with phosphorus the whole continues in
a state of tranquil fusion; but being withdrawn from the fire, at
the moment of congelation, a quantity of phosphorus becomes suddenly
volatile and burns vividly, and the surface of the metal becomes
uneven. The metal on being cooled, is found to have gained from 12 to
15 per cent.; and he apprehends that when fluid it contains 10 per
cent. more, making in all 25 phosphorus to 100 silver.
The phosphuret of silver is white and crystalline, brittle under the
hammer, but capable of being cut with a knife. By a strong heat the
phosphorus is dissipated and leaves the silver pure.
Both Raymond and Thomson observe that phosphuretted hydrogen water
precipitates silver from its solutions of a black colour. I find that
a solution of sulphate of silver containing one grain of the metal,
requires water containing 90 grain measures of phosphuretted hydrogen
to saturate it; the whole of the silver falls readily and leaves
nothing but the acid in the water. Now the weight of 90 measures of
this gas is nearly ⅑ of a grain; hence the proportions of metal and
phosphorus are as 10 to 1, which shows that they combine atom to atom,
or 90 silver to 9⅓ phosphorus. This is somewhat less of phosphorus than
is determined above by Pelletier.
10. _Phosphuret of mercury._
M. Pelletier made several attempts to combine phosphorus and mercury.
He seems to have succeeded best, by exposing mercury in an extreme
state of division, to phosphorus under water in a moderate heat. The
phosphuret is a black compound, which is resolved again into its
elements by distillation.
When nitrate of mercury is treated with phosphuretted hydrogen water, a
copious dark brown or black precipitate is instantly formed, as Raymond
and Thomson have observed. This black precipitate, Raymond adds, soon
becomes white and crystalline in passing from phosphuret to phosphate,
by attracting oxygen.
I have found the black powder when dried in a moderate heat to abound
in small shining globules, which have all the appearance of revived
mercury. However this may be, I find that a certain weight of mercurial
salt requires a certain portion of gas to saturate it, so as that the
whole mercury shall be precipitated. One grain of mercury requires
rather more than ¹/₁₈ of its weight or 50 grain measures of the gas
for its saturation. This proves the combination to be the most simple,
or atom to atom; that is, 167 mercury take 9⅓ phosphorus; or 100
mercury take 5½ phosphorus nearly.
11. _Phosphuret of palladium._
When nitrate of palladium is dropped into phosphuretted hydrogen water,
a copious black flocculent precipitate is immediately formed, which
doubtless consists of palladium and phosphorus.
Into 800 grains of phosphuretted hydrogen water containing 20 grain
measures of gas, were put by degrees, 22 grain measures of muriate
of palladium (sp. gr. 1.01) containing .12 acid and .14 oxide,
corresponding to .12+ metal; mutual saturation was produced, and a
finely distinct black powder precipitated, leaving the water clear
and colourless, which was found by lime water to contain .12 parts
of a grain of muriatic acid. The black powder collected and dried,
corresponded as nearly as could be determined in weight to the
ingredients. Now 20 measures of gas would weigh .025 of a grain, of
which .0025 would be hydrogen and .0225 phosphorus; whence we have
.12+ metal joined to .0225 phosphorus or 50 to 9 nearly, indicating
one atom of each. Hence 100 palladium would take 18 or 19 phosphorus.
12. _Phosphuret of copper._
M. Pelletier combined copper and phosphorus by the same means as the
preceding compounds. One hundred grains of copper united by heat with
15 of phosphorus; the fused mass when cooled was white and very hard.
As part of the copper gets oxidized during the process he thinks
it probable, with M. Sage, that copper may acquire 20 per cent. of
phosphorus.
In the 3d VOL. of Memoirs of the Society of Arcueil, page 432, M.
Dulong converts fine copper wire into phosphuret by heating it to a
low red, and passing the vapour of phosphorus over it in hydrogen gas.
In the sequel he observes that 10 grammes of phosphuret of copper
contained 1.97 of phosphorus; that is, the copper was to the phosphorus
as 8.03 ∶ 1.97, or as 100 ∶ 24.5. This exceeds much Pelletier’s result,
and is, I think, too high. For, he found that the above phosphuret
converted into phosphate of copper by nitric acid yielded 14.44
grammes. Now supposing the atom of phosphorus to weigh 9⅓, that of
phosphoric acid 23⅓, and that of the black oxide of copper 70, we have
an atom of phosphate of copper = 93⅓: and if 93⅓ ∶ 9⅓ ∷ 14.44 ∶ 1.444,
for the phosphorus in 10 grammes; and hence the copper would be 8.556:
this would give 100 copper to 17 phosphorus nearly, which would accord
well with Pelletier’s determination, and very nearly agree with the
theoretic result of 100 copper to 16⅔ phosphorus.
Both Raymond and Thomson remark that phosphuretted hydrogen water
produces a black or dark brown precipitate in sulphate of copper. I
have not found any precipitate from any of the salts of copper by the
same means. But if the blue hydrate be first precipitated by lime
water, and then the phosphuretted hydrogen water admitted, the hydrate
is immediately converted into a dark olive, which in all probability is
a phosphuret of copper. From some experiments I am inclined to believe
that this compound is the deutophosphuret, or two atoms of phosphorus
to one of copper; and hence the copper is to the phosphorus as 100 ∶
33⅓.
13. _Phosphuret of iron._
M. Pelletier formed a phosphuret of iron by both the methods above
described for gold. He describes the phosphuret as very hard, of
a white colour, striated and magnetic. He estimates, with some
uncertainty, that 100 iron may combine with 20 phosphorus.
Berzelius produced a phosphuret of iron by reducing the phosphate
of the metal by charcoal and heat. (An. de Chimie, July 1816). He
describes it as having the colour of iron, brittle and slightly acted
upon by the magnet. By his analysis it was constituted of 100 iron and
30 phosphorus. The true proportion probably would be one atom to one,
or 25 iron to 9⅓ phosphorus; that is, 100 iron to 37 phosphorus.
Both Raymond and Thomson found that sulphate of iron yields no
precipitate by phosphuretted hydrogen water; and I may add, that the
precipitated oxide or hydrate is also unaffected by the same.
14. _Phosphuret of nickel._
By projecting phosphorus amongst red hot nickel, Pelletier united 20
parts of the former to 100 of the latter. A part of the combined
phosphorus, he observes, flies off on cooling, so that the above
proportion may perhaps be too low. Theoretically one atom of nickel
should combine with one of phosphorus; that is, 26 with 9⅓, or 100 with
36.
I find that neither the nitrate of nickel nor the hydrate are affected
by phosphuretted hydrogen water.
15. _Phosphuret of tin._
Margraff was the first who combined phosphorus and tin by fusing the
metal along with fusible salt from urine (phosphate of ammonia).
Pelletier succeeded also in this way, as well as by the direct one of
projecting phosphorus into melted tin. The compound was of a white
colour; it gained 12 per cent. of weight; but as part of the tin was
oxidized and adhered to the crucible in form of glass, he conjectures
that tin would take from 15 to 20 per cent. of phosphorus. The atom of
tin being 52, and that of phosphorus 9⅓, the due proportion would be
100 tin to 18 phosphorus.
Phosphuretted hydrogen water does not seem to precipitate tin from
solutions, nor yet to act upon the precipitated oxide.
16. _Phosphuret of lead._
Lead combines with phosphorus by the same methods as tin; but it is
difficult to ascertain the proportions, according to Pelletier, from
the oxidation and vitrification of part of the lead. Muriate of lead
distilled with fusible salt of urine, also yielded phosphuret of lead.
He conjectures the increase by phosphorus to be 12 or 15 per cent.; but
by theory it should only be 10 or 11 per cent.
Raymond says that the nitrate of lead is decomposed by phosphuretted
hydrogen water, but with less force than salts of silver and mercury;
and that a phosphuret of lead is formed, of which he gives no
character, except that it becomes in time a phosphate. Thomson says a
slight white powder is formed by the mixture. This was the case with
me; but I suspected that the white powder was merely a little sulphate
of lead, arising from the impurity of the (rain) water; and this was
found to be the fact; for the milkiness was just the same with like
water unimpregnated with the gas. Besides, after the phosphuretted
hydrogen water has been saturated with nitrate of lead till no more
effect is produced, still the water retains its peculiar smell, and a
copious black precipitate is instantly produced by nitrate of silver or
mercury. It appears then that phosphuret of lead cannot be formed this
way. Neither does phosphuretted hydrogen water seem to have any effect
on the recently precipitated oxide of lead.
17. _Phosphuret of zinc._
Both zinc and its oxide seem to combine with phosphorus, according to
Pelletier; but the proportions were not ascertained. By theory, zinc
should take 32 per cent. of phosphorus.
18. _Phosphuret of potassium._
Some account was given by Davy, of the combination of potassium and
phosphorus in essays from 1807 to 1810; and by Gay Lussac and Thenard
in others from 1808 to 1811. According to Davy, when potassium and
phosphorus are heated together, they combine in one uniform ratio of 8
to 3 nearly; and the compound, when acted upon by muriatic acid, gives
out from .8 to 1 cubic inch of phosphuretted hydrogen gas, resulting
from one grain of the former and ⅜ of a grain of the latter substances
combined. Also be observed that half a grain of potassium decomposed
nearly 3 cubic inches of phosphuretted hydrogen, and set free more than
4 cubic inches of hydrogen; the phosphuret seemed to be of the same
kind as the former, or that by direct combination of the two elements.
Gay Lussac and Thenard combined the elements by heat; the potassium is
scarcely fused till the phosphuret is formed. The excess of phosphorus
sublimes, and the phosphuret is always of a chocolate colour; the
proportions were not ascertained. By treating this phosphuret with
warm water, a quantity of phosphuretted hydrogen was uniformly given
out, about 40 per cent. more than the hydrogen which would have been
yielded by the potassium alone in water. But if the phosphuret was
treated with dilute acid instead of water, then less gas was given out
than otherwise; and the stronger the acid the less gas, so as sometimes
to reduce the gas in volume to that yielded by potassium alone. They
also found, as Davy had done, that potassium heated in phosphuretted
hydrogen decomposed it, uniting with the phosphorus and producing the
same compound as in the direct way.
The results of Davy and the French chemists appear to be discordant;
but I apprehend they may be reconciled. It appears probable from both,
that the phosphuret of potassium must be a compound of one atom of
each, or 35 potassium and 9⅓ phosphorus; that is, 100 potassium and
27 phosphorus nearly. Now in Davy’s method of treating the compound
with acid, it is most probable that the atom of potassium takes one
of oxygen to form potash, and the atom of phosphorus takes one of
hydrogen to form one of phosphuretted hydrogen; but 3 volumes of pure
phosphuretted hydrogen contain 4 volumes of hydrogen, (see page 178);
and Davy obtained nearly ¾ of the volume of gas which the potassium
alone would have produced, which therefore accounts for the fact as
stated by him.
On the other hand, the French chemists by treating the phosphuret
with hot water, probably determined the resolution in this way: the
potassium resolved the water into oxygen and hydrogen the last of which
was liberated in a free state, and of course produced the usual volume;
the phosphorus also resolved the water into oxygen and hydrogen, one
half of it taking the oxygen to form phosphorous acid, and the other
half taking the hydrogen to form phosphuretted hydrogen, which of
course would produce phosphuretted hydrogen amounting to ⅜ of the
volume of free hydrogen or 38 per cent. nearly, which would make up
the volume of gas to 138, or nearly 140, as observed by them. It is
not unlikely that 2 or 3 per cent. of hydrogen might be added by the
further decomposition of water by the phosphorous acid, in order to
make it into phosphoric acid.
19. _Phosphuret of sodium._
No particular experiments having been detailed of this compound, we
must infer it is similar to the last mentioned, and consists of one
atom of sodium, 21, and one atom of phosphorus, 9⅓; that is, 100 sodium
and 44 phosphorus nearly.
20. _Phosphuret of bismuth._
If we may judge from M. Pelletier’s experiments, bismuth has but a weak
affinity for phosphorus. By projecting portions of phosphorus amongst
melted bismuth, he succeeded in uniting some of it to the metal; he
estimates the quantity at 4 per cent.; whereas by theory it ought to be
15 per cent. supposing them to unite atom to atom.
I do not find that the salts or oxide of bismuth are materially
affected by phosphuretted hydrogen water.
21. _Phosphuret of antimony._
Phosphorus may be combined with antimony, according to Pelletier, by
the same means as with the other metals. The phosphuret has a white,
metallic appearance and lamellar fracture. The ratio of the elements
was not determined. By theory supposing one atom to unite with one, it
would be 40 to 9⅓, or 100 antimony to 23 phosphorus nearly.
Phosphuretted hydrogen water seems to have no effect on the salts or
oxide of antimony.
22. _Phosphuret of arsenic._
From the experiments of Margraff and Pelletier, it seems probable
that phosphorus unites both with arsenic and its oxide. By distilling
a mixture of equal parts of arsenic and phosphorus in a carefully
regulated heat, Pelletier obtained a residuum of a black shining
substance, containing a good proportion of phosphorus. The same was
obtained in the humid way, by keeping phosphorus in fusion on arsenic
under water for some time. The phosphuretted oxide may be obtained by
distilling phosphorus and the white oxide of arsenic together, the
phosphuretted oxide sublimes mixed with arsenic and phosphorus in a
separate state. It is of a red colour. The proportions in neither case
were ascertained. It is probable that the compounds are of the most
simple kind, or one atom to one; in that case we shall have 21 arsenic
and 9⅓ phosphorus, or 100 arsenic and 44 phosphorus for phosphuret of
arsenic; and 28 oxide and 9⅓ phosphorus, or 100 oxide and 33 phosphorus
for phosphuretted oxide.
No precipitation is occasioned by phosphuretted hydrogen water in
solutions of arsenic.
23. _Phosphuret of cobalt._
Cobalt unites with phosphorus in the direct way as well as by being
heated with phosphoric glass. The colour of the compound is a blueish
white; it is brittle and crystalline in the fracture. The metal
acquires 7 per cent.; this is below the theoretic quantity, which is 25
per cent. if the atom of cobalt be 37.
Solutions of cobalt give no precipitate by phosphuretted hydrogen water.
24. _Phosphuret of manganese._
This compound may be formed like the preceding ones. It is of a white
colour, brittle and of a granular texture. It is not liable to be
altered by the air like the pure metal. The proportions of the compound
Pelletier did not determine. Reasoning from theory, it should consist
of 25 metal and 9⅓ phosphorus; or 100 metal and 37 phosphorus.
The salts and oxide of manganese are not sensibly affected by
phosphuretted hydrogen water.
* * * * *
The combinations of the remaining metals with phosphorus can scarcely
be said to have been investigated.
SECTION 16.
CARBURETS.
On the supposition that metals combine with charcoal, the appropriate
names for the compounds would be _carburets_ of the respective metals.
This combination, if it exist at all, seems very rare, that with iron
being the only one generally acknowledged. No combinations of carbone
with the earths and alkalies, have, as far as I know, been noticed;
and those with the elements oxygen, hydrogen, sulphur and phosphorus
have been described in the former volume. Since that was printed an
ingenious experimental essay on the “_Sulphuret of carbon_ or alcohol
of sulphur,” has been published by Berzelius and Dr. Marcet. Some
account of this compound, under the name _carburetted sulphur_, has
been given (VOL. 1. page 462); but the additional information is of
sufficient importance to require notice here. The pure liquid is of sp.
gr. 1.272; and the elasticity of its vapour at 66° is equal to 10.76
inches. It burns with a blue flame and sulphureous odour, without
sensibly depositing water on cold glass exposed to the fumes. It has an
acrid, pungent taste, and a nauseous smell, differing from sulphuretted
hydrogen. By various experiments it was found to consist of sulphur and
carbone in the ratio of 85 to 15 nearly; that is, 2 atoms of sulphur to
1 of carbone. From other experiments it did not appear to contain any
hydrogen.
From some experiments I made in June 1818, on the combustion of the
vapour of carburet of sulphur in oxygen gas, I was led to suspect at
least, that an atom of hydrogen attaches to the two of sulphur and one
of carbone in its constitution. But not having an opportunity to pursue
the subject, I merely make the observation for future experience to
determine upon the question.
1. _Carburets of iron._
There are three distinct substances which are now commonly believed to
be constituted of carbone and iron, known by the names of _Plumbago_,
or black lead, _Cast Iron_ and _Steel_.
Plumbago is a natural production, found in greatest perfection in
the Borrowdale mine, near Keswick, Cumberland. It is chiefly used in
making pencils.--It seems to be constituted of carbone and iron by the
concurrent experience of all who have examined it: but the proportions
are not uniform, some having found 10 and others only 5 per cent. of
iron in it. From this circumstance it would seem doubtful whether iron
is an essential element. As carbone is known to be exhibited in various
forms of aggregation, it is not improbable that plumbago may be one of
those forms; it is evidently not a mere mixture of common charcoal and
iron, or its oxide.
_Cast iron_ or crude iron is the metal when first extracted from the
ore; it usually contains carbone, oxygen, phosphorus and silica, in
small proportions, with perhaps other earths occasionally. It cannot
be considered as having these elements united in definite proportions;
for they vary much, and probably give to crude iron its several
modifications. Cast iron contains about 80 per cent. of its weight
of iron in a state capable of solution in dilute sulphuric acid, and
yielding a corresponding quantity of hydrogen gas. The residue, in
a specimen I examined, was nearly as magnetic as iron itself. When
treated with boiling muriatic acid, the insoluble part was reduced to
2½ per cent. upon the original weight of the iron, and some hydrogen
gas given out. It was then about as magnetic as the common black oxide
of iron; when heated it assumed a glowing red and lost nearly ½ grain;
it was still magnetic, and boiling muriatic acid extracted more iron
from it.
The hydrogen gas from dilute sulphuric acid and cast iron contains no
carbonic acid in my experience; neither does it yield any when exploded
with pure oxygen gas.
The small residuum after treating cast iron with acids was found by
Bergman and others to resemble plumbago, being constituted chiefly of
carbone and iron.
From the above it would seem that cast iron consists chiefly of pure
iron, with the addition of very small proportions of oxygen and
carbone; the oxygen may be about 1 per cent. and the carbone about 2.
These proportions, though sufficient to modify the properties of iron
to a certain extent, can scarcely be considered as constituting cast
iron a homogeneous mass.
_Steel._ This most important modification of iron has engaged the
attention of many chemists and metallurgists. It may be procured, but
not equally pure, by different methods. One is to keep the cast iron
for a considerable time in fusion and in a very high degree of heat;
whilst its surface is covered with melted scoriæ, so as to preclude the
contact of the atmosphere with the iron. This, it is conceived, gives
time for the carbone and oxygen to combine and escape in the form of
carbonic acid. This steel is of inferior purity.
Steel of cementation is made by stratifying bars of pure iron with
charcoal powder in large earthen crucibles, carefully closed up with
clay. These are exposed to a high degree of heat in a furnace for 8
or 10 days. This is called _blistered_ steel, from the appearance of
blisters on its surface.
Cast steel is made from blistered steel by breaking the bars and
putting them into a large crucible with pounded glass and charcoal. The
crucible is closed with a lid of the same ware and placed in an air
furnace. When the fusion is complete the metal is cast into ingots.
This is the most valuable and probably the purest steel.
When steel is heated red and plunged into cold water, it is _hardened_;
that is, it becomes much harder than iron or than steel without this
operation. Hardened steel is brittle, and cannot be extended by the
hammer or corroded by a file till it is again softened by being heated
and then gradually cooled.
One of the most remarkable properties of hardened steel is that of
being _tempered_, as it is called; by which it is adapted to the
different purposes of the manufacturing artists. Tempering consists
in heating the hardened steel till it acquires a straw colour for
edge tools, a blue colour for watch springs, and elastic articles in
general; &c. &c.
Hardened steel is qualified to acquire magnetism, and to retain it so
as to become a permanent magnet. This power of retaining magnetism
distinguishes steel from pure iron.
From the above account of steel, it is evident there is an essential
difference between it and pure iron. That difference consists,
according to the common opinion, in steel being a _carburet_ of iron,
or carbone and iron united. The fact of the union of carbone and iron
in the formation of steel does not seem to me satisfactorily proved.
Mr. Collier asserts that iron gains about ¹/₁₈₀th of its weight by
being converted into steel.[18] But Mr. Mushet found that though steel
gains weight upon the iron when copiously imbedded in charcoal, yet it
loses weight if the charcoal is only ¹/₉₀ or ¹/₁₀₀ of the weight of the
iron.[19] The same ingenious gentleman seems to estimate the carbone in
cast steel, from synthetic experiments, to be ¹/₁₀₀th of its weight.
[Footnote 18: Manchester Memoirs, Vol. v. page 120.]
[Footnote 19: Philos. Mag. Vol. xiii.]
From analytic experiments, however, there does not appear reason to
believe that steel contains so much, if any charcoal. Pure steel
dissolved in dilute sulphuric acid gives hydrogen gas containing no
carbonic acid nor oxide, neither is there any appreciable residuum of
any kind in general.
On considering all the circumstances, I am inclined to believe, that
the properties which distinguish steel from iron are rather owing to a
peculiar crystallization or arrangement of the ultimate particles of
iron, than to their combination with carbone or any other substance.
In all cases where steel is formed, the mass is brought into a liquid
form, or nearly approaching to it, a circumstance which allows the
particles to be subject to the law of crystallization. We see that
great change is made in steel by the mere _tempering_ of it, which
cannot be ascribed to the loss or gain of any substance, but to some
modification of the internal arrangement of its particles. Why then
may not its differences from iron be ascribed to the same cause? It is
allowed that steel, by being repeatedly heated and hammered, becomes
iron: that is, it should seem, the change of figure disturbs the
regular arrangement of the particles. And it may be further observed,
in corroboration of the opinion that cast iron is capable of being made
permanently magnetic, from its having been in fusion more probably than
from its near approximation to steel in its component parts. The most
powerful artificial magnets, after being forged of steel, are said to
undergo the operation of steelifying again, before they are hardened
finally to receive the magnetic virtue.
SECTION 17.
METALLIC ALLOYS.
When two or more metals of different specific gravities are melted
together and intimately mixed, they frequently enter into chemical
union and form a new compound, called an alloy of the metals. These
alloys often possess important properties which their constituents
singly do not, and hence become valuable acquisitions to the arts.
The metals thus combined may be fused together in any proportion; but
if one of them greatly exceed the other in specific gravity, their
intimate union is sometimes rendered difficult and even impracticable,
partly from the weak affinity and partly from the gravitating principle
causing the metal of least specific gravity to arise to the surface.
Notwithstanding this union of metals in seemingly indefinite
proportions, there are only a few proportions in which the alloys
possess peculiar excellences so as to entitle them to the attention of
artists. These proportions have in many instances been discovered by
experience; and it only remains for theory to point out the reason for
such proportions, and to suggest other proportions which may bid fair
to possess desirable qualities, and thereby diminish the unsuccessful
attempts for improvement in these combinations.
That the metals thus alloyed constitute true chemical compounds and not
merely mechanical mixtures, may be inferred from the change made in
their primary qualities; such as
1. _Tenacity_, _hardness_, &c. Some alloys are
much superior to their ingredients in tenacity and hardness,
whilst others affect a kind of medium between them. This
last is often the case too in regard to ductility and
malleability.
2. _Fusibility._ Several alloys fuse at temperatures
intermediate between the fusing temperatures of their
ingredients, but mostly lower than the mean; there are
others which fuse below the temperature of the lowest, and
few if any require a temperature above the mean for their
fusion.
3. _Colour._ In many cases the colour of alloys is such
as would be produced by the mixture of the colours of the
metals; but in others, remarkably different; for instance,
the alloys of copper and zinc,--forming the various kinds of
brass.
4. _Specific gravity._ This is not always what might be
inferred from a mixture of the two ingredients. Sometimes
it is greater and other times less; but this is not a
decisive mark of chemical union, as the same metal varies
in specific gravity, by hammering, rolling, tempering, &c.
very considerably. Besides, it is more than probable that
the differences said to have been observed, have in some
instances arisen from inaccurate experiments; as it is a
delicate operation to find the specific gravity of small
pieces of metal with sufficient precision for comparisons of
this kind.
Many of the simple metals, when fused and exposed to the air for some
time, without a covering of charcoal, or some similar principle,
acquire less or more of oxygen, and retain it even in a fluid state,
as is proved from Mr. Lucas’s interesting communication in the 3d Vol.
of the Manchester Society’s Memoirs (new series). Hence by frequent
fusions of the same metal its quality becomes impaired in regard to
tenuity and other properties.
This is more eminently the case with regard to alloys. Thus, zinc
at the temperature in which brass melts is combustible; and hence a
portion of it escapes by combustion. Hence the proportions of brass are
changed less or more at each fusion, unless fresh zinc be added. The
same observation applies to alloys of copper and tin with regard to
the tin. The mixtures of lead, tin, bismuth and other soft and easily
fused metals, are still more remarkable in this respect. They should be
fused under a cover of oil or tallow in order to keep them of the same
proportions; otherwise, some of them, particularly the tin, is liable
to great oxidation, and no two successive fusions will present the
same alloy. Hence in some degree the use of fluxes in metallurgy which
serve to cover the surface of the metals and prevent oxidation from the
atmosphere.
When an alloy is made, it seldom happens that the metal is perfect
and compact the first fusion; it is more or less porous, especially
when the two metals fuse at very different temperatures. By a second
fusion, which usually takes place at a much lower temperature than that
requisite for the first, the metal becomes compact and free from pores.
This is particularly the case with speculum metal; and I have little
doubt it is so with regard to many other alloys.
_Alloys of Gold with other Metals._
Gold unites with many of the metals by heat, and forms various alloys,
on which it may be proper to make a few remarks.
1. _Gold with platina._ Platina in a small proportion changes the
colour of gold towards white. 1 part to 20 gold makes it much paler.
1 to 11 gives it the colour of tarnished silver. 1 part with 4 of
gold has much the appearance of platina. The colour of gold does not
predominate till it becomes ⁸/₉ of the alloy. The alloy of 1 platina
and 11 gold is very ductile, and elastic when hammered. _Lewis.
Klaproth. Vauquelin._
2. _Gold with silver._ These two metals may be combined in almost any
proportion by fusion and proper treatment. Homberg found that when
equal parts of gold and silver are kept in fusion for a quarter of an
hour and then cooled, there were two masses, the uppermost pure silver,
the undermost an alloy of 5 parts gold and 1 silver. 1 part silver to
20 gold produces a sensible whiteness in the alloy. 2 parts gold and 1
of silver are stated to form the alloy of greatest hardness; this will
consist of 3 atoms of gold to 1 of silver.
3. _Gold with mercury._ See amalgams.
4. _Gold with copper._ Gold and copper form an alloy by fusion
together. 11 parts gold and 1 copper form the alloy used for gold coin.
The copper heightens the colour of the gold, and makes it harder and
less liable to wear. The current gold coin, however, usually contains
both silver and copper, but the weight of both does not much exceed
one twelfth of the whole. According to Muschenbroeck the maximum of
hardness is when 7 parts of gold and 1 part of copper are united. This
corresponds nearly to 6 atoms of gold and 1 of copper, the atom of gold
being estimated at 66 and that of copper at 56.
Other alloys of gold besides the above standard is that for watch
cases, which must contain at least ¾ pure gold. Watch chains, and
trinkets, are usually made of inferior alloy, called jewellers gold,
which is under no control. It rarely contains less than 30 per cent. of
pure gold.
5. _Gold with iron._ Gold and iron may be united by fusion in various
proportions. 11 parts gold and 1 iron form a ductile alloy which may
be rolled and stamped into coin. Its specific gravity is 16.885. The
colour is a pale yellowish gray approaching to white. The alloy is
harder than gold. When the iron is three or four times the weight
of gold, the alloy has the colour of silver. This last compound is
constituted of 1 atom of gold and 8 of iron nearly. _Lewis. Hatchett._
6. _Gold with nickel._ Mr. Hatchett fused 11 parts gold and 1 nickel
together, and obtained a brittle alloy of the colour of fine brass.
7. _Gold with tin._ Gold combines with tin and forms a brittle alloy.
10 parts gold and 1 tin form a pale alloy and less ductile than gold.
One fiftieth of tin does not materially injure the ductility. Heat, up
to a visible red, does not impair the alloy; but beyond that the tin
fuses and the alloy falls to pieces. _Hatchett._
8. _Gold with lead._ The effect of uniting even a very small proportion
of lead to gold is remarkable. When the alloy contains ¹/₂₀₀₀ part
of lead, it is brittle like glass. The vapour of fused lead in close
vessels is sufficient to injure gold. _ibid._
9. _Gold and zinc._ These two metals combine in almost any proportion.
When 11 parts gold and 1 zinc are alloyed, the compound is of a pale
greenish yellow like brass, and very brittle. Equal parts of these
metals form a very hard, white alloy, susceptible of a fine polish.
_ibid._ & _Hellot._
10. _Gold and bismuth._ Gold unites with bismuth, but the colour is
injured and the ductility of the alloy destroyed by a very small
portion of the latter metal, the same as with lead. _ibid._
11. _Gold and antimony._ These metals combine and produce a brittle
alloy, much of the same kind as those with bismuth and lead. _ibid._
12. _Gold and arsenic._ There seems a considerable affinity between
gold and arsenic, but the volatility of arsenic in the fusing
temperature of gold renders it difficult to bring them into contact.
A very small proportion of arsenic makes the alloy brittle, and this
property increases with the arsenic. _Hatchett._
13. _Gold with cobalt._ These unite and form a brittle alloy, even when
the cobalt only makes ¹/₆₀ of the compound. _ibid._
14. _Gold and manganese._ Gold and manganese may be united, and the
alloy is very hard and less fusible than gold. One alloy was found to
consist of 7 or 8 parts of gold and 1 of manganese. _ibid._
_Alloys of Platina with other Metals._
1. _Platina and silver._ It does not appear very clear that these two
metals combine by fusion; at least if they do, the difference in their
specific gravities is sufficient to overcome their affinity.
2. _Platina and mercury._ See amalgams.
3. _Platina and copper._ These two metals unite with difficulty by a
strong heat and form a malleable alloy. This alloy has been preferred
for specula for telescopes, as it is hard, polishes well, and is not
liable to tarnish. _Lewis._
4. _Platina and iron._ Platina and soft or pure iron do not seem to be
easily combined by heat, by reason of the infusibility of iron. But it
combines with cast iron and steel by heat. The alloy is very hard, and
in some decree ductile when the iron forms ¾ of the alloy. _ibid._
5. _Platina and tin._ Equal parts of platina and tin unite by fusion,
and form a dark coloured brittle alloy. But when the platina falls
short ⁷/₉ of the alloy, the ductility and whiteness proportionally
increase. _ibid._
6. _Platina and lead._ These two metals may be combined in various
proportions by heat; but the compounds are not stable, part of the
platina falling down, when the alloy is subsequently melted. _ibid._
7. _Platina and zinc._ Platina may be combined with zinc, by being
exposed to the fumes of the metal as reduced from its ore. Three parts
of platina become four of alloy. It is hard, brittle, of a blueish
white colour, and easily fusible. _ibid._
8. _Platina and bismuth._ Platina and bismuth combine readily in a high
temperature in almost any proportions. The alloys are brittle. _ibid._
9. _Platina and antimony._ Platina easily combines with antimony by
heat. The alloy is brittle. _ibid._
10. _Platina and arsenic._ When white oxide of arsenic is projected
upon strongly heated platina, an imperfect union takes place with a
partial fusion of the mass; it is brittle, of a greyish colour and a
loose granulated texture. _Lewis._
_Alloys of Silver with other Metals._
1. _Silver with mercury._ See amalgams.
2. _Silver with copper._ Silver and copper are easily alloyed in any
proportion by fusion. The compound is harder than silver, and retains
its white colour when the copper is half of the alloy or more.--The
silver coin is a compound of 12⅓ silver and 1 copper, which nearly
corresponds to 8 atoms of silver and 1 of copper. The hardest alloy is
said to be when 5 silver unite to 1 copper; that is, 3 atoms of silver
and 1 of copper.
3. _Silver with iron._ The alloys of silver and iron have not been very
minutely examined. The two metals are said to unite by fusion, but the
iron still retains its magnetism. The alloy is of a white colour, hard
and ductile. When kept in fusion for some time the two metals separate,
but not entirely. These circumstances shew the affinity between silver
and iron to be weak.
4. _Silver with tin._ Silver and tin form a hard brittle alloy, which
is of little if any use. The modifications arising from various
proportions have not been particularly investigated.
5. _Silver and lead._ Silver and lead unite in any proportion and form
a brittle alloy of a lead colour. The union is not very intimate; for
when urged by heat the lead parts from the silver, as in the process of
cupellation.
6. _Silver and zinc._ These two unite and form a brittle alloy of
a blueish white colour. The proportions have not been particularly
noticed.
7. _Silver and bismuth._ Silver and bismuth readily unite by heat. The
alloy is brittle and its colour inclines to that of bismuth.
8. _Silver and antimony._ These metals unite by fusion and form
a brittle alloy, which does not seem possessed of any remarkable
properties.
9. _Silver and arsenic._ These two metals unite according to Bergman,
the fused silver taking up ¹/₁₄ of its weight of arsenic; the alloy
corresponds nearly to 3 atoms silver and 1 arsenic. It is brittle and
of a yellowish colour.
_Alloys of Mercury and other Metals: Amalgams._
The alloys of Mercury with the various metals have been commonly
denominated amalgams.
1. _Mercury and gold._ Gold amalgamates pretty easily with mercury and
forms an alloy much used in gilding metals. For this purpose six parts
of mercury may be heated nearly to the ebullition of the liquid, and
one part of pure gold in thin plates may be gradually added. In a few
minutes the whole becomes one fluid mass of a yellowish white colour.
It is constituted of 1 atom of gold and 2 of mercury. By squeezing it
through leather one half of the mercury is separated nearly pure, and
the other remains combined with the gold, and forms a soft white mass,
consisting of 1 part gold and 2½ mercury nearly, which is the alloy of
1 atom to 1, and may be subsequently used for gilding. A ready way of
making this amalgam I find is to put 3 parts of gold, precipitated by
green sulphate of iron, to 8½ or 9 parts of mercury; by a few minutes
trituration the whole becomes a fine crystalline amalgam.--When this
amalgam of gold is exposed to a heat just below red, the mercury
sublimes and leaves the gold; hence its use in gilding.
2. _Mercury and platina._ These two metals may be combined, but not
very easily, as little affinity seems to exist betwixt them. This is
manifest from the circumstance that platina wire may be long immersed
in mercury without any sensible effect. An union may be produced by
immersing thin platina foil into boiling mercury for some time; also by
triturating the ammonio-muriate of platina with mercury and exposing it
to a due heat. The proportions have not been determined.
3. _Mercury and silver._ Silver and mercury have a considerable
affinity and are easily combined by putting lamina of silver into
heated mercury and agitating the mixture. When 1 part silver and 2
mercury are mixed as above, a fluid mass is obtained which being heated
to the temperature of boiling mercury, a little mercury evaporates
and the remainder crystallizes into a soft white mass, which in time
grows hard and brittle. A higher heat than boiling mercury expels the
mercury. Hence this amalgam may be used for giving a thin coating of
silver to the surface of metals, like that of gold. The compound is
evidently one atom of silver (90) with one of mercury (167).
4. _Mercury and copper._ I have made several unsuccessful attempts to
combine mercury and copper.
When a plate of copper is kept immersed in mercury for some time, the
mercury adheres to its surface in a small degree and is not easily
rubbed off; the plate is rendered brittle by it and the fracture has a
brilliant mercurial appearance; but a low red heat expels the mercury
and the copper resumes its colour and tenacity, with scarcely any loss
of weight, being only about 5½ per cent. in two or three trials.
Recently precipitated copper in powder, dried and triturated with
mercury, produced no union. Neither did Dutch-leaf (which is copper
with a very little zinc) unite with mercury by trituration. Mercury
precipitated from deutonitrate by a plate of copper gave pure running
liquid. The plate of copper appeared as if it had been immersed in
mercury, was brittle with a shining fracture, but recovered its colour
and texture by heat, and lost scarcely any weight.
The method recommended by Boyle was tried: 2½ parts of crystallized
verdigris, 2 parts of mercury and 1 of common salt, were triturated
together till the mercury disappeared, the powder was then digested
awhile with vinegar over a fire and frequently stirred. The mass was
then put on a filter and dried. It contained a little fluid mercury,
but was chiefly composed of acetate of copper and oxide or muriate of
mercury. The liquid contained acetate of copper and muriate of soda.
From the above it is manifest that mercury has some chemical action
upon copper; but it has not yet been found, I apprehend, that the two
metals unite so as to form a proper amalgam.
5. _Mercury and iron._ These two metals have little if any affinity for
each other. I do not know that any chemical combination of them has
ever been formed.
6. _Mercury and tin._ These two metals readily combine, especially if
assisted by heat. I heated 52 parts of tin and 167 of mercury together,
that is, 1 atom of each, till they united in a fluid mass. The amalgam
crystallized in about 180°. By hard pressure in the hand nearly 50
parts of fluid mercury were separated from the amalgam when cool,
containing in appearance very little tin. After this an amalgam was
formed of 104 parts of tin and 167 mercury (2 atoms tin to 1 mercury);
this congealed about 230°, and remained a hard, dry, crystalline
substance, agreeing in appearance with that which adheres to mirrors.
For the purpose of silvering mirrors however much more mercury is
employed than is indicated by the above proportion; but after the glass
is slid upon the tinfoil previously covered with mercury, a great
pressure is applied, which expels the superfluous mercury nearly in a
state of purity.
7. _Mercury and lead._ To 90 parts of lead I put 167 of mercury (1 atom
of each); they united in a moderate heat and crystallized in about
180°. In a few days the mercury partly separated from the amalgam, and
56 parts were squeezed out, the whole was then put together with 90
parts more of lead (now 2 atoms lead to 1 mercury), and fused together;
the amalgam crystallized in about 200°, and remained in a solid uniform
mass.
8. _Mercury and zinc._ When 29 parts zinc and 167 mercury (1 atom
to 1) are heated together, they combine and form an amalgam which
crystallizes about 200°. A little of the mercury may be squeezed out
when cold. By putting 29 parts more of zinc (2 atoms to 1) we obtain an
amalgam which fuses considerably above 200°, and when cooled becomes a
permanent hard crystalline mass.
9. _Mercury and bismuth._ When 62 parts bismuth are fused with
167 mercury (1 atom to 1), the compound remains fluid at common
temperature, but crystallizes partially by standing; about ⅓ of the
weight may be poured off like fluid mercury. If we put 62 bismuth more
to the whole (so as to be 2 atoms to 1), the fluid amalgam crystallizes
about 150 or 180°: the mass is soft however and by pressure one may
squeeze out about 20 per cent. of a fluid amalgam. If we put 62 more
bismuth (so as to be 3 atoms to 1), then the compound crystallizes
between 200 and 300° into a darkish coloured granular soft mass which
continues without any change. Higher than this of bismuth I have not
examined.
10. _Mercury and antimony._ Antimony is said to form a feeble
union with mercury, which is soon loosened by time. I made several
unsuccessful trials to combine these two metals, which it seems
unnecessary to detail, as the compound when formed is no ways
interesting.
11. _Mercury and arsenic._ On the authority of Lewis an amalgam of
mercury and arsenic may be made by keeping them over the fire for some
time and constantly agitating the mixture. It is grey-coloured, and
composed of 5 parts of mercury and 1 of arsenic.
Most of the other metals are incapable, as far as is known, of
combination with mercury, excepting potassium and sodium considered
as metals, which combine with mercury; but these alloys are of little
interest, and the proportions have not been particularly investigated.
_Triple, quadruple, &c. Amalgams._
Besides those amalgams which are formed of mercury and each single
metal, there are others formed of mercury and alloys of two or
more metals, which in some instances possess properties differing
essentially from mere mixtures.
1. _Mercury with bismuth and lead._ When the amalgam formed of 2 atoms
bismuth and 1 of mercury is mixed with that formed by 1 atom of lead
and 1 of mercury, in such proportion that the mercury is the same in
both, the two powders, though dry and crystalline at first, soon become
a permanently fluid amalgam by trituration. The liquid in running along
_drags a tail after it_, and is disposed to separate into portions
less and more fluid, but the most fluid part is much inferior to pure
mercury in this respect. Specific gravity of the amalgam, 11.
2. _Mercury with fusible metal composed of 7 bismuth, 5 lead and 3
tin._ A mixture of 4 parts fusible metal with 5 parts mercury compose
the most fusible amalgam with a minimum of mercury that I have found.
It is formed of 2 atoms bismuth, 1 lead, 1 tin and 2 mercury. Its
specific gravity is 12.
3. _Mercury, zinc and tin._ This amalgam is found the most effectual
for the excitation of electric machines. Mr. Cuthbertson recommends
1 part zinc, 1 tin and 2 of mercury for the plate machine amalgam.
But for a cylinder the best amalgam I have made contains more than
twice the above portion of mercury. I form an alloy of 58 parts zinc
and 52 tin, (2 atoms to 1). To this alloy I add 250 mercury, and fuse
the mixture; the liquid mass crystallizes about 222° into a white,
moderately hard amalgam. This is pulverized in a mortar and mixed up
with ¹/₁₂ of its weight of hog’s lard. A small portion then is spread
upon a piece of leather and applied to the machine when in action. It
is probable however that a harder and less unctuous amalgam may be
better adapted to the plate machine. This amalgam of mine consists of 4
atoms of zinc, 2 of tin and 3 of mercury.
I have tried the amalgams of zinc and tin separately and find that they
answer for electric excitation as well as when combined. They ought to
be formed of 2 atoms zinc and 1 of mercury (58 parts to 167), and of 2
atoms tin and 1 of mercury (104 parts to 167). If we choose to combine
them, we have only to take 2 parts of the zinc amalgam and 1 of the tin
amalgam and triturate them together.
Bismuth amalgam is not good for electric excitation; lead amalgam is
better; but they are much inferior to those of tin and zinc.
_Alloys of Copper with other Metals._
1. _Copper and iron._ These two metals may be united with difficulty by
heat; but the compound possesses no useful property.
2. _Copper and nickel._ A white, hard, brittle alloy is said to be
formed by combining these two metals. The alloy is scarcely known.
3. _Copper and tin._ The metals of copper and tin, may be fused
together and united in almost any proportion by skilful treatment;
but it is found that only a few of the proportions constitute alloys
possessing properties eminently valuable to the arts.
The alloys of copper and tin are commonly called _bell-metal_; but they
receive more particular names according to the purposes for which they
are destined, as _bronze_, _speculum metal_, _gun-metal_, &c. those of
them which are yellow are frequently confounded in common language with
brass, as _brass guns_, &c. Indeed the ancient Greeks and Romans seem
to have been in possession of these two alloys, under one and the same
name. The =χαλκος= of the Greeks, being used for cutting-instruments,
must have signified _bell-metal_, or the alloy of copper and tin as
well as brass, as indeed is proved by the analysis of them. The _æs_
of the Romans seems also to have included the same compound. Ancient
copper coins too are usually found to contain tin.
Tin united to copper in certain proportions gives a surprising
degree of hardness and tenacity to the alloy, much superior in these
respects to either of the ingredients. In other proportions it makes
the compound highly sonorous, as in _bell-metal_ properly so called.
Tin also increases the fusibility of the compound in proportion as it
abounds, being itself fusible at the low temperature of 440° Fahrenheit.
The principal varieties in the alloys of copper and tin are enumerated
below, beginning with those in which the copper is most abundant.
The atom of copper is taken at 56 and that of tin at 52 weight, the
hardness of these metals is denoted by 7.5 and 6 respectively, by
Kirwan.
(_a_). _Gun-metal._ The alloy for brass guns or cannon is made of 100
parts of copper and 11 or 12 of tin. A small portion of iron is found
to improve the metal; this is best added in the state of tin-plate,
as it more readily fuses and unites with the metal.[20] This compound
is hard and extremely tenacious, exceeding in this respect any other
alloy of the two metals. The addition or subtraction of 1 or 2 parts of
tin materially impairs the tenacity of the alloy. It is constituted of
8 atoms of copper and 1 of tin.
[Footnote 20: See a very excellent essay on the alloy of copper and tin
by M. Dussaussoy, in the Annales de Chimie & Physique. 5--113.]
(_b_). _Alloy for edge tools, printers’ cylinders, &c._ The best
proportion for this compound seems to be 100 parts copper and 15 or
16 tin. When hammered and tempered duly it is fit for making edge
tools not inferior to some kinds of steel. It is a compound of greater
density than the preceding, though containing more tin; the grain
is fine and the metal free from blisters and suited for turning in
the lathe. It seems to be the best alloy of the kind for printers’
cylinders; but an analysis which I lately made of some turnings from
one of these cylinders gave me much less tin than the above proportion.
The alloy (_b_) is constituted of 6 atoms of copper and 1 of tin.
(_c_). _Alloy for the Chinese gong, cymbals, &c._ An alloy formed of
100 parts copper and 23 tin, appears from Dussaussoy’s experiments to
form the compound of minimum density. It is used for making cymbals;
and nearly accords with the composition of the Chinese gong. It is
formed of 4 atoms of copper and 1 of tin. The Chinese gong analysed by
Klaproth was composed of 100 copper and 28.2 tin; that by Dr. Thomson
of 100 copper and 23.4 tin.
(_d_). _Common bell-metal used for casting bells._ This alloy is
commonly made of 3 parts copper and 1 of tin; but to be in due
proportion for 3 atoms of copper and 1 of tin, it should be formed of
100 copper and 31 tin. It is hard, of a white colour, less malleable
than the preceding alloys, and more sonorous. A specimen I analysed
consisted of 100 copper and 36 tin. The exact proportion of 100 copper
and 31 tin is not essential to produce a sonorous alloy.
(_e_). _Speculum metal._ This compound has been investigated with great
care by opticians. According to Mr. Mudge the best proportion is 32
parts copper to 14.5 tin, but Mr. Edwards finds 15 parts tin, 1 brass,
1 silver and 1 arsenic. The slightest variation in the proportions of
copper and tin impairs the metal. The alloy is white, hard and close
grained; it takes a beautiful polish. The use of the minute portions
of zinc, silver and arsenic is perhaps to correct the colour of the
alloy; though it seems in several alloys that very minute portions of
metals apparently foreign to the alloy, improve the density and texture
of the metal. It is remarkable with what precision this alloy accords
with the atomic combinations of 2 copper with 1 tin. By calculation 32
copper would require 14.8 tin. Mr. Mudge finds 32 copper to 14½ tin,
and observes that if ½ a part more of tin be added the metal is too
hard. Mr. Edwards indeed says 32 copper and 15 tin; but then he adds
1 part brass, which containing ⅔ of a part of copper, it reduces his
proportion to 32 copper and 14.7 tin, almost exactly that required by
the theory. When 32 copper and 13½ tin are combined, Mr. Mudge asserts
the metal is too soft.[21]
[Footnote 21: This author obtained the Royal Society’s gold medal for
his essay on the composition, &c. of specula for telescopes. Philos.
Transact. 1787.]
(_f_). _Copper and tin, equal parts._ This alloy is of blueish white
colour, and of no particular use that I am acquainted with. It consists
of the union of 1 atom of copper with 1 of tin.
The other alloys of copper with a higher proportion of tin appear to be
uninteresting, and have not been objects of much attention.
* * * * *
Not having an opportunity of forming these alloys synthetically, I
contented myself with the analysis of several of them.
The mode of analysis I adopted with compounds of copper and tin, is
simple and easy. The alloy is treated with nitric acid, which dissolves
the copper, and on being diluted with water throws down the tin in
the state of deutoxide. This last is collected on a filtre, dried,
and heated to a low red; then ²⁶/₃₃ of this is allowed for the tin
(the other 7 parts being oxygen); and the rest of the alloy may be
considered as copper. But if thought proper the copper may be thrown
down by immersing a plate of lead in the solution, which succeeds
better than a plate of iron in nitric solutions of copper.
4. _Copper and lead._ Copper unites with boiling lead and forms a grey
brittle alloy of granular texture. This alloy being heated above the
melting point of lead, causes the last metal to run off, leaving the
copper nearly pure. The alloy is scarcely of any use.
5. _Copper and zinc._ Copper and zinc combined form _brass_, one of
the most useful of all alloys. Though this is a general name for such
combinations, yet several of the proportions form compounds to which
peculiar names are given, some of which will be noticed below.
It may be proper to remark that copper is estimated by Mr. Kirwan
at 7½° in hardness, whilst zinc is 6½. The former metal is highly
tenacious and malleable; the latter is brittle and malleable only in
a small degree. According to Lewis a very small proportion of zinc
dilutes the colour of copper and renders it pale; when the copper
has imbibed ¹/₁₂ of its weight, the colour inclines to yellow. The
yellowness increases with the zinc till the weight of that metal in the
alloy equals the copper. Beyond this point if the zinc be increased the
alloy becomes paler and paler and at last white, like zinc.
The tenacity of brass is greater than that of either copper or zinc
according to Muschenbroek. His experiments give brass nearly twice as
strong as copper, and 18 times as strong as zinc. It seems to me most
probable that the tenacity of brass increases with the increase of zinc
in the alloy to a certain proportion, when it becomes a maximum, and
thence diminishes with the further increase of zinc, but experiments
are yet wanting, I presume, to ascertain what proportion of the two
metals must be taken to form the alloy of greatest tenacity. The
same observation may be made as to the maximum hardness; it is not
improbable that the two maxima may be found in different kinds of
brass.
The point of temperature at which copper fuses is stated to be 27° of
Wedgwood’s thermometer, whilst that of zinc is much lower, namely, 680°
of Fahrenheit. Common brass is stated to melt at 21° of Wedgwood. It is
very probable that all kinds of brass melt at temperatures intermediate
between those of copper and zinc; and that the more of zinc the
lower will be the fusing temperature; but there have not been direct
experiments to ascertain the degrees, as far as I know.
In enumerating the different proportions of such alloys as have come
under my notice I shall begin with that containing the maximum of
copper, and proceed in gradation to that with the maximum of zinc.
(_a_). _Brass for the manufacture of plated goods._ This alloy is
composed, judging from one specimen I analysed, of 12 atoms of copper
and 1 of zinc; or of nearly 28 parts of copper by weight and 1 of zinc.
The atom of copper is here estimated at 56 and that of zinc at 29, or
very nearly ½ that of copper. This alloy had much the same qualities
apparently as copper itself, only a little more yellow.
(_b_). _Dutch gold, gilding metal._ This is the alloy which may be
beaten out into thin leaves, after the manner of gold leaf. I have not
been able to find any proportions for this compound in books. It seems
to have been kept as a secret by the manufacturers. By analysis however
I find it composed of 6 atoms of copper and 1 of zinc, or nearly 12
parts copper and 1 zinc by weight. This alloy is probably the most
malleable of all the kinds of brass. A leaf containing 12 square inches
weighs about ⁷/₁₀ of a grain. The colour, as is well known, makes a
good approach to that of gold. It is the composition used for making
articles to be gilt, as buttons, &c.
(_c_). _Dipping metal for stamped brass goods._ This is a well known
article of Birmingham manufacture. It is an alloy both tenacious and
malleable, as is manifest from the perfection of the articles. It
possesses a beautiful gold colour. A specimen was composed, by my
analysis, of 4 atoms of copper to 1 of zinc; or of 8 lbs. of copper and
1 of zinc; or of 4 lbs. copper and 3 of common brass; but it is varied
according to the colour wanted.
(_d_). _Soft, fine coloured brass._ According to M. Sage, a very
fine kind of brass may be made by mixing oxide of copper, calamine,
black-flux and charcoal powder together and fusing the mixture in a
crucible till the blue flame disappears. The brass is found to weigh ⅙
more than the copper resulting from the weight of oxide. He says when
the copper retains ⅕ of zinc the colour is not so fine; and the excess
of zinc will be burned off by heat, but the zinc cannot be reduced by
burning below ⅙; so that this appears to be a natural limit. Hence
this compound, being formed of 6 parts copper and 1 of zinc, must be
constituted of 3 atoms of copper and 1 of zinc.
(_e_). _Soft brass preferred for watch movements._ There is a kind
of brass greatly preferred by watch-makers on account of its working
well with steel. I have not met with a specimen; but Dr. Thomson has
analysed one and found it to consist of 2 atoms of copper and 1 of
zinc;[22] or 4 parts copper and 1 of zinc by weight nearly.
[Footnote 22: An. of Philos. Vol. 12.]
(_f_). _Common hard brass._ This constitutes the great bulk of brass,
as manufactured in the large way. It is made by exposing granulated
copper, calamine, that is, a native oxide of zinc, and powdered
charcoal in mixture to a red heat for some hours, and then increasing
the heat so as to melt the compound of copper and zinc, the charcoal
having carried away the oxygen of the calamine. The metal is then cast
into ingots or plates as may be required. This is called brass of
cementation as distinguished from the other species, which are usually
made from this by fusion with copper or zinc as the case requires.
It is found that 40lbs. of copper with 60lbs. of calamine yield 60 lbs.
of brass; hence a great part of the zinc burns away during the process.
The brass thus resulting, consisting of 2 parts of copper and 1 of
zinc, is of course constituted of 1 atom of each metal united together.
Common brass is malleable, when cold, like the preceding species;
but probably does not possess that property in so high a degree. It
seems better adapted for turning in the lathe than any other kind of
brass. The specific gravity of this brass before it is hammered or
rolled is generally about 8.1 or 8.2 by my experience. When rolled it
receives a great increase of density, amounting to .5 according to M.
Dussaussoy[23], so that what is 8.2 when cast will be 8.7 when rolled;
or it is condensed nearly ¹/₁₆ of its volume by the operation of
rolling. The same author finds that brass is hardened very considerably
by rolling, but rendered less tenacious; however by being heated and
consequently softened after rolling, it becomes stronger than ever,
and nearly of an intermediate specific gravity between cast and rolled
brass.
[Footnote 23: An. de Chim. & Physique. 5--233.]
(_g_). _Prince’s metal, pinchbeck_, &c. This compound, as far as I can
learn, is usually formed by combining equal weights of copper and zinc,
or by fusing together 3 parts of common brass with 1 of zinc. According
to Lewis the yellow colour of brass is a maximum in this proportion.
The alloy is brittle, or at least much less malleable than common
brass. I find the composition of _spelter_ solder, as it is called, or
that used for soldering both brass and copper, to be nearly equal parts
of copper and zinc. Hence it appears that 1 atom of copper unites to 2
of zinc to form this alloy.
The other alloys of copper and zinc in which the zinc gradually
exceeds the copper, become gradually paler in colour and more brittle.
They do not promise to be of much utility in the arts, and have not
therefore been very particularly investigated by metallurgists.
Besides the binary combinations of copper and zinc and copper and tin,
there are _ternary_ combinations of these metals, namely, alloys of
copper, zinc and tin. For instance, the metal of which common white
buttons are made. I had occasion to analyse a specimen of this metal
and found it to be constituted of 4 parts copper, 1 of zinc and 1 of
tin; or 4 atoms of copper, 2 of zinc and 1 of tin.
It will be proper to subjoin the methods of analysis which I adopted
in regard to brass. Twenty grains, more or less, of the particular
articles were dissolved in nitric acid, and the metals were
precipitated in the state of sulphurets by hydrosulphuret of lime.
The copper is thrown down in the state of a black powder, and the
zinc in that of a white powder turning to grey. Great care was taken
to add the precipitating liquor gradually in order that the copper
might be obtained distinctly from the zinc. The whole of the copper
is thus thrown down before any of the zinc precipitate appears. The
precipitates were collected and dried in a temperature not exceeding
150°, and then weighed. In both cases one third of the weight was
allowed for sulphur, and the remaining two thirds were estimated to
be metal; which is agreeable to the known constitutions of these
sulphurets. Another method I sometimes practised, which also answers
very well; namely, to throw down the whole or greatest part of the
copper by a plate of lead, then to throw down the lead by sulphuric
acid; after this the liquor was tested by hydrosulphuret of lime to
precipitate the copper remaining, if any; and lastly to throw down the
zinc by hydrosulphuret of lime.
6. _Copper and bismuth._ The alloy is brittle and of a pale colour. It
is not much known.
7. _Copper with antimony._ Copper and antimony unite by fusion and form
a violet coloured, brittle alloy.
8. _Copper and arsenic._ These metals unite by fusion in a close
crucible, the surface of the mixture being covered with common salt
to prevent the oxidizement of the arsenic. The alloy is white and
brittle, and is known by the names of _white copper_, and _white
tombac_.
9. _Copper and manganese._ These may be united by fusion, and form a
red coloured, malleable alloy, according to Bergman.
10. _Copper and molybdenum._ These metals may be alloyed in various
proportions, but the compounds exhibit nothing peculiarly remarkable.
_Alloys of Iron with other Metals._
1. _Iron with tin._ These two metals are alloyed with some difficulty
by fusion in a close crucible. The difficulty seems to arise from
the very unequal temperatures at which the metals individually fuse.
Bergman always found two alloys when the metals were fused together;
the one composed of 21 parts tin and 1 of iron, that is, 10 atoms of
tin to 1 of iron; and the other of 2 parts iron, and 1 of tin; that is,
4 atoms of iron and 1 of tin. The first was very malleable, harder than
tin and not so brilliant; the second but moderately malleable and too
hard to yield to the knife.
The formation of common _tin-plate_ is a proof of the affinity of tin
and iron. Thin plates of iron, thoroughly cleaned, are dipped into
melted tin, when the tin adheres to the surface of the iron, forming
with that metal a true chemical union.
2. _Iron and lead_, &c. Iron combines by fusion more or less perfectly
with lead, zinc, bismuth, antimony, arsenic, cobalt, manganese, &c.
but the proportions have in few instances been ascertained, and the
compounds are generally of little importance.
_Alloys of Nickel and other Metals._
_Nickel and arsenic._ As nickel and arsenic are naturally found in
combination, though mostly along with small quantities of other bodies,
it is to be presumed that an affinity subsists between them; but I
do not know that the proportions have been ascertained in which they
unite, or the nature of the alloys.
_Alloys of Tin with other Metals._
1. _Tin with lead._ Tin and lead unite by fusion in any proportion.
This alloy, according to Muschenbroek, is harder and much more
tenacious than either tin or lead, especially when 3 parts tin and 1
lead are its constituents.
I fused various proportions of tin and lead together, as per the
following table, in order to find some of the more prominent
characteristics of the several alloys. The specific gravity of the
tin was 7.2, that of the lead was 11.23; and the portions taken were
such as to combine, 1, 2, or more atoms of tin with 1 of lead. The
several metals were melted and the compounds formed under a few drops
of tallow, otherwise the oxidation is so rapid that the proportions are
disturbed and the quantity of pure alloy is not equal to the weight of
the ingredients. Without this precaution it is no uncommon occurrence
in small experiments to obtain only 3 parts of fusible alloy from 4 of
metal.
Atoms. | Weights | Sp. Gr. by | Sp Gr. by | Fusing
| |calculation.| experim. | Point.
Tin. Lead. | Tin. Lead. | | |
1 + 1 | .58 + 1 | 9.32 | 9.17 | 430°
2 + 1 | 1.16 + 1 | 8.64 | 8.79 | 350
3 + 1 | 1.73 + 1 | 8.25 | 8.49 | 340
4 + 1 | 2.3 + 1 | 8.00 | 8.10 | 345
5 + 1 | 2.9 + 1 | 7.93 | 8.00 | 350
6 + 1 | 3.47 + 1 | 7.81 | 7.90 | 360
From the above table it appears that when 1 atom of tin is united to
1 of lead there is an expansion of volume; but when more than 1 of
tin are combined to 1 of lead there is a contraction of volume, or
the density is above that by calculation. This increase of density is
greatest when 3 atoms of tin are combined with 1 of lead; and it is
not improbable the tenacity may then be a maximum; though Muschenbroek
finds it more tenacious when 3 parts tin are united to 1 of lead, which
answers more nearly to 4 atoms tin and 1 of lead; this opinion is
countenanced by the fact that tin is much the most tenacious of the two
metals taken singly.
It is remarkable that the fusing point of these alloys is below those
of either tin or lead. The lowest of all (340°) is when 3 atoms of tin
are alloyed with 1 of lead.
Common pewter, I find, is an alloy of 4 atoms of tin and 1 of lead
nearly, and fuses about 345 or 350°. This is perhaps the best
proportion; it is hard, tenacious and of a good colour. More of lead
would impair the colour, and more of tin would impair the tenacity and
increase the expence, though it might improve the colour.
Certain articles for family use, such as tea-pots, spoons, &c. are made
of white metal, which commonly, though I apprehend improperly, goes by
the name of _tutenag_. This metal in colour approaches more to silver
than pewter does. A spoon of this description I found to be pure tin.
2. _Tin and zinc._ This alloy is easily made by fusion. The metals seem
to unite in any proportion. I melted together 29 parts zinc and 52 tin
(1 atom of each), and obtained a white hard alloy of about 6.8 specific
gravity. When 2 atoms tin and 1 zinc are united the specific gravity is
6.77, which is below the mean. The alloy appears to be very hard and
tenacious; and probably might be put to some use.
3. _Tin and bismuth._ These metals readily combine by fusion in any
proportion. When 52 parts tin and 62 bismuth are fused together (1
atom to 1), a fine, smooth, hard but brittle alloy is obtained of the
specific gravity 8.42. It fuses at 260°. Two atoms tin and 1 bismuth
give an alloy of 8 specific gravity, which fuses about 320°. The alloy
of 1 atom tin and 2 of bismuth is of 8.67 specific gravity, and fuses
about 260°. The alloy of 3 atoms tin and 1 bismuth is of 7.73 specific
gravity, and fuses at 350°. The alloy of 1 atom tin and 3 bismuth is of
specific gravity 9.14, and fuses at 330°.
4. _Tin with antimony._ This compound is said to be white and brittle
when formed of equal parts. I did not succeed in uniting the two metals
by fusion on a small scale.
5. _Tin with arsenic._ When 15 parts of tin and 1 of arsenic are fused
together the alloy crystallizes in large plates like bismuth, according
to Bayen. It is brittle and less fusible than tin. This alloy must be
composed of 5 atoms of tin and 1 of arsenic, that is, 312 tin and 21
arsenic.
_Alloys of Lead with other Metals._
1. _Lead and zinc._ These two metals seem to have a weak affinity. They
are easily united, or rather mixed, in any proportion by fusion under a
little tallow. But however they may be mixed there is a strong tendency
to separate again, which no doubt is occasioned in part by their great
difference in specific gravity.
I have fused lead and zinc together in various proportions, from 6
parts lead to 1 of zinc, to 1 part lead to 2 of zinc. The compound
usually gives a specific gravity rather greater than the mean; but upon
being broken the fracture is often like that of zinc in one part and
not so in another; and the analysis of fragments proves that a great
difference exists in their composition. Subsequent fusion sometimes
improves the combination and at other times the contrary. Six parts
lead and 1 of tin gave a compound as nearly uniform as any. It was
11 specific gravity, harder and whiter than lead and had much the
appearance of pewter, that is, the alloy of tin and lead.
2. _Lead and bismuth._ These metals alloy well. Three parts lead and 2
of bismuth unite by fusion and form a tenacious alloy which fuses about
340°. Muschenbroek found it ten times stronger than lead. It grows dark
coloured soon by keeping. Its specific gravity by my observation is
10.85, which is rather greater than the mean. It is constituted of 1
atom of each metal, or 62 bismuth to 90 lead.
Three parts lead and 4 bismuth (1 atom lead to 2 bismuth) fuses at
250°. This is the lowest temperature at which any alloy of two metals
fuses. With a little tin it makes the triple alloy which fuses lower
than any other metallic compound, without mercury, as will be shown in
the sequel. The specific gravity of this alloy of lead and bismuth is
10.7, which is greater than the mean.
The alloy of 1 part lead and 2 bismuth (1 atom of lead and 3 bismuth),
fuses at 280°, and is of 10.1 specific gravity, or rather less than the
mean.
The alloy of three parts lead and 1 bismuth (2 atoms of lead and 1 of
bismuth) fuses at 450°. The specific gravity is 11, or rather greater
than the mean.
3. _Lead and antimony._ These two metals combine by fusion in any
proportion. The alloy is of a fine grain and is brittle or flexible
as the antimony or lead prevails. The principal use of this alloy,
I believe, is in the formation of printers’ types. The small types
require a harder alloy or one with more antimony; the large types
have a greater share of lead as being less expensive. On examination
of the different types I find 3 proportions of the alloy principally
in use. The smallest types are cast from a mixture which very nearly
corresponds with 40 parts of antimony to 90 of lead (or 1 atom to 1).
It is hard, has a fracture like steel and is of the specific gravity
9.4 or 9.5 nearly, and fuses about 480 or 500°. The proportions were
determined both by analysis and by inference from the specific gravity
of the metal.
The middle sized types are made of metal composed of 1 atom of
antimony and 2 of lead, or 40 parts antimony and 180 of lead. This
alloy fuses about 450° or 460° and has the specific gravity of 10
nearly.
The largest types or letters of 2 or 3 inches diameter are made of
metal composed of 1 atom antimony and 3 of lead, or 40 parts to 270.
This alloy also fuses about 450 or 460°, which is a very remarkable
fact. Its specific gravity is usually 10.22. After several trials I
could not determine whether the fusing point of this or the preceding
alloy was lower; and equal parts of the two alloys fused together were
liquified at the same temperature of 450 or 460°.
All the intermediate sizes of types appear to be made of one or other
of the three preceding proportions or of mixtures of them, the smaller
the type the more of antimony being required to give the requisite
hardness. The largest types might, I conceive, be made with a much
greater proportion of lead.
When 40 antimony and 360 lead (1 atom to 4) are fused together, the
melting point is about 470°. The specific gravity was found 10.4, but
probably too low from blisters or air bubbles. The alloy was more
flexible than the preceding, but brittle with a fine grained fracture.
Forty parts antimony with 450 lead (1 atom to 5) fused at 490°, and
gave 11 specific gravity. This alloy bends and breaks with a fine
grained fracture.
Forty parts antimony with 540 lead (1 atom to 6) fused at 510°, and
gave 10.8 specific gravity, which in all probability was owing to air
bubbles. Now the alloy soft and malleable.
4. _Lead and arsenic._ When lead is fused in contact with the white
oxide of arsenic under a film of tallow and stirred frequently, an
union of the two metals takes place and the excess of white oxide is
partially converted into arsenic and partly driven off, seemingly
taking with it a portion of the lead. A considerable portion of
the mass assumes the form of a black spongy compound infusible at
the temperature. It contains a portion of the lead and is probably
a compound of the metals with oxygen. The fusible alloy has the
appearance of lead, but is brittle, breaks without bending and exhibits
a fracture like that of antimony and lead. The specific gravity of the
alloy is 10.6, or more if not saturated with lead. By treating it with
an excess of nitric acid it is dissolved, and the lead may be thrown
down by sulphuric acid, and the arsenic acid or oxide by lime. In this
way I find the alloy is composed of about 9 parts of lead with 2 of
arsenic, or 1 atom of each of the metals. The spongy mass treated with
nitric acid yields a similar solution, accompanied with a precipitation
of oxide of arsenic.
5. _Lead and cobalt._ The alloy of these two metals is not easily
obtained, probably from the great difference of the temperature at
which they fuse. Gmelin fused 1 part cobalt with 1, 2, 4, 6 and 8
parts of lead respectively. Alloys were obtained of the specific
gravities 8.12, 12.28 (query 8.28?), --, 9.65 and 9.78 respectively.
From these specific gravities it is plain the lead had been in great
part dissipated by the heat. For the last or greatest specific gravity
corresponds nearly to 2 parts lead and 1 of cobalt. (An. de Chimie,
19--357.)
_Triple Alloys, Solders; Fusible Metal, &c._
Though it may seem premature to treat of triple compounds in the
present chapter, which professedly is limited to compounds of two
elements, yet as the triple alloys are few and so immediately connected
with the preceding, it will scarcely require an apology for introducing
them here.
_Soft solders._ Solders for plumbers and tin-workers, are required
to melt easily, and yet not too low, as they should withstand a heat
greater than boiling water. The fusing point of the soft solders is
usually between 300-400°. Plumbers’ solder I believe is commonly
formed by mixing equal parts of tin and lead. I procured a specimen of
8.9 specific gravity, and its fusing point was 380°. Probably a more
perfect compound would be formed by mixing 104 parts tin with 90 lead
(2 atoms to 1), which would give a specific gravity of 8.8 and the
fusing point 350°.
Tin workers’ solder is made rather more fusible than that of the
plumbers. A specimen I got from the workmen was 8.87 specific gravity
and fused at 345°. A mixture of 3 parts tin and 2 of lead would have
formed an alloy of the same fusibility, but the specific gravity would
have been 8.6 or 8.7 only. Probably a rather less proportion of tin
with a little bismuth entered into the composition.
_Fusible Metal._ Tin, bismuth and lead are metals which melt at
comparatively low temperatures; and it has been shewn that the alloys
of any two of them usually melt at lower temperatures than the mean,
or even than the lower extreme. By analogy it might be inferred that
an alloy of tin and lead fused with one of tin and bismuth, would melt
below either of the two ingredients. It has been shewn that proportions
of bismuth and lead of easiest fusion are 2 atoms bismuth with one of
lead; this alloy melts at 250°. An alloy of 2 atoms of bismuth and 1 of
tin melts at 260°; and so does that of 1 atom bismuth and 1 tin. These
alloys being much more easily fused than any other proportions of these
metals, it is from their combinations we are to expect a still further
reduction of the fusing point. In fact, a combination of either of
the tin and bismuth alloys, with the lead and bismuth alloy, produces
almost exactly the same reduction of the fusing temperature.
Thus if 4 atoms of bismuth, 1 of tin and 1 of lead be fused together,
the compound melts in boiling water or below 212°. It is equally the
case if 3 atoms bismuth, 1 of tin and 1 of lead, are fused together.
The double alloy next to those above mentioned in regard to easy fusion
is that of 2 atoms tin, and 1 bismuth. It fuses at 320°. This alloy,
united to the one of 2 atoms bismuth and 1 lead, gives a compound of 3
atoms bismuth, 2 tin and 1 lead, which fuses very nearly at the same
temperature as the above triple alloys.
In reference to weights, the above proportions for the most fusible
metals will nearly be,
Bismuth 14 parts -- Lead 5 -- tin 3
------- 10 ----- -- ---- 5 ------ 3
------- 5 ----- -- ---- 2½ ------ 3
Most of the elementary books have given the proportions of 8 bismuth, 5
lead and 3 tin; or 5 bismuth 2 lead and 3 tin, which nearly agree with
some of the above, and give an alloy fusing below 212°.
Wishing to investigate this subject more fully, and it being obvious
from the preceding facts that there are only two proportions of tin and
lead to be united with bismuth, to produce the desired effect, namely,
either 1 atom of tin with 1 of lead, or 2 atoms of tin with 1 of lead,
I proceeded as follows:
1 atom tin (52) + 1 atom lead (90) + 1 atom bismuth (62), were fused
together; the fusing point was 270°. The alloy was flexible to a
certain degree; and the fracture very small grained. To this alloy 31
grains of bismuth were added successively till it was evident the alloy
was growing less fusible; the results were as follows:
1 atom tin + 1 lead + 1 bismuth; fuses at 270°
1 -------- + 1 ---- + 1½ ------ -------- 235°
1 -------- + 1 ---- + 2 ------ -------- 205°
1 -------- + 1 ---- + 2½ ------ -------- 200°
1 -------- + 1 ---- + 3 ------ -------- 197°
1 -------- + 1 ---- + 3½ ------ -------- 200°
1 -------- + 1 ---- + 4 ------ -------- 220°
1 -------- + 1 ---- + 4½ ------ -------- 205° semi fluid.
1 -------- + 1 ---- + 5 ------ -------- 240° semi fluid.
but it retains a little fluidity down to nearly 200°
From this it appears that 3 parts by weight of tin, 5 of lead, and any
proportion of bismuth from 7 to 14 will produce an alloy fusing below
212°; but of these the best is 10 or 11 parts.
Again, 2 atoms of tin were combined with 1 of lead and 3 of bismuth, by
gradually adding one half of the tin. The several alloys fused without
any material difference at or below 200°. A further addition of tin
impaired the property as in the above case with bismuth. I did not
think it important to mix 2 atoms of tin and 1 of lead with any other
proportion than 3 atoms of bismuth.
APPENDIX.
Since the publication of the second part of the first volume, (1810)
some important essays on the subject of heat have appeared, which have
a direct bearing upon some points of the doctrine on that subject
inculcated in the said volume. It may be proper to state the results,
with such remarks and reflections as have occurred in the consideration
of them.
In the Annales de Chimie for January 1813, also in the Annals of
Philosophy, vol. 2, we find a Memoir on the specific heat of different
gases, by M. M. De la Roche and Berard. This exhibits a most laborious
and refined series of experiments on this most difficult subject. Great
merit seems to be due to them, both for invention and execution.
It is unnecessary to describe the particulars of the apparatus and the
mode of conducting the experiments, as a description may be found as
above referred. It is sufficient to observe that the _calorimeter_ used
was a copper cylinder of 3 inches diameter and 6 in length, filled with
water, and having a serpentine tube 5 feet in length, running through
the interior and opening at both ends on the outside of the vessels. By
means of this tube a regular current of any gas of a given temperature
(212°) might be passed through the vessel so as to part with its excess
of temperature to the water. The quantity of water and the capacity
of the vessel for heat were previously determined; and the quantity
of heated gas passed through the calorimeter was determinable at any
time, as well as the temperature of the water, from the judicious
arrangements.
It is easy to see that when an apparatus of this kind is at work, the
gas will impart heat, more or less according to its capacity, to the
water; and that the temperature of the calorimeter will gradually
ascend till it arrives at a maximum; that is, till the refrigerating
effect of the surrounding atmosphere upon the calorimeter is equal to
the heating effect of the current of gas.
_The following Table exhibits the results of their experiments._
+----------------+---------------------------------------+
| | Specific Heat |
| | Of the same bulk.| Of the same weight.|
+----------------+------------------+--------------------+
| Air | 1.0000 | 1.0000 |
| Hydrogen | 0.9033 | 12.3401 |
| Carbonic Acid | 1.2583 | 0.8280 |
| Oxygen | 0.9765 | 0.8848 |
| Azote | 1.0000 | 1.0318 |
| Nitrous Oxide | 1.3503 | 0.8878 |
| Olefiant Gas | 1.5530 | 1.5763 |
| Carbonic Oxide | 1.0340 | 1.0805 |
| Aqueous Vapour | 1.9600 | 3.1360[24] |
+----------------+------------------+--------------------+
[Footnote 24: The result for this last article must be considered more
uncertain than any of the previous ones, the experiment being more
complicated.]
They found the specific heats of equal volumes of air of the pressures
29.2 and 41.7 inches of mercury to be nearly as 1 ∶ 1.2396, differing
from the ratio of the pressures or densities, which is 1: 1.358.
The above table of the specific heat of the permanent gases (excluding
aqueous vapour) was corroborated by the results of another series of
experiments in which the principle was varied a little: namely, to find
how many cubic inches of each gas at a given temperature were required
to raise the temperature of the calorimeter a given number of degrees,
and inferring the capacities for heat to be inversely as the quantities
of gas employed. The differences in the results were from 1 to 10 per
cent., which may be considered small, in experiments of such delicacy.
The ratios of the specific heats of several gases being found, it was
highly expedient to find the ratio of the specific heat of water, and
that of some one gas, as common air. This was effected by passing a
small current of hot water through the calorimeter, and comparing
the effect of this current with that of the larger one of air, the
requisite care being taken to ascertain the quantity of water passing
in a given time and its temperature at the ingress. The result of this
experiment was that the specific heat of water is to that of common air
as 1 ∶ .25 nearly. By two other experiments, varied from the above,
results not much differing were obtained, so that the average of the
three gave, water to air, as 1 ∶ .2669.
Reducing the specific heats of the gases to the standard of water as
unity, we have the following Table of the specific heats of equal
weights of the respective bodies:
Water 1.0000
Air 0.2669
Hydrogen 3.2936
Carbonic Acid 0.2210
Oxygen 0.2361
Azote 0.2754
Nitrous Oxide 0.2369
Olefiant Gas 0.4207
Carbonic Oxide 0.2884
Aqueous Vapour 0.8474
Before we animadvert upon these results, it will be expedient to give
an abstract of the not less interesting experiments of Messrs. Dulong
and Petit, on heat, as given in the Annales de Chimie and de Physique,
vol. 7 and 10.
These gentlemen begin by an investigation of the expansion of air by
heat. The absolute expansion of air from freezing of water to boiling
had been previously determined by Gay Lussac and myself to be from 8
to 11 nearly: they however extended the enquiry above and below these
points of temperature, namely to those of freezing and boiling mercury.
From the temperature of freezing mercury or thereabouts, to that of
boiling water, they find the expansion of air to keep pace with that of
mercury, as indicated by the common thermometer; but from the boiling
point of water to that of mercury, the latter expands somewhat more in
a proportion gradually increasing: as by the following Table.
TABLE I.
+------------------------+-----------------+-----------------------+
| | | Temperature by an |
| | | air Thermometer, |
|Temperature by Mercurial| Corresponding | corrected for |
|Thermometer. |volume of a given| expansion of glass. |
| | mass of air. | |
|Fahrenheit.| Centigrade.| | Centigrade. |
+-----------+------------+-----------------+-----------------------+
| -33° | -36°| 0.8650 | -36.8 |
| 32 | 0 | 1.0000 | 0 |
| 212 | 100 | 1.3750 | 100 |
| 302 | 150 | 1.5576 | 148.70 |
| 392 | 200 | 1.7389 | 197.05 |
| 482 | 250 | 1.9189 | 245.05 |
| 572 | 300 | 2.0976 | 292.70 |
| 680 |M. boil 360 | 2.3125 | 350.00 |
+-----------+------------+-----------------+-----------------------+
The absolute dilatation of mercury claims their attention. They quote
nine authorities for the expansion from freezing to boiling water
temperatures; the extremes of these nine are, Casbois ¹/₆₇ of original
volume, and mine ¹/₅₀ of the same. They determine it to be ¹/₅₅.₅.
By doubling and tripling the elevation of the temperature, they made
observations from which are deduced the results of the following Table.
The dilatations are for each degree of the thermometer centigrade, to
which I have added the corresponding ones for Fahrenheit’s.
TABLE II.
+---------------------+-----------------+-------------------------+
| | Mean absolute | Temperatures indicated |
|Temperature by an air| dilatations |by dilatation of mercury,|
| Thermometer. | of mercury. | supposed uniform.[25] |
+---------------------+-----------------+-------------------------+
| Fahr. Cent. | Fahr. Cent. | Fahr. Cent. |
| 32° 0° | 0 0 | 32° 0° |
| 212 100 | ¹/₉₉₉₀ ¹/₅₅₅₀ | 212 100 |
| 392 200 | ¹/₉₉₄₅ ¹/₅₅₂₅ | 400.3 204.61 |
| 572 300 | ¹/₉₅₄₀ ¹/₅₃₀₀ | 597.5 314.15 |
+---------------------+-----------------+-------------------------+
[Footnote 25: That is, the temperature that would be denoted by mercury
inclosed in a vessel having no expansion by heat; or else in one that
expanded in the same rate as mercury.]
By a series of observations on the apparent dilatation of mercury
in glass vessels, compared with the results in the above tables,
they deduce the absolute dilatation of glass for each degree of the
thermometer, and the temperature that would be indicated by supposing
the uniform expansion of a glass rod adopted as the measure of
temperature as under:
TABLE III.
+---------------+--------------+-------------------+--------------+
| |Mean apparent | Absolute |Temperature by|
|Temperature by |dilatation of | dilatation of |a Thermometer |
|an air Thermom.| mercury | glass in |made of glass.|
| | in glass. | volume. | |
+---------------+--------------+-------------------+--------------+
| Fahr. Cent. | Fahr. Cent.| Fahr. Cent. | Fahr. Cent. |
| 212° 100° |¹/₁₁₆₆₄ ¹/₆₄₃₀| ¹/₆₉₆₆₀ ¹/₃₈₇₀₀ | 212 100 |
| 392 200 |¹/₁₁₄₃₀ ¹/₆₃₇₈| ¹/₆₅₃₄₀ ¹/₃₆₃₀₀ | 415.8 213.2 |
| 572 300 |¹/₁₁₃₇₂ ¹/₆₃₁₈| ¹/₅₉₂₂₀ ¹/₃₂₀₀₀ | 667.2 352.9 |
+---------------+--------------+-------------------+--------------+
The absolute dilatations of iron, copper, and platina were investigated
with great address, from 0° to 100° and from 0° to 300° centigrade;
and were found as per Table below, for each degree of the centigrade
thermometer.
TABLE IV.
+--------+---------------+--------+---------------+
|Temp. by|Mean dilatation|Temp. by|Mean dilatation|
| the air| of iron, |iron rod| of copper |
| Therm. | in volume. | Therm. | in volume. |
+--------+---------------+--------+---------------|
| Cent. | | | |
| 100° | ¹/₂₈₂₀₀ | 100° | ¹/₁₉₄₀₀ |
| 300 | ¹/₂₂₇₀₀ | 372.6 | ¹/₁₇₇₀₀ |
+--------+---------------+--------+---------------+
+-----------+---------------+-----------+
| Temp. by |Mean dilatation| Temp. by |
|copper rod | of platina |platina rod|
| Therm. | in volume. | Therm. |
+-----------+---------------+-----------+
| | | |
| 100° | ¹/₃₇₇₀₀ | 100° |
| 328.8 | ¹/₃₆₃₀₀ | 311.6 |
+-----------+---------------+-----------+
Connected with this subject was another important enquiry, whether
the capacities of bodies for heat remain constant at different
temperatures, or whether they diminish or increase as the temperature
advances. In other words, does a body that requires a certain quantity
of heat to raise it from 0° to 100° centigrade, require the same
quantity to raise it from 100° to 200°, and from 200 to 300°, &c.; or
does it require less or more as we ascend? This enquiry involves that
of the measure of temperature. They adopt the uniform expansion of air,
or the air thermometer, as the proper measure, and find the capacity of
iron,
From 0° to 100° = .1098
0 to 200 = .1150
0 to 300 = .1218
0 to 350 = .1255
the capacity of an equal weight of water being 1.
The following Table exhibits the capacities of seven other bodies
according to their results.
TABLE V.
+---------+--------------+--------------+
| |Mean capacity |Mean capacity |
| | between 0° | between 0° |
| | and 100° | and 300° |
+---------+--------------+--------------+
|Mercury | .0330 | .0350 |
|Zinc | .0927 | .1015 |
|Antimony | .0507 | .0549 |
|Silver | .0557 | .0611 |
|Copper | .0949 | .1013 |
|Platina | .0335 | .0355 |
|Glass | .1770 | .1900 |
+---------+--------------+--------------+
According to this table the capacities of bodies _increase_ with the
temperature in a small degree: and the increase, though it would still
exist, would be less, if the common mercurial thermometer were the
measure of temperature.
Also supposing that thermometers made of these bodies and graduated by
immersion in freezing and boiling water into 100°; if these were all
immersed in a fluid in which an air thermometer stood at 300°. Then the
relative temperatures of the several thermometers would be as under, if
measured by the absolute quantity of heat acquired, namely,
Iron 322.2°
Silver 329.3
Zinc 328.5
Antimony 324.8
Glass 322.1
Copper 320.0
Mercury 318.2
Platina 317.9
From these observations they infer that the law which has been
promulgated for the refrigeration of bodies, cannot be strictly true:
namely, that bodies part with heat in proportion as their temperature
exceeds that of the surrounding medium.
Some animadversions on the general laws relative to the phenomena of
heat, announced in my elements of Chemical Philosophy (page 13) then
follow, together with a table drawn up to show the discordance between
the air thermometer and the mercurial thermometer, both being graduated
in the manner I proposed in the said elements. On these points I may
have to remark in the sequel.
The first part of the Essay concludes with some remarks to shew why a
preference should be given to the air thermometer, or more strictly,
the thermometer whether of mercury or any other body, supposed to be
graduated so as to correspond with an air thermometer of equal degrees.
The Second Part of the Essay is on
_The Laws of Refrigeration_.
Adopting the air thermometer as the most eligible measure of
temperature, Messrs. Dulong and Petit proceed to investigate the laws
of the refrigeration of bodies, under a great variety of circumstances,
in _vacuo_ and in air or gases of different kinds and densities. The
inquiry abounds with experiments and observations evincing great skill
and acuteness; but which it will not suit our purpose to detail. It
may suffice for us to give a general summary of the Laws deduced by
them from their experiments, at the same time recommending all those
who feel sufficient interest in the subject to peruse the essay at
large, which exhibits a profound philosophical train of experiments,
the results of which are illustrated by the aid of mathematical
generalization.
“_Law 1._ If one could observe the cooling of a body placed in a
vacuum, and surrounded by a vessel absolutely destitute of heat, or
otherwise deprived of the power of radiating heat, the velocities of
cooling would decrease in geometrical progression when the temperatures
diminished in arithmetical progression.”
“_Law 2._ The temperature of a vessel containing a vacuum being
constant, and a body being placed in it to cool, the velocities of
cooling for excesses of temperature in arithmetical progression,
decrease as the terms of a geometrical progression diminished by a
constant number. The ratio of this progression is the same for the
cooling of all kinds of bodies, and is equal to 1.0077.”
“_Law 3._ The velocity of cooling in a vacuum for the same excess of
temperature, increases in geometrical progression, the temperature of
the vessel circumscribing the vacuum increasing in an arithmetical
progression. The ratio of the progression is the same as above, namely
1.0077 for all kinds of bodies.”
“_Law 4._ The velocity of cooling due to the sole contact of a gas
is entirely independent of the nature of the surface of the cooling
bodies.”
“_Law 5._ The velocity of cooling due to the sole contact of a gaseous
fluid varies in a geometrical progression, while the excess of
temperature itself varies in a geometrical progression. If the ratio of
this second progression be 2, that of the first is 2.35, whatever be
the nature of the gas and its elastic force.”
“This Law may be likewise announced by saying that the
quantity of heat carried off by a gas is in all cases
proportional to the excess of the temperature of the
heated body raised to the power whose index is 1.233.”
“_Law 6._ The cooling power of a gaseous fluid diminishes in a
geometrical progression, when its tension itself diminishes in a
geometrical progression. If the ratio of this second progression is 2,
the rate of the first is 1.366 for atmospheric air; 1.301 for hydrogen;
1.431 for carbonic acid; and 1.415 for olefiant gas.”
“This law may also be presented as follows: The
cooling power of a gas, all other things being alike,
is proportional to a certain power of the pressure.
The exponent of this power depends on the nature of
the gas, and is for air 0.45; for hydrogen 0.315; for
carbonic acid 0.517; and for olefiant gas 0.501.”
“_Law 7._ The cooling power of a gas varies with its temperature in
such a manner that if the gas can dilate so as to preserve the same
uniform tension, the cooling power will be as much diminished by the
rarefaction of the gas, as it is increased by its augmentation of
temperature; so that definitively it depends only on its tension.”
* * * * *
Another ingenious Essay was published by Messrs. Dulong and Petit,
in the Annal. de chimie et de physique, vol. 10, namely, “Researches
on some important points of the theory of heat.”--One object is to
ascertain the specific heats of bodies with superior precision. A table
of the specific heats of certain metals, found by their method, is
given, together with the weights of the atoms of those metals, and the
products of the specific heats and weights of the atoms, as under:
+----------+---------------+--------------+--------------+
| | | |Product of the|
| | | |weight of each|
| |Specific heats,|Weights of the| atom by the |
| | that of water |atoms, that of|corresponding |
| | being 1 |oxygen being 1| capacity. |
+----------+---------------+--------------+--------------+
|Bismuth | 0.0288 | 13.300 | 0.3830 |
|Lead | 0.0293 | 12.950 | 0.3794 |
|Gold | 0.0298 | 12.430 | 0.3704 |
|Platinum | 0.0314 | 11.160 | 0.3740 |
|Tin | 0.0514 | 7.350 | 0.3779 |
|Silver | 0.0557 | 6.750 | 0.3759 |
|Zinc | 0.0927 | 4.030 | 0.3736 |
|Tellurium | 0.0912 | 4.030 | 0.3675 |
|Copper | 0.0949 | 3.957 | 0.3755 |
|Nickel | 0.1035 | 3.690 | 0.3819 |
|Iron | 0.1100 | 3.392 | 0.3731 |
|Cobalt | 0.1498 | 2.460 | 0.3685 |
|Sulphur | 0.1880 | 2.011 | 0.3780 |
+----------+---------------+--------------+--------------+
The inference intended from this Table is pretty obvious, namely, that
the atoms or ultimate particles of the above bodies contain or attach
to themselves the same quantity of heat, or have the same capacity.
This principle the authors think will apply to the simple atoms of
all bodies, whether solid, liquid, or elastic; but they hold it does
not apply to compound atoms. It differs therefore essentially from
a suggestion of mine, made eighteen years ago, (see Vol. I. page
70,) that _the quantity of heat belonging to the ultimate particles
of all elastic fluids, must be the same under the same pressure and
temperature_. They seem to apprehend, from experience, that a very
simple ratio exists between the capacities of compound atoms and
that of the elementary atoms. They draw another inference from their
researches, that the heat developed at the instant of the combination
of bodies, has no relation to the capacity of the elements; this
loss of heat, they argue, is often not followed by any diminution in
the capacity of the compounds. They seem to think that electricity
developes heat in the act of combination; but they do not deny that a
change of capacity may sometimes ensue, and heat be developed from this
cause.
_Remarks on the above Essays._
Results nearly agreeing with those of De la Roche and Berard, on the
capacity of certain elastic fluids for heat, were about the same time
obtained by M. M. Clement and Desormes. (See Journal de Physique, Vol.
89--1819.) Such results, impugning some of the most plausible doctrines
of heat, could not be admitted but upon very good authority. I remained
doubtful, in some degree, till satisfied by my own experience. I
procured a calorimeter of the construction of De la Roche’s, and to
simplify the experiment, instead of forcing a given volume of hot air
through the calorimeter to impart heat to the water, I drew, by means
of an air-pump, a certain volume of atmospheric (or other air) of the
common temperature, through the calorimeter filled with hot water, in
order to find how much this process would accelerate the cooling. From
several experiments of this kind, I am convinced that the capacity of
common air for heat is very nearly such as the above ingenious French
chemists have determined. That is, it is about ¹/₇ part only of what
Dr. Crawford deduced from his experiments, and nearly the same part of
what I inferred from my theoretic view of the specific heats of elastic
fluids. (See Vol. I. pages 62 and 74.)
Indeed M. M. De la Roche and Berard appear to have been puzzled with
the admission of their own results. The combined heats of oxygen and
hydrogen gases give only .6335 for the specific heat of water; whereas
by experiment the heat of water is found to be 1, notwithstanding an
immensity of heat is evolved during the combination of these gases.[26]
[Footnote 26: By recent experiments I find the heat evolved in the
union of oxygen and hydrogen, would raise the temperature of the same
weight of water 6500°.]
“It is necessary therefore,” they observe, “to abandon the hypothesis
which ascribes the evolution of heat in cases of combination to a
diminution of specific heat in the bodies combined, and admit with
Black, Lavoisier, and Laplace, and many other philosophers, the
existence of caloric in a state of combination in bodies.” I am not
aware of any writer that denies the existence of caloric in a state
of combination of bodies. Dr. Crawford, who would be thought the
most likely to err in this respect, maintains, “that elementary fire
is retained in bodies partly by its attraction to those bodies and
partly by the action of the surrounding heat,” and that “its union
with bodies will resemble that particular species of chemical union
wherein the elements are combined by the joint forces of pressure and
of attraction.” (On animal heat, 2d edition, page 436.) He is perhaps
somewhat unfortunate in his instance in the combination of carbonic
acid and water; muriatic acid or ammonia and water would have been more
in point.
The truth is, these important experiments shew that in elastic fluids
the increments of temperature are not proportional to the whole heat,
compared with the like increments of temperature and whole heat in
those bodies when in the liquid and solid states.
The specific heats of bodies, it is well known, are determined by means
of the relative quantities of heat necessary to raise the temperature
of those bodies a certain number of degrees. They are expressed by the
ratios of those quantities. If the capacities of the same bodies for
heat were permanent at all temperatures, then these ratios would also
express those of the whole quantities of heat in bodies. In fact, most
authors represent the specific heats as expressing both the ratio of
the total quantities of heat in bodies, and of the relative quantities
to raise their temperature a given number of degrees; but it is the
latter only which they accurately represent, and the former only
hypothetically.
In regard to bodies in the solid and liquid forms, all experience
shews that their capacities for heat are nearly if not accurately
constant within the common range of temperature; it seems therefore
not unreasonable to infer that the whole quantity of heat in each is
proportional to their increments. When, however, a solid body by an
increase of temperature assumes a fluid form, and absorbs heat without
any increase of its temperature, its total quantity of heat is thus
increased; and it is contended by the writers on capacity, that the
increments of heat afterwards are increased in the same proportion
as the total quantities. This is probable enough; but it ought to be
proved in several instances by direct experiment before it can safely
be admitted as a general principle; more especially now since the
analogy in the case of a liquid becoming an elastic fluid is found to
fail in this particular. As an instance of uncertainty, the capacity
of ice to water has been found as 9 to 10 by one person, and as 7.2 to
10 by others; such wide difference in the results shows there must be
a difficulty in determining the specific heat of ice, and that it may
even be doubted whether the specific heat of ice or water is greatest.
From the foregoing detail of experiments on elastic fluids, it appears
evident that such fluids exhibit matter under a form in which it has
the greatest possible capacity for heat, when capacity is understood
to denote the total quantity of heat connected with the fluid; but if
the capacity or specific heat is meant to denote the quantity of heat
necessary to raise the body a given number of degrees of temperature,
then the elastic fluid form of matter is that which has the least
capacity for heat of any known form of the same matter. When therefore
we use the terms _specific heat_ as applied to elastic fluids we should
henceforward carefully distinguish in what sense they are used; but the
terms may still be indifferently used in the one or the other sense
as applied to liquids and solids, till some more decisive experiments
shew that a distinction is required. Probably the anomalies that have
occurred in investigations of the zero of cold, or point of total
privation of heat, are in part due to the want of accordance between
the ratio of the total quantities of heat in bodies, and the ratio of
the quantities producing equal increments of temperature.
The greatest possible quantity of heat which a given weight of elastic
fluid can contain is when the dilatation of the fluid is extreme.
For, condensation, whether arising from mechanical pressure or from
increased attraction of the atoms of matter for each other, tends to
dissipate the heat, by increasing its elasticity. Hence increase of
temperature, at the same time that on one account it increases the
absolute quantity of heat in an elastic fluid, diminishes the quantity
on another account by an increase of pressure, if the fluid be not
suffered to dilate. This is well known from the fact that condensation
produces increase of temperature in elastic fluids.
When it is considered that all elastic fluids expand the same quantity
by the same increase of temperature, it might be imagined that all of
them would have the same capacity, or require the same quantity of
heat to produce that expansion. The results of De la Roche and Berard
do not seem to admit of this supposition, though the differences of
the capacities of elastic fluids of equal volumes are not very great.
There is a remarkable difference too between their results and those
of Clement and Desormes, in regard to hydrogen gas: namely, .9033 and
.6640; also in carbonic acid gas, 1.2583 and 1.5. The subject deserves
further investigation.
In reference to the experiments of Dulong and Petit, on the relative
expansions of air and mercury by heat, I have no doubt their results
are good approximations to the truth. My former experiments were
chiefly made in temperatures between 32° and 212°, and I found, as
General Roi had done, the expansion of air to be somewhat greater in
the lower half than in the upper half of that interval, compared with
mercury. On a repetition of the experiments, I think the difference is
less than I concluded it to be, and I find that the like coincidence of
the air scale and mercurial, continues down to near freezing mercury;
at least the difference will not be so great as my new table of
temperature makes it at page 14. I have made some experiments on the
expansions of air above 212°, which lead me to adopt the results of
Dulong. On a comparison of the air and mercurial thermometer upon the
laws which I pointed out, namely, the former expanding in geometrical
progression to equal intervals of temperature, and the latter expanding
as the square of the temperature reckoned from its freezing point, it
appears that in the long range of 600° from freezing water to boiling
mercury, the greatest deviation of the two thermometers does not
exceed 22°. However, the great deviation of the scales between the
temperatures of freezing water and freezing mercury, is sufficient to
shew, as Dulong and Petit have observed, that their coincidence is
only partial. Like the scales of air and mercury, which are so nearly
coincident from -40° to 212° that scarcely any difference is sensible,
though no one doubts of its existence; yet afterwards the differences
become obvious enough, and the greater the farther we advance.
_Expansion of Mercury._ See page 34, vol. I. I have overrated the
expansion of glass bulbs (as will be seen presently,) and hence that of
mercury; my expansion of mercury corrected on account of the glass,
will be ¹/₅₃ nearly, which leaves it still greater than Dulong’s.
The 2nd table of Dulong is valuable, on account of its affording
us information of the rate of expansion in the higher degrees of
temperature, from a given or standard air thermometer.
_Iron, Copper, and Platina._
_Expansion of Glass._--By the 3rd Table of Dulong and Petit, it appears
these ingenious chemists found the expansion of glass for 180°, or from
32° to 212°, very nearly the same as had been determined previously by
Smeaton and others. It also expands increasingly with the temperature,
whether it is estimated by the air or mercurial standard. This was
observed by Deluc, but more extensively by the present authors. The
expansions of iron, copper, and platina, from 32° to 212° as detailed
in the 4th table, agree nearly with the results of others; but the
expansions in the higher part of the scale manifest some remarkable
facts not before known. Platina not only expands the least of the
above bodies, but its expansion is almost equable; iron expands more
than glass and less than copper, but the most unequally of any one,
the expansion increasing rapidly as the temperature advances. These
facts explain some others which have fallen under my observation. I was
formerly surprised to find glass and iron expand so nearly alike (see
vol. I. page 31); but it now appears that iron increases more slowly
in proportion than glass about the freezing point. More recently I
procured a small thermometrical vessel of platina to contain water like
those described at page 31, vol. I, and having filled it and treated
it as the other metallic vessels, I was again surprised to find that
the apparent greatest density of water in this vessel was at 43°,
whereas I expected to have found it below 42°, the point for glass
vessels. This observation, in conjunction with Dulong’s, shews, that
platina expands more than iron at low temperatures, though for a range
of 300° the whole expansion of the platina is to that of the iron as 2
to 3 nearly. Hence the error (for I now consider it as such) which I
was led into with respect to the expansion of glass bulbs, (see vol.
I. page 32) and subsequently into that of the expansion of mercury
abovementioned. It is not the expansion of glass which approaches that
of iron, but it is the reverse, which occasions the two bodies to meet
so nearly in the table, page 31. This consideration will affect the
point of greatest density of water also; for, the less the expansion
of iron and glass, the nearer will be the points of real and apparent
greatest density of water, contained in vessels of those materials. My
observations on brown earthenware are scarcely to be relied upon from
the difficulty of making such vessels water tight: but the common white
ware I have verified repeatedly since the publication of that table,
and am satisfied the point of apparent greatest density, is at or near
40° in such vessels; hence the real maximum density of water must be
below 40°. I am inclined to adopt 38° as the most proximate degree.
_Capacities of bodies for heat._ In the 5th table of Dulong, we have
the specific heats of glass and of six metals, determined between
freezing and boiling water: that of iron is given before. So far
the question does not involve that of the measure of temperature.
Their results afford no striking differences from those previously
determined; however, it is desirable to find a greater accordance
amongst philosophers in this respect. The experiments which give
the specific heats between 0° and 300° centigrade, are original and
interesting. The results go to shew that the capacities of bodies
increase in a small degree with the temperature. But supposing that
these results may be relied upon as accurate (which can scarcely be
affirmed of any former ones) still the character of them may be changed
by adopting a different measure of temperature.
The Essay of M. M. Dulong and Petit, in the 10th vol. of the An.
de chimie (see An. of Philosophy, vol. 14th, 1819) manifests great
ingenuity. It does not appear, however, so fortunate either in theory
or experiment as the former one. It would be difficult to convince any
one, either by reasoning or by experience that a number of particles
of mercury at the temperature of -40°, whether in the solid,, liquid,
or elastic state, have all the same capacity for heat. Indeed the
experiments of De la Roche and Berard, if they are to be credited,
demonstrate the inferior capacity of condensed air to rarefied air;
and if the same body changes its capacity in the elastic form, it may
well be concluded that all the three forms have not the same capacity.
M. M. Dulong and Petit have themselves shewn, in their former essay,
(see page 276) that solid bodies vary in their capacities for heat,
and that scarcely any two bodies, vary alike; hence it is impossible
that the product of the weight of the atom and specific heat of the
body should be a constant quantity. Their specific heat of certain
metals differ greatly from what is found by others. For instance, they
make the specific heat of lead .0293; the lowest authority I have
seen is Crawford, .0352, and the highest Kirwan .050; from repeated
trials I have lately found it, upon an average, .032. The weights of
some of the atoms in their table, differ materially from what are
commonly received; for instance, bismuth is 13.3 instead of 9; also
copper, silver, and cobalt, are only half the weights of some authors.
The gases too are unfortunate examples. Oxygen gas gives a product of
.236 instead of .375; azotic gas gives a product .1967, if oxygen be
to azote as 7 to 5, but a product of .393 if oxygen be to azote as 7
to 10: by Dr. Thomson’s ratio of oxygen to azote, 4 to 7, the product
will be .482, very different from .375. Hydrogen will give a product of
.47 or .41 instead of .375. All these differences, it may be said, are
occasioned by errors in the specific heats of the gases; but if errors
of this magnitude can still subsist after all the care that has been
taken, we shall scarcely know what to trust in experimental philosophy.
If M. Dulong would assume all his simple elements in an elastic state
and under one uniform pressure, the hypothesis would then make a
part of mine (vol. 1. page 70), and there is great reason to believe
it would be either accurately true or a good approximation; but to
suppose that some of the bodies should be in a solid state, having
their particles united by various degrees of attraction, others fluid,
and others in the elastic state, without any material modifications of
their heat arising from these circumstances, appears to me to be in
opposition to some of the best established phenomena in the mechanical
philosophy.
Their observations on the specific heat of compound elements, on
the relation of the heat developed by combination, as compared with
the heat of the elements before and after the combination, &c., are
not supported by a detail of actual experience. Heat given out by
chemical changes they suppose not to have been previously in a state of
combination with the elements. As an argument, the heat given out by
charcoal kept in a state of ignition, by a current of galvanic fluid,
is adduced. It is true this case is most easily explained, by allowing
that the galvanic fluid is in such circumstances converted into heat.
But the charcoal does not undergo any chemical change, and therefore
this is not a case in point.
All modern experience concurs in shewing that the heat of combustion
is primarily dependent on the quantity of oxygen combining. The heat
evolved by the combustion of phosphorus and hydrogen is very nearly,
if not accurately, in proportion to the oxygen spent. The heat by the
combustion of charcoal is not in a much less ratio: and I find the heat
in burning carbonic oxide, carburetted hydrogen and olefiant gas is the
same as in burning hydrogen gas, _provided the combining oxygen is the
same_.
One difficulty seems to have occurred to M. M. Dulong and Petit. They
all along conceive that the specific heats of bodies, that is, the
heats producing equal increments of temperature, must necessarily
be proportionate to their whole heat. This is purely hypothetical,
till established by experiment. The generality of writers on specific
heat had conceived it almost confirmed by experiment. The results of
Delaroche and Berard have shewn that in elastic fluids the increments
of heat are not proportional to the whole quantities, but on the
contrary are less when a body is elastic than when liquid. Indeed
some writers have argued this should be the case; because a body
nearly saturated with another has less affinity for it left.[27] It
is plain then that oxygen gas or any other elastic fluid, may have a
small specific heat in the sense above defined, and yet have an almost
unlimited quantity of heat. I am not aware of any one established
fact that does not admit of an explanation upon the hypothesis that
heat exists in definite quantities in all bodies, and is incapable of
any change, except perhaps into one of the other equally imponderable
bodies, light or electricity.
[Footnote 27: See Dr. Henry’s note, Manch. Memoirs, vol. 5, page 679.]
NEW TABLE OF THE
_Forces of Vapours in Contact with the
Generating Liquids at Different Temperatures._
(A) = Temperatures by the common thermometer.
(B) = Ether vapour, ratio 2 Spec. Gravity .72
(C) = Sulphuret of carbon vapour, ratio 1.978
(D) = Alcohol vapour, ratio 2.7 Spec. Gravity .82
(E) = Acetic acid vapour, ratio 2.57
(F) = Water, ratio 2.602()
-----+--------+--------+--------+--------+-------
(A) | (B) | (C) | (D) | (E) | (F)
-----+--------+--------+--------+--------+-------
| Inches | Inches | Inches | Inches |Inches
| of M. | of M. | of M. | of M. | of M.
-----+--------+--------+--------+--------+-------
7° | 3.75 | 3.134 | .193 | | .11
35 | 7.5 | 6.20 | .560 | .27 | .29
65+ | 15. | 12.26 | 1.51 | .69 | .75
97 | 30 | 24.26 | 4.07 | 1.77 | 1.95
133 | 60 | 48. | 11.00 | 4.54 | 5.07
173 | 120 | | 29.70 | 11.7 | 13.18
220 | 240 | | 80.2 | 30. | 34.2
272 | | | | | 88.9
340 | | | | | 231
-----+--------+--------+--------+--------+-------
This is an improved and extended table of the force
of vapour, similar to that at page 14, vol. I. It
shews that the different vapours increase inforce
in geometrical progression, to certain intervals
of temperature, the same to most or all liquids.
These intervals of temperature were presumed in the
former table, to be in reality _equal_ to one
another; but the accuracy of this last notion has been
questioned.
TABLE,
_Shewing the expansion of air, and the elastic
force of aqueous and ethereal vapour, at different
temperatures._
----------+---------+---------------+----------------+-------------
| | Utmost force of |
Temperat. | Vol. +---------------+----------------+Weight of 100
| of air. |Aqueous vapour.|Ethereal vapour.| cubic inches
----------+---------+---------------+----------------+ of aqueous
-28° | 420 | | | vapour.
-20 | 428 |Inches of Merc.|Inches of Merc. |
-10 | 438 +---------------+----------------+-------------
0 | 448 | .08 | | Grains.
10 | 458 | .12 | |
20 | 468 | .17 | |
30 | 478 | .24 | |
----------+---------+---------------+ |
32° | 480 | .26 | 7.00 | .178
33 | 481 | .27 | 7.18 | .184
34 | 482 | .28 | 7.36 | .191
35 | 483 | .29 | 7.54 | .197
36 | 484 | .30 | 7.73 | .203
37 | 485 | .31 | 7.92 | .209
38 | 486 | .32 | 8.11 | .216
39 | 487 | .33 | 8.30 | .222
40 | 488 | .34 | 8.50 | .229
41 | 489 | .35 | 8.70 | .235
42 | 490 | .37 | 8.90 | .245
43 | 491 | .38 | 9.10 | .255
44 | 492 | .40 | 9.31 | .267
45 | 493 | .41 | 9.52 | .275
46 | 494 | .43 | 9.74 | .284
47 | 495 | .44 | 9.96 | .293
48 | 496 | .46 | 10.18 | .303
49 | 497 | .47 | 10.41 | .313
50 | 498 | .49 | 10.64 | .323
51 | 499 | .50 | 10.87 | .329
52 | 500 | .52 | 11.10 | .341
53 | 501 | .54 | 11.34 | .354
54 | 502 | .56 | 11.59 | .366
55 | 503 | .58 | 11.85 | .378
56 | 504 | .59 | 12.12 | .384
57 | 505 | .61 | 12.39 | .396
58 | 506 | .62 | 12.66 | .402
59 | 507 | .64 | 12.94 | .414
60 | 508 | .65 | 13.22 | .420
61 | 509 | .67 | 13.51 | .432
62 | 510 | .69 | 13.80 | .444
63 | 511 | .71 | 14.10 | .456
64 | 512 | .73 | 14.41 | .468
65 | 513 | .75 | 14.72 | .480
66 | 514 | .77 | 15.04 | .492
67 | 515 | .80 | 15.36 | .509
68 | 516 | .82 | 15.68 | .521
69 | 517 | .85 | 15.90 | .539
70 | 518 | .87 | 16.23 | .551
71 | 519 | .90 | 16.56 | .569
72 | 520 | .92 | 17.00 | .580
73 | 521 | .95 | 17.35 | .598
74 | 522 | .97 | 17.71 | .610
75 | 523 | 1.00 | 18.08 | .627
76 | 524 | 1.03 | 18.45 | .645
77 | 525 | 1.06 | 18.83 | .662
78 | 526 | 1.09 | 19.21 | .680
79 | 527 | 1.12 | 19.60 | .700
80 | 528 | 1.16 | 20.00 | .721
----------+---------+---------------+----------------+-------------
_Applications of the above Table._
These tables will be found of great use in reducing volumes of air from
one temperature or pressure to any other given one: also in determining
the specific gravities of dry gases from experiments on those saturated
with or containing given quantities of aqueous or other vapours.
As several writers, and some of considerable eminence, have given
erroneous or imperfect formulæ on these subjects, more particularly
with regard to the effect of aqueous vapour in modifying the weights
and volumes of gases, it has been thought proper to subjoin the
following precepts and examples for the use of those who are not
sufficiently conversant in such calculations.
The 5th column of the above table, or weight of aqueous vapour, is
new, and may therefore require explanation. Gay Lussac is considered
the best authority in regard to the specific gravity of steam; but it
would be well if his results were confirmed or corrected, as they are
of importance. According to his experience, the specific gravities of
common air and of pure aqueous vapour, _of the same temperature and
pressure_, are as 8 to 5, or as 1 to .625. Now I assume that 100 cubic
inches of common air, free from moisture, of the temperature 60° and
the pressure of 30 inches of mercury, weigh 31 grains nearly. It is an
extraordinary fact that philosophers are not agreed upon the absolute
weight of a given volume of common air. Most authors now assume the
weight of 100 inches = 30.5 grains, whilst according to my experience
it is more than 31 grains. If common air be assumed 31 grains, steam
would be 19⅜ grains for 100 cubic inches, at the same temperature and
pressure, could it subsist; but as it cannot sustain that pressure
at the temperature of 60° we must deduct according to the diminished
pressure, the utmost force of steam at 60° being .65 parts of an inch
of mercury, we have 30 inches ∶ 19⅜ grains ∷ .65 ∶ .420 grains = the
weight of 100 cubic inches of aqueous vapour at 60° and pressure .65
parts of an inch; which is the number given above in the table. The
like calculation is required for any other pressure: but in addition
to this, there is to be an allowance for the temperature from the 2d
column: Thus, let the weight of 100 cubic inches of steam at 32° be
required. We have 30 inch. ∶ 19⅜ grs. ∷ .26 inch. ∶ .1679 grs.; the
weight of 100 inches of steam at 60°; then if 480 ∶ 508 ∷ .1679 ∶ .178
grs. = weight of 100 cubic inches of steam at 32° and pressure .26
parts of an inch, the tabular number required.
_Examples._
1. How many cubic inches of air at 60° are equivalent in weight to 100
cubic inches at 45°?
By the column headed _volume of air_ we have this proportion, if 493 ∶
508 ∷ 100 inch. ∶ 103.04 inches, the volume required.
2. How many cubic inches of air with the barometer at 30 inches height,
are equal in weight to 100 cubic inches when the barometer stands at
28.9 inches?
_Rule._ The volume of air being inversely as the pressure, we have, 30
∶ 28.9 ∷ 100 inches ∶ 96⅓ inches the answer.
3. How many cubic inches of dry air are there in 100 inches saturated
with aqueous vapour, at the temperature of 50°, and pressure 30 inches
of mercury?
Here the formula
(_p_ - _f_)
-----------
_p_
applies, where _p_ denotes the atmospheric pressure at the time, and
_f_ denotes the utmost force of vapour in contact with water at the
temperature. Hence _p_ = 30, _f_ = .49 per table, and we have
(_p_ - _f_) (30 - .49) 29.51
----------- = ----------- = ----- = 98¹¹/₃₀, or
_p_ 30 30
98¹¹/₃₀ percent dry air.
& 1¹⁹/₃₀ vapour.
---------
100.
If the vapour of ether is assumed, then _f_ = 10.64, and we have
(_p_ - _f_) (30 - 10.64) 19.36
----------- = ----------- = ----- =
_p_ 30 30
.645, ... or 64½ per cent dry air.[28]
35½ per cent ethereal vapour.
-----
100
[Footnote 28: The aqueous vapour in this case maybe considered as
insignificant.]
4. Suppose we find by trial the weight of 100 cubic inches of common
air saturated with vapour at 60°, the barometer standing at 30 inches
to be 30.5 grains, and the weight of hydrogen gas in like circumstances
to be 2.118 grains; query the weights of 100 cubic inches of each gas
free from vapour, and their specific gravities, the temperature and
pressure being as above?
If 30.5 ∶ 2.118 ∷ 1 ∶ .0694 = sp. gr. of vapourized hydrogen, that of
vapourized air being 1. Subtracting .42 grs. (weight of vapour per
table) from 30.5 grs., leaves 30.08 grains; and subtracting .65 parts
of an inch from 30 inches, leaves 29.35 inches. Hence 100 cubic inches
of dry air at the pressure of 29.35 inches, weigh 30.08 grains; and we
have 29.35 ∶ 30 ∷ 30.08 ∶ 30.746 grains, the weight of 100 inches of
dry air. Again, subtracting .42 grs. from 2.118, leaves 1.698 grains
= weight of 100 cubic inches of hydrogen of 60° and sustaining the
pressure of 29.35 inches; whence if 29.35 ∶ 30 ∷ 1.698 ∶ 1.736 grains,
weight of 100 inches of dry hydrogen; and 30.746 ∶ 1.736 ∷ 1 ∶ .05645
= sp. gr. of dry hydrogen, that of dry air being unity. Or the results
may be exhibited as under:
Weight of 100 cubic inches. Sp. Gravities.
Vap. air 30.5 grains 1 14.4
Vap. hydrogen 2.118 ---- .0694 1
Dry air 30.746 grains 1 17.7
Dry hydrogen 1.736 ---- .05645 1
FORMULÆ FOR DETERMINING THE PROPORTIONS OF COMBUSTIBLE GASES IN
MIXTURES.
It frequently happens, especially in the decomposition of vegetable
substances by heat, that the product consists of several combustible
gases in mixture, and it is desirable to determine the proportions of
each of those which collectively constitute the mixture. The following
forms will be found useful for this purpose.
1. _Carbonic oxide and hydrogen._
Let _x_ = the volume of carbonic oxide, _y_ = that of hydrogen, _w_ =
that of mixture, and _a_ = that of carbonic acid, produced by exploding
the mixed gases with oxygen over mercury.
Then the carbonic oxide, or _x_ = _a_,
and the hydrogen, or _y_ = _w_ - _a_.
2. _Sulphuretted hydrogen and hydrogen._
Let _x_ = the volume of sulphuretted hydrogen, _y_ = that of hydrogen,
_w_ = that of the mixture, and _g_ = the oxygen spent in the combustion
of _w_.
Then because _x_ + _y_ = _w_,
and 1½_x_ + ½_y_ = _g_;
we have _x_ = _g_ - ½_w_,
and _y_ = 1½_w_ - _g_.
3. _Phosphuretted hydrogen and hydrogen; also carburetted hydrogen and
hydrogen, and carburetted hydrogen and carbonic oxide._
The notation being as above, we have _x_ + _y_ = _w_, and 2_x_ + ½_y_ =
_g_ (see page 171): and,
2_g_ - _w_ 4_w_ - 2_g_
_x_ = -----------, and _y_ = -----------.
3 3
4. _Olefiant gas and carburetted hydrogen._
The notation being as above, we have
_x_ + _y_ = _w_, and
3_x_ + 2_y_ = _g_; whence
_x_ = _g_ - 2_w_ and
_y_ = 3_w_ - _g_.
5. _Carburetted hydrogen, carbonic oxide and hydrogen._
Let _x_ = carburetted hydrogen, _y_ = carbonic oxide, _z_ = the
hydrogen, _g_ = the oxygen spent in the combustion of _w_ volumes of
mixed gas, and _a_ = the carbonic acid produced.
Then _x_ + _y_ + _z_ = _w_,
_x_ + ½_y_ + ½_z_ = _g_,
and 2_x_ + _y_ = _a_.
whence we have
2_g_ - _w_ 3_a_ - 2_g_ + _w_
_x_ = -----------, _y_ = -----------------
3 3
and _z_ = _w_ - _a_.
6. _Olefiant gas, carburetted hydrogen and carbonic oxide._
Let _a_ = the olefiant gas, _y_ = the carburetted hydrogen, and _z_ =
equal the carbonic oxide, _g_ = the oxygen entering into combination,
and _a_ = the carbonic acid produced; also _w_ = the whole volume as
before.
Then we have _x_ + _y_ + _z_ = _w_,
3_x_ + 2_y_ + ½_z_ = _g_,
and 2_x_ + _y_ + _z_ = _a_.
Whence _x_ = _a_ - _w_,
_y_ = 4_w_ - 5_a_ + 2_g_
-------------------,
3
and _z_ = ⅔(_w_ + _a_ - _g_).
7. _Superolefiant gas,[29] carburetted hydrogen, and carbonic oxide._
[Footnote 29: A gas found in oil and coal gas. See Manchester Memoirs,
vol. 4 (new series), page 73.]
Let _x_ = volume of superolefiant, _y_ = volume of carburetted
hydrogen, _z_ = volume of carbonic oxide, _g_ = the oxygen combining,
_a_ = carbonic acid produced, and _w_ = volume of mixed gas.
Then _x_ + _y_ + _z_ = _w_,
4½_x_ + 2_y_ + ½_z_ = _g_,
and 3_x_ + _y_ + _z_ = _a_.
Whence _x_ = _a_ - _w_
----------,
2
_y_ = 3_w_ - 4_a_ + 2_g_
------------------,
3
and _z_ = 3_w_ - 4_g_ + 5_a_
-------------------.
6
8. _Superolefiant gas, carburetted hydrogen, carbonic oxide, and
hydrogen._
This is the mixture of gases obtained by a red heat from coal and oil,
after being freed from carbonic acid, &c., by the usual means.
This mixture requires a very complicated formula, in consequence of
the specific gravities of the gases entering into the calculus. The
importance of the subject however may be an apology for the labour.
Let _x_ = vol. of superolefiant, _S_ its sp. gr.
_y_ = vol. of carb. hydrogen, ∫ its sp. gr.
_z_ = vol. of carbonic oxide, _c_ its sp. gr.
& _u_ = vol. of hydrogen, _s_ its sp. gr.
_C_ = specific gravity of the mixture, _g_ = oxygen, _a_ = carbonic
acid, and _w_ = whole volume of mixture as before.
Then we have _x_ + _y_ + _z_ + _u_ = _w_
4½_x_ + 2_y_ + ½_z_ + ½_u_ = _g_
3_x_ + _y_ + _z_ = _a_
and _Sx_ + ∫_y_ + _cz_ + _su_ = _Cw_.
Whence _u_ =
(3_S_ + 5_c_ - 8∫)_a_ - (4_c_ - 4∫)_g_ - (3_S_ + 6_C_ - 6∫ - 3_c_)_w_
--------------------------------------------------------------------
8∫ + _c_ - 3_S_ - 6_s_.
The value of the hydrogen being obtained, it may be subtracted from
_w_, and the remainder will be best divided into three portions, by the
preceding formula.
HEAT PRODUCED BY THE COMBUSTION OF GASES.
Subsequent experience to that detailed at page 77, Vol. 1. has
furnished the following more correct results of the heat produced by
the combustion of pure gases.
Hydrogen, combustion of it raises an equal volume
of water 5°
Carbonic Oxide 4½
Carburetted Hydrogen, or Pond Gas 18
Olefiant Gas 27
Coal Gas (varies with the gas from 10° to) 16
Oil Gas (varies also with the gas from 12° to) 20
Generally the combustible gases give out heat nearly in proportion to
the oxygen they consume. See note at the end of Vol. 4, new series of
the Manchester memoirs.
ABSORPTION OF GASES BY WATER, &c.
This curious subject has attracted much less attention than it
deserves. Very little has been published relating to it since the time
of Dr. Henry’s essays and my own, now more than twenty years ago.
The only author I remember is M. Saussure of Geneva, who published a
similar essay about twelve years afterwards. See Thomson’s Annals of
Philosophy, Vol. 6. He investigates the quantities of gases absorbed
by various solid bodies, in a manner which I do not fully comprehend;
he then treats of the absorption of gases by liquids, adverting at
the same time to Dr. Henry’s experiments and mine. My enquiries were
principally confined to _one_ liquid, water; but I made a few trials
with others, such as weak aqueous solutions of salts, alcohol, &c.,
and observing no remarkable differences, I concluded somewhat too
hastily that “most liquids free from viscidity, such as acids, alcohol,
&c., absorb the same quantity of gases as pure water.” Manchester
memoirs, new series, Vol. 1. M. Saussure however asserts that there
are considerable differences in liquids in this respect. He finds
sulphuretted hydrogen to be more absorbable by water than Dr. Henry
and I did; in this I find he is right. Water takes about 2½ its bulk
of this gas when pure; and it seldom had been obtained unmixed with
hydrogen when Dr. Henry and I made our experiments upon its absorption.
In regard to carbonic acid, nitrous oxide, and olefiant gas, M.
Saussure nearly agrees with us; but his results with oxygen gas,
carbonic oxide, carburetted hydrogen, hydrogen and azote, would prove
that water absorbs twice the quantities of each that we have assigned.
I have no doubt he is wrong in the less absorbable gases. In the case
of absorption of mixed gases, Saussure has given four examples, in
which he finds the results to militate against my theoretic view, as
stated at page 201, Vol. 1.; namely, that water takes the same quantity
of each in a mixed state as it would do if they were separate, and in
other respects in like circumstances. But I have shewn in the Annals of
Philos. Vol. 7, 1816, that his results coincide as near as any one can
expect with the views which I have all along taken of this subject.
It will be seen, page 173, that another gas has been found to coincide
with olefiant gas in absorbability; namely, phosphuretted hydrogen.
FLUORIC ACID.--DEUTOXIDE OF HYDROGEN.
In treating of Fluoric acid, (Vol. 1, page 277) we came to the
conclusion that this acid was probably constituted of two atoms of
oxygen, and one of hydrogen, and have figured it accordingly (Plate 5,
fig. 38). Subsequent experience however has shewn that deutoxide of
hydrogen, though it can be formed synthetically, is not the same thing
as fluoric acid. We are indebted to M. Thenard for the discovery of
this curious compound, the deutoxide of hydrogen or oxygenated water.
An ingenious memoir on the subject was published by him in 1818, in
which the formation and the properties of this compound are fully
detailed. I had no small satisfaction in 1822, when at Paris, in being
obligingly favoured by M. Thenard with a view of the process of the
formation, and of the more distinguishing properties of this singular
liquid.
The nature of fluoric acid is still enveloped in obscurity. My
experience led me to adopt the composition of fluate of lime to be 40
acid and 60 lime per cent. I had not then seen Scheele’s admirable
essay on the subject. From the 5th section of his 2d. essay on fluor
mineral, 1771, it may be deduced that fluate of lime is composed of
72.5 lime and 27.5 acid per cent. In 1809 Klaproth, and near the same
time, Dr. Thomson found about 67½ lime and 32½ acid per cent. in
fluor spar. They both erred, no doubt, as I did, by not repeating the
treatment of the mineral with sulphuric acid often enough. Since then
most authors, as Davy, Berzelius, Thomson, &c., agree with Scheele
nearly, in assigning 27.5 acid, and 72.5 lime, in 100 parts of fluate
of lime. My experience in 1820 gave me 1 per cent. less of lime; and
Dr. Thomson now finds about 1 per cent. more of lime than Scheele’s
analysis gives.
If we estimate the atom of lime at 24, that of fluoric acid must be
about 9, according with the above proportion; this is much below 15,
the weight of an atom of deutoxide of hydrogen.
Should Sir H. Davy’s view of fluate of lime be found correct, its
atomic constitution would be one atom of _calcium_, the metallic
substance of which lime is the protoxide, and one atom of _fluorine_,
the name he has assigned to the other element, which with hydrogen is
supposed to constitute the fluoric acid. The atom of fluor spar would
then be 1 atom of calcium, 17, united to one atom of fluorine 16.
MURIATIC ACID.--OXYMURIATIC ACID, &c.
From the articles _muriatic acid_ and _oxymuriatic acid_ in the former
volume, published now 16 years ago, as well as from the appendix
to said volume, in which sundry animadversions are found on the
fluctuating opinions entertained in regard to these acids, the reader
will not be surprised to find some further addition.
Three notions have been submitted to the public in the last twenty
years in regard to the nature of muriatic acid. First, the gas detached
from common salt by sulphuric acid has been thought to be the acid in
a state of purity, and constituted of a certain base or radical united
to oxygen; this was the notion inculcated in the articles alluded to
above. Second,--it is stated as a fact that when oxymuriatic acid and
hydrogen in equal volumes are united by the electric spark, a volume
of muriatic acid gas is the result equal to the sum of both the other
volumes, and that this gas perfectly agrees with the gas obtained from
common salt by sulphuric acid; this suggested the idea that muriatic
acid gas is a compound of what has been called _real_ or _dry_ muriatic
acid one atom, and water one atom. And, third, it is argued, that
the element we have called oxymuriatic acid gas, is, for aught that
appears, a _simple_ body, and consequently, that muriatic acid gas is
the _real acid_, and is constituted as above, of one atom of hydrogen,
and one atom of oxymuriatic acid (now called _chlorine_.) It is not
intended here to enter into a discussion of the arguments and facts
adduced in support of the different conclusions. More experience
must be had before all the doubts and difficulties are removed from
the subject. But it will be proper to illustrate these different
positions by an example. For instance, common salt, muriate of soda or
chloride of sodium. By the first notion 50 parts of dry common salt
will consist of one atom of muriatic acid gas, 22, and one atom of
caustic soda, 28. By the second notion the same salt will be formed of
30 parts of muriatic acid gas, and 28 of caustic soda; but 8 parts of
water evaporate when the salt is dried. By the third view common salt
consists of oxymuriatic acid, or chlorine and sodium, or the metal of
which caustic soda is the protoxide; and 50 parts of salt will consist
of 29 chlorine and 21 sodium, or one atom of each.
NITRIC ACID--COMPOUNDS OF AZOTE AND OXYGEN.
Since the account of nitric acid (Vol. 1, page 343) was printed, a
change has universally taken place in estimating the weight of the
nitric acid atom, and of the proportion of azote and oxygen in the
same. This has been effected chiefly by a more correct analysis of
nitre than existed at that time. Nitre is now found to consist nearly
of 52 parts acid and 48 parts potash per cent. Hence if the atom of
potash be 42, that of nitric acid must be 45; for, 48 ∶ 52 ∷ 42 ∶ 45,
nearly. That is, the nitric acid atom consists of 10 azote + 35 oxygen
by weight; or of 2 atoms of azote (according to my estimate) and 5 of
oxygen. There appear to be _two_ nitrous acids; namely, the one which I
have designated by that name, which may now be called _subnitrous_, or
as Gay Lussac terms it _pernitrous_; and the other what I considered as
_nitric acid_ in the former volume, composed of 1 atom azote, and 2 of
oxygen.
Real nitric acid then is that combination which is effected by uniting
oxygen with a minimum of nitrous gas; or 1 measure of oxygen with
1.3 nitrous gas, (See Vol. 1, page 328). The oxynitric acid, which I
was led to infer from the last mentioned combination, (1 azote with
3 oxygen) does not appear to exist. The Table of nitric acid (Vol.
1, page 355) will require some correction. An increase of about 4
per cent. should be made, I apprehend, on the quantities of acid
corresponding to the several specific gravities.
Since my former volume of Chemistry was printed, several essays on
the compounds of azote and oxygen have been published, with some new
and some additional experiments, the chief of which may be seen in
Sir H. Davy’s Elements of Chemical Philosophy, the Annales de chimie
et de physique, Vol. 1; Annals of philosophy, Vol. 9 and 10; and
the Manchester Society’s Memoirs, Vol. 4, _second series_; also Dr.
Thomson’s first principles of Chemistry. Notwithstanding all that has
been written on the subject, there still appears uncertainty as to the
number of combinations formed by these two elements, their relative
weights, and the number of atoms in the several compounds.
The results of an experiment I lately made on the decomposition
of nitrate of potash by heat seem to be worthy of record, as I am
not acquainted with those of any other person who has pursued the
experiment to the same extent.--I took an iron retort of 6 cubic inches
capacity, and cleaned it as well as I could from carbonaceous matter
which it had previously contained, first by heating nitre to redness
for an hour or more in it, and then washing it repeatedly with water
till the liquid came out tasteless, and only mixed with a little red
rust; I then put in 480 grains of purified nitre, and having secured
a copper tube to the retort so as to be air tight, the retort was put
into a fire and gradually raised to a red heat, and the fire was
occasionally urged with a pair of bellows, in order to keep up a
glowing red on the retort for nearly two hours; the air was received
over water in jars; the first 4 or 5 inches were thrown away, and the
rest was preserved and transferred to a graduated jar; the products
were examined in successive portions as under, namely,
Inches.
1 produce, 85 cubic inches, 83 per cent. pure = 70.5
2 5 77 = 3.85
3 25 50 = 12.5
4 6 30 = 1.8
----- -------
Total 121 Oxygen 88.65
Oxygen 88.65 = 30 grains.
------
Residue 32.35 = 10 grains.
About 1 per cent. on the whole gas was carbonic acid, the rest oxygen
and azote, the weights of which would be nearly as above.
Towards the last the gas came very slowly, and being of inferior
quality, the operation was discontinued.
The remaining contents of the retort were diluted with water, and
well washed till the water ceased to shew alkali; the liquid was then
concentrated and gave 1600 water grain measures of the sp. gr. 1.153.
There were obtained also 64 grains of red oxide of iron from the
washing of the retort, containing 19 grains of oxygen.
The liquid was divided into portions and examined; the original nitre
consisted of 250 grains of nitric acid united to 230 of potash = 480
grains. After the process there appeared to be,
10 grains of carbonic acid united to 21 grains potash.
62 grains of subnitrous acid to 84 ” ”
134 grains nitric acid to 125 ” ”
---
230
The quantity of carbonic acid was determined by lime water: the
quantity of potash uncombined with nitric acid was found by
precipitating it by tartaric acid, and manifested 105 grains of potash
in the bitartrate = that combined with the carbonic and subnitrous
acids; from which subtracting 21, it was inferred the remainder 84 must
have been in union with subnitrous acid, or else with nitrous acid;
the rest of the potash, not being acted upon by tartaric acid, was
understood to be combined with nitric acid.
The quantity of subnitrous acid given above, appeared somewhat
hypothetical, till it was confirmed by treating a portion of the liquid
with oxymuriate of lime solution of known strength; it was found that
32 grains of oxygen were required to be combined with the subnitrous
acid, in order to restore it to the state of nitric acid; that is,
when oxymuriate of lime, containing that quantity of oxygen, was
added to the liquid, and this was afterwards rendered acidulous by the
addition of sulphuric acid, neither nitrous vapour nor oxymuriatic gas
was perceptible; but a greater or less quantity of the oxymuriate being
applied, and the liquid made acidulous, the fumes of the one or the
other were abundantly manifest.
It remains to account for the oxygen. There were 250 grains of nitric
acid at first in the nitre; of which 200 grains were oxygen and 50
azote, nearly. One-fifth part of the oxygen = 40 grains, corresponds
to 1 atom of oxygen. Now the whole of the oxygen derived from the
nitre in the course of the experiment, seems to be 30 grains in gas, 7
grains in the carbonic acid, and 19 grains in the iron oxide, together
equal to 56 grains. Now the azote and oxygen in the gas collected, were
very nearly in the proportion of those elements in nitric acid; so
that a portion of the acid (about ⅙) might be considered as completely
decomposed, whilst the rest was only losing a small part of its
oxygen: this is remarkable, and I think indicates that the carbonic
acid (formed from the carbon of the retort, or from the adhering
carbon) unites to the potash, expelling the _nitrous_ acid, which
is immediately decomposed into its elements azote and oxygen. This
would not however account for the whole of the azote: for, 40 grains
of nitric acid would be united to 37 potash; whereas we find only 21
potash with carbonic acid; and I cannot believe that an error in the
estimate of carbonate of potash could exist to that amount. The fact,
however, was, that the elements of 40 grains of nitric acid were found
in the evolved gas, and hence we have to account for the remainder 210
grains. From this there appears to have been expelled 26 grains of
oxygen, nearly 19 and 7 as related above; of which the 19 grains cannot
be correctly estimated by reason of the uncertainty as to the real
quantity of oxide formed during the operation: there might be some left
adhering to the retort, or on the other hand there might be more than
the due share, derived from former experiments. Supposing then, that
26 grains of oxygen were extracted from the nitric acid, the remaining
acid would require the same to be added to re-form the nitric; but
by the experiments with oxymuriate of lime it seemed to require 32
grains of oxygen. This difference wants an explanation; I believe the
greater error must belong to the 26 grains; perhaps the truth might be
approximated best by supposing both to be 30 grains.
When the liquid decomposed nitre is treated with any acid, a gas is
instantly expelled which produces red fumes in the air; it is pure
nitrous gas, which joining with the oxygen of the atmosphere, generates
nitrous acid vapour. At the same time, no doubt, the subnitrous acid is
disengaged from the potash, but that part of it which is real nitrous
acid (1 atom azote to 2 of oxygen) is retained by the water, whilst the
other part, (1 atom azote and 1 of oxygen) assumes the gaseous form. In
order to be satisfied respecting this point, I made several experiments
with the liquid over mercury: taking a given portion of the liquid,
and sending it to the top of a graduated tube filled with mercury, I
passed up as much muriatic acid as was sufficient to engage the potash;
immediately there was a disengagement of nitrous gas and carbonic
acid gas, and afterwards a slow evolution of gas, evidently arising
from the liquid in contact with the mercury. Wishing to ascertain the
quantities, I sent up 25 grain measures of liquid, and to that nearly
half its bulk of muriatic acid; in 2 or 3 minutes there was,
1.1 cubic inch of gas. H. M.
1.4 in 0 45
1.5 1 5
1.7 2 45
1.75 7 45
1.78 9 45
The gas was washed in lime water, and lost .33 parts of an inch of
carbonic acid; the rest, 1.45 cubic inch, was nitrous gas. It is
obvious that ½ of the nitrous gas, together with the carbonic acid, was
liberated instantly; the rest of the nitrous gas was due to the nitrous
acid, slowly acting upon the mercury. At the end of the process, there
was a little black oxide floating upon the mercury. Calculating from
this, the whole quantity of nitrous gas would be 31 or 32 grains,
whereas it ought to have been 48 grains to constitute 62 of subnitrous
acid. It is probable that whilst a portion of the subnitrous acid is
oxidizing the mercury, another portion may be forming nitric acid and
dissolving the oxide.
From some trials, I have reason to think that even carbonic acid will
expel nitrous gas from the liquid sub-nitrite of potash.
In the essay of Dr. Henry, already alluded to, published in the 4th
Vol. of the Manchester Society’s Memoirs, a new and interesting
discovery is made; namely, that a mixture of nitrous and olefiant
gases, though not explosive by an electric spark, may still be exploded
by the more powerful impetus of a shock from a charged jar. Dr. Henry
has adduced the results obtained in this way, as corroboratory of those
which shew the constitution of nitrous gas to be 1 volume of azote and
1 of oxygen united to form 2 volumes of nitrous gas. (See page 507 of
the Memoirs.)
Some time ago in repeating these experiments of Dr. Henry, I found
some extraordinary circumstances attending them. After determining
that 1 volume of olefiant gas may be fired with from 6 to 10 volumes
of nitrous, I found a shock from a jar sometimes inadequate to fire
the mixture, which, however, when repeated a second or third time,
succeeded. This is not a novelty; for, mixtures of olefiant gas as
well as other gases and vapours, with a minimum of oxygen, frequently
require several sparks before the explosion: but this case occurs at
times with nitrous and olefiant gas, when they are mixed in the most
favourable proportions for exploding. The most remarkable circumstance,
however, was, that when a phial was filled with the mixture of the
two gases in the proportion of 1 volume olefiant to 6 or 7 nitrous,
(exclusive of small portions of azote), the decomposition of the
nitrous gas and the combustion of the olefiant were scarcely ever
perfect; and what increased the perplexity more, was, the results
obtained from the same mixture scarcely ever agreed one with the
other. After about 30 experiments, I was inclined to adopt the
conclusion, that the uncertainty was occasioned by the oblong form of
the eudiometer. The spark or shock, in my eudiometer, is imparted at
one extremity of a column of air, which is often 10 times as much in
length as in diameter: it mostly was found that the larger the quantity
of mixture exploded at once, the more imperfect and incomplete was the
combustion. I imagine the intensity of heat is not sufficient to carry
on the combustion through the length of the column, owing, perhaps, to
the cooling power of the sides of the tube. Hence it was, I apprehend,
that in one or two instances, when a small quantity of gas was used,
I got nearly complete results, as Dr. Henry reports his; but in the
majority both gases were found in the residue after the explosion.
In pursuing this enquiry into the decomposition of nitrous gas
by combustible gases, I found that it might be effected by any
combustible gas or vapour: at least it succeeded in all I tried. The
method I pursued, and which was suggested by the known properties of
phosphuretted hydrogen, is this: it has been shewn (page 181) that
a mixture of phosphuretted hydrogen and nitrous gas exploded by an
electric spark, the former gas being completely burned in case the
proportions are duly adjusted; now, it occurred to me, that as the
above combustible gas is usually a mixture of pure phosphuretted
hydrogen and of hydrogen, and that the latter of these is also
burned as well as the former, the effect must be produced through
the heat occasioned by the combustion of the former. Having some old
phosphuretted hydrogen by me, at the time, which on examination, I
found to be 91 per cent. combustible gas, and 9 azote; and the 91
combined with 156 of oxygen, consequently was 74 pure, and 17 hydrogen;
I tried this mixture with nitrous gas, when it exploded by the spark,
as usual; but on trying it with an excess or defect of nitrous gas, the
spark was inefficient, but the shock instantly fired the mixture. As
there did not appear to be any of the pure hydrogen left unburned in
these experiments, I proceeded to mix the old phosphuretted hydrogen
with hydrogen; and then this new mixture with nitrous gas. The first
experiment was made with 4 parts of old phosphuretted hydrogen + 16
hydrogen + 36 nitrous gas = 56 total. On this mixture the spark, of
course, had no effect; but it exploded the first trial by the jar, and
left 20 measures, of which 2 were found to be oxygen, and the rest
azote. This experiment succeeding so well, I next tried mixtures of
phosphuretted hydrogen, with carbonic oxide, carburetted hydrogen, and
ether vapour successively, along with nitrous gas; and found that all
these mixtures refused combustion by the spark, but were instantly
exploded by the shock, yielding carbonic acid and water, the same as if
the combustion had been effected by free oxygen. In some instances the
combustion was complete, leaving neither combustible gas nor nitrous
gas; but generally there was a residue of one or both of the gases.
From these experiments it may be concluded that the heat, produced by
the combustion of phosphuretted hydrogen and nitrous gas or oxygen
gas, disposes other gases, accidentally in the mixture, to chemical
changes. In conformity with this view, I mixed phosphuretted hydrogen
and oxygen, in the proportion of mutual saturation; and taking a
small proportion of this mixture, and as much ammoniacal gas as would
saturate the phosphoric acid to be formed, I found that causing an
explosion over mercury, the phosphoric acid combined with the ammonia,
and nearly the whole gas disappeared. In this case, the heat was not
sufficient to decompose the ammonia. But in another experiment, with a
portion of the same explosive mixture and a less proportion of ammonia,
after the firing a residue of azote and hydrogen was found, amounting
nearly to the quantity due from the decomposition of the ammonia. Here
the heat produced, had evidently decomposed the ammonia.
ON AMMONIA.
The constitution of ammonia still remains undecided. The latest
experiments on this article are those of Dr. Henry, in his essay on
the analysis of the compounds of nitrogen. (Memoirs of the Manchester
Society, vol. 4, 1824.) By electrifying ammoniacal gas over mercury, as
carefully as could be devised, Dr. Henry found results as under:
1st experiment 44 measures became 88+
2d 157 320
3d 60 122
4th 120 240
The evolved gases carefully analysed by combustion with oxygen, were
found to consist of 3 volumes of hydrogen and 1 of azote. The analysis
of ammonia was also effected by exploding it with nitrous oxide, with
the requisite precautions. The results confirmed the previous ones
by electricity, both in regard to doubling the volume of ammonia,
and establishing the ratio of 3 to 1 in the volume of hydrogen and
azote.--These experiments are highly interesting as far as regards the
question of ammonia, as they exhibit the latest investigations of one
who has previously shewn uncommon skill and perseverance in this kind
of analysis. (See Philos. Transact. 1809, &c.)
Dr. Henry’s analysis of ammonia, in 1809, has been adverted to in our
article on the subject, vol. 1, page 429. The results of that Essay are
given in a tabular form; and the mean of six experiments was nearly
as we have stated, namely, that ammonia consists of 27¼ measures of
azote, and 72¾ hydrogen. To this it may be proper to add, that the two
extremes were, 26.1 azote and 73.9 hydrogen, and 28.2 azote with 71.8
hydrogen; also that a small error has crept into the table, which being
corrected, the average results are reduced to 27 and 73, very nearly.
Subsequently, both Dr. Henry and Sir H. Davy concurred in assigning 26
and 74 for the most approximating numbers. (See Nicholson’s Journal,
25, page 153). The true quantity of gases procured by the decomposition
of ammoniacal gas by electricity, was concluded by both these
authorities, to be 180 for each 100 of ammonia, when the requisite
precautions were taken, as we have related in vol. 1.
From what is stated above, it is evident the subject is one which
requires extraordinary skill and attention. This I can attest from my
own experience, which has been frequently renewed and varied; but the
results have not been sufficiently accordant to yield me satisfaction.
About ten years ago, I made several experiments on the decomposition
of ammonia, which, though they are not convincing, deserve, perhaps,
to be recorded in their results.--Some more recent experiments are
incorporated with them.
_Decomposition of ammonia by nitrous oxide._--I made many experiments,
by exploding mixtures of nitrous oxide and ammoniacal gases over
mercury. The excess of gas was mostly on the side of ammonia, but the
proportions were varied in the different experiments, from 10 vol.
nitrous oxide to 11 ammonia or to 5, which are about the extremes
capable of being fired by the electric spark.
When 10 parts nitrous oxide and 5 of ammonia are exploded over mercury,
the residuary gas contains some free oxygen and some nitrous acid
derived from the decomposition of the excess of nitrous oxide used;
with 6 parts of ammonia there is rarely any free oxygen. When 10 parts
of nitrous oxide, and 7 of ammonia are fired, I never found any free
oxygen or hydrogen; but when the ammonia is at or near 8 parts, I
find from ¹/₂₀ to ⅒ of the hydrogen from the ammonia in the residuary
gases. The two gases appear to be completely decomposed; the oxygen of
the nitrous oxide, as far as it can, unites with the hydrogen of the
ammonia, without forming any portion of nitrous acid or of free oxygen,
and the residue contains the azote of both gases, and the unburnt
hydrogen from the ammonia, as Dr. Henry first observed. This continues
to be the case till the ammonia becomes 11 parts, when the hydrogen
amounts to about ⅓ of the whole quantity which the ammonia yields.
From the above it would seem that the proportions for mutual saturation
must be 10 nitrous oxide with from 7 to 8 parts of ammonia. This
agrees with the deduction in Dr. Henry’s first essay that 13 nitrous
oxide require 10 of ammonia; or that 10 require 7.7: but according to
the theory of volumes 10 would require 6⅔; and Dr. Henry recommends
in his late essay 10 nitrous oxide to 7.7 or 8⅓ parts of ammonia, in
order to secure a small excess of the last, and consequently some
free hydrogen after the explosion. The former of these proportions
would have nearly ⅐ of the residue hydrogen, and the latter nearly ⅕,
supposing the gases pure originally. This gives more hydrogen than I
have ever found; but the azote in my experience nearly agrees with the
doctrine of multiple volumes.
_Decomposition of ammonia by nitrous gas._--About 30 experiments
carefully made on mixtures of nitrous gas and ammoniacal gas gave very
discordant results. At one time 10 parts nitrous gas with 14 ammonia
gave ⅓ of hydrogen in excess, and another time 10 nitrous with 12
ammonia gave excess of hydrogen = ⁹/₂₀; generally 10 parts with 6 or
less gave oxygen, and 10 with 8 or more gave hydrogen in the residue.
_Decomposition of ammonia by oxygen._--The limiting proportions of
oxygen and ammonia which I have fired, are 10 oxygen to 4 ammonia
for the minimum, and 10 oxygen to 22 ammonia for the maximum. When
10 oxygen were fired with 4 ammonia, there were ²⁵/₃₇ of the oxygen
left, and there was a deficiency of azote amounting to ¹/₁₂ of what was
expected from the ammonia, owing no doubt to nitrous acid generated
by the explosion. When 10 oxygen to 1.8, or from that to 2.2 ammonia
are used, there is a surplus of about ¼ or ⅓ of the hydrogen contained
in the ammonia, left in the residue of the gas. When the ammonia is
between 13 and 14 there is usually a trace of oxygen or hydrogen as
it approaches either of these limits. By the theory of volumes, 10
oxygen should saturate 13⅓ of ammoniacal gas. I have not any instance
of hydrogen being left when 14 ammonia were used, though there ought
to be ¹/₂₀ of the whole left; and much smaller quantities than that
are appreciable by well known methods. The azote resulting from the
decomposition of ammonia is usually very nearly ½ the volume of the
ammonia.
On the whole the results from firing ammonia and oxygen gas appear to
me more satisfactory than those obtained from nitrous oxide and nitrous
gas, as they are more simple and less perplexed with any theoretic
views.
It may be proper to remind the reader that when we speak of 10 parts
of one gas uniting with 8, 10, or more, of another in the above and
other cases, it is to be understood of gases _absolutely pure_; not
that we ever obtain them in that state, but approximating as near as we
can to it, we mix given portions of such gases as we can obtain, and
then in our calculations of results deduct for the impurities.
One source of uncertainty in these experiments on firing mixtures of
ammonia, is that the real quantity of ammoniacal gas operated upon
is not known. If a certain measure of ammonia be transferred through
mercury ever so dry, some portion of it gets entangled in the mercury,
and 100 measures become perhaps 95: now in the explosion it is a
question whether any part of the 5 measures absorbed is decomposed.
I have marked this attentively, and am persuaded that generally
speaking, little if any of that portion is decomposed; but some trace
of it appears mostly afterwards in the residue as it is liberated from
the pressure of its own kind of gas, and hence easily rises into the
gaseous mixture. Notwithstanding, when the loss of gas by transfer
amounts to 10 or 20 per cent., I have reason to believe that some part
of it suffers combustion occasionally.
_Volume of gases from the decomposition of ammonia._--It has been
observed (vol. 1. Ammonia) that Sir H. Davy obtained 180 measures of
gases, by means of electricity, from 100 of ammonia as the maximum when
the operation was performed with great care, and Dr. Henry in like
circumstances, produced 181, whilst I found 187 measures; since that,
as has been related, Dr. Henry has found 200 measures. It is not easy
to account for these differences; I am inclined to the opinion that the
volume of gases is very nearly doubled, but probably rather less than
more. I find the experiments on the rapid combustion of ammonia agree
best with that opinion.
_Decomposition of ammonia by a red heat._--A short time since I
repeated the decomposition of ammonia by passing the gas through a red
hot copper tube. The proportion of azote to hydrogen, due allowance
being made for a minute portion of atmospheric air, was upon the
average of a number of experiments, 26 of the former to 74 of the
latter.
_Decomposition of ammonia by oxymuriatic acid._--I have made several
experiments on this mode of decomposition since the results published
in vol. 1, page 435. It is well known that a solution of oxymuriate
of lime decomposes ammoniacal salts; water and muriatic acid are
produced, azote liberated, and the acid previously combined with the
ammonia is evolved. But this is not all; an excessively pungent gas or
perhaps vapour is produced, exciting sneezing, and inducing catarrh;
the constitution of this vapour is not well understood; it is never
formed, as far as I know, without the presence of both oxymuriatic acid
and ammonia. The results of such mixtures are of course complicated and
likely to be unsatisfactory; it may notwithstanding be useful to relate
some of them.
When clear oxymuriate of lime solution, and a salt of ammonia are mixed
together with a little excess of oxymuriate, the ammonia is mostly
decomposed, the oxymuriate being converted into muriate of lime by the
hydrogen of the ammonia, whilst the azote is evolved, and the acid
previously combined with the ammonia is liberated; hence oxymuriatic
acid gas is also liberated along with the azote; and it is required to
be taken out before the azote can be estimated. This circumstance may
be obviated by previously adding the requisite quantity of pure potash
or soda, to engage the acid, or by leaving a little undissolved lime in
the oxymuriatic solution. I could never obtain a volume of azote equal
to half that of the ammonia (supposed to be in a gaseous state) though
it is universally allowed not to be less than that, if the whole of the
azote be evolved; on one occasion only I got so much as ¹⁴/₁₅ of that
quantity. The residue of liquid has the extremely pungent smell; but
the azotic gas after passing through pure water has no smell. When this
experiment is made over mercury, the oxymuriatic acid acts upon it, and
hence the excess of oxymuriate should be such as to leave a portion of
that undecomposed at the conclusion.
When the object is to ascertain the hydrogen in ammonia, a portion
of salt known to contain a given weight of ammonia is to be treated
with oxymuriate of lime solution, the strength of which is accurately
determined by means of green sulphate of iron, or otherwise. The
ammoniacal salt in solution is then to be mixed with a moderate
redundance of the oxymuriate liquid, and with a few drops of caustic
potash, and the mixture must be repeatedly agitated for some time. At
length the liquid must be tested by the green sulphate of iron, and
hence the quantity of acid spent upon the ammonia will be determined.
I have mostly found the hydrogen this way below the common estimate,
allowing the ammoniacal salts to be correctly determined.
SULPHURET OF CARBON.
Since the article at page 462, vol. 1, was written, an excellent essay
on the sulphuret of carbon has been published in the Philosophical
Transactions, (1813) by Professor Berzelius and Dr. Marcet. After an
extensive series of experiments, they infer the atom of the sulphuret
to consist of 2 atoms sulphur and 1 of carbon. The investigation did
not seem to warrant their including hydrogen in the atom. I have made
several experiments on the combustion of the vapour of sulphuret of
carbon in oxygen gas by electricity. My method generally was, to
vapourize a given portion of atmospheric air over mercury, taking
care that the vapour was below the maximum for the temperature; this
is easily effected by putting the liquid into a phial of air, drop by
drop, and inverting it over mercury till the liquid is evaporated.
This vapourized air, I find may be transferred through mercury with
very little loss, and even through water several times, without a
total condensation of the vapour. The vapour of ether is much more
condensible by water than that of sulphuret of carbon. A given portion
of this vapourized air is to be mixed with oxygen gas, in Volta’s
eudiometer, and then exploded by the electric spark over mercury. One
volume of vapour combines with nearly 3½ of oxygen, and therefore
requires 4 or 5 times its bulk of that gas before firing, in order
that the combustion may be complete. The results of the combustion are
carbonic acid and sulphurous acid; and I suspect a small portion of
water; though Professor Berzelius and Dr. Marcet could not detect any.
By evaporating a given weight of the sulphuret of carbon, in a given
volume of atmospheric air, at the temperature of 60°, I find the
specific gravity of the vapour to be 2.75 nearly, air being 1. Now if
we assume the atom of vapour to be nearly of the same volume as that of
hydrogen, and to consist of 1 atom hydrogen, 2 sulphur, and 1 carbon,
it will require 7 atoms of oxygen to form water, sulphurous acid, and
carbonic acid, which will accord very well with my experience. When
vapourized hydrogen gas is electrified for some time, there is no
change of volume, though there is some appearance of decomposition.
Probably the hydrogen of the sulphuret is liberated. It is difficult
to conceive how so volatile a liquid as the one in question, could be
constituted out of sulphur and carbon without the addition of hydrogen.
POTASSIUM, SODIUM, &c.
Two views of the nature of these bodies have been given in vol. 1,
(see pages 260, and 484, &c.). In the former they are considered as
simple metals; in the latter, as compound bodies resulting from the
abstraction of oxygen from the hydrates of potash and soda; or as being
constituted of 1 atom of hydrogen united to 1 atom of pure potash or
soda respectively. Those who have had the most experience on these
elements, Sir H. Davy, and M. M. Gay Lussac and Thenard, seem now to
concur in the former view, and it has been adopted by most chemists.
Part of the objections which we made to this view have been obviated,
it should seem, by establishing the fact, that oxymuriatic gas and
hydrogen gas united, form muriatic acid gas. There are still, however,
difficulties to remove before this view can be considered perfectly
satisfactory; but they are not greater perhaps than would attach
to any other explanation of the facts connected with the subject.
Besides potassium and sodium, experience as well as analogy would seem
to render probable, if not to establish, the existence of barium,
strontium, and calcium as metals, of which barytes, strontites, and
lime are the protoxides, as potash and soda are of the other two
metals; (other oxides of potassium and sodium are stated, see page
55-57); barium has a deutoxide, and probably calcium likewise. The
rest of the earths, as magnesia, alumine, silex, &c. are by analogy
considered by most chemists as oxides of particular metals, but the
proportions of their elements have not been determined.
ALUM.
At page 531, vol. 1, we have given the constitution of this important
salt, as under: since that time Mr. R. Phillips has announced another
view of it; and Dr. Thomson has published one differing from both of
these. They are as follow:
_Dalton_-- 1 atom sulphate of potash.
4 atoms sulphate of alumine.
30 atoms water.
_Phillips_-- 1 atom bisulphate of potash.
2 atoms sulphate of alumine.
22 atoms water.
_Thomson_-- 1 atom sulphate of potash.
3 atoms sulphate of alumine.
25 atoms water.
Notwithstanding these differences, there is a near approximation in all
three, in regard to the quantities of acid, alumine, potash, and water
in the salt. This is accounted for partly in the different relative
weights of the atoms, as estimated by the different analysts, but
chiefly in that of alumine.
Some very curious results occurred to me about 10 years ago in
analysing alum; they were new to me, but I have since found they had
been previously discovered by Scheele. (See his essay on silex, clay,
and alum, 1776.) As his observations are not to be found in any of our
elementary books that I have seen, I shall give the particulars of my
own experiments here.
I take 24 grains of alum and dissolve them in water; of these 8 grains
may be allowed for sulphuric acid, ⅕ of which = 1.6 grain = 1.1 grain
of lime = 880 grains of lime water, such as I commonly use. To the
solution of alum I put 880 grains of lime water; a slight precipitate
appears which soon becomes redissolved almost completely. The liquid is
then acid by the colour test.
To this liquid I put 880 more of lime water, and agitate; a copious
precipitate appears and continues; after subsidence the clear liquid is
still acid by the colour test.
Another 880 grains are added, and the whole is then well agitated; the
agitation is repeated two or three times after the precipitate has
partly subsided, so as to diffuse it equally again through the liquid;
finally, the clear liquid is found to be neutral by the colour test,
and to contain no alumine; for, lime water produces no precipitate when
poured into it.
Another 880 grains being added, and the whole stirred well, the clear
liquid after the subsidence of the precipitate is still neutral by the
colour test.
The fifth portion of 880 grains being then added, and the mixture well
agitated, a considerable portion of the precipitate will evidently
disappear, and the mixture become semitransparent; after a time the
clear supernatant liquid is found strongly alkaline; a little of it
touched with an acid becomes milky, and adding more acid clears it
again. The liquid is now 1.0025 sp. gr., or a little heavier than lime
water.
The sixth portion of 880 grains being now added to the whole mixture,
and agitated, the precipitate rather diminishes, and an increase of
specific gravity takes place in the liquid; it is now 1.003.
The seventh and last portion of 880 grains being added to the mixture,
and agitation being continued for some time, a dense bulky precipitate
is formed, which falls with great celerity, carrying with it the
greatest part of the acid, the alumine and the lime, and leaving the
liquid of the sp. gr. 1.0012. It is a subsulphate into which acid,
potash, lime and alumine enter, as will be shewn.
These phenomena appear to me to be best explained by adopting a
constitution of alum, such as to make it consist of 1 atom bisulphate
of potash and 3 atoms of sulphate of alumine; after which the following
explanation will apply.
The first portion of lime water saturates the excess of acid.
The second portion throws down a correspondent portion of alumine. The
clear liquid is acid, because it contains sulphate of alumine, which is
essentially acid by the colour test, because alumine is not an alkaline
element.
The third portion throws down another portion or atom of alumine; but
by continued agitation the two atoms of alumine liberated, join the
remaining atom of sulphate of alumine, and the whole compound falls
down, being then the common subsulphate of alum. Hence the liquid,
containing nothing but sulphate of lime and sulphate of potash, is
neutral by the test, and yields no alumine by the addition of lime
water.
The fourth portion of lime water being put in and duly agitated, the
atom of sulphuric acid is drawn from the subsulphate to join the lime,
and then the floating subsulphate of alumine becomes pure alumine, and
the clear liquor is still neutral.
The fifth portion of lime water tries to decompose the sulphate of
potash, but is unable of itself; however, the floating alumine assists
it, and by double affinity the potash leaves the acid to join the
alumine, and the lime takes the acid. Hence as ⅓ of the alumine enters
into solution with the potash, the precipitate is less copious, and the
liquid is alkaline; a small portion of acid put into the clear liquid
engages the potash, and liberates the alumine, but a larger portion
redissolves the alumine also.
The sixth portion of lime water seems to complete the effect which the
fifth commences, and hence the density of the liquid increases, whilst
the precipitate rather diminishes.
The seventh portion of lime, together with the sixth, after due
agitation and some time, unite the lime with the alumine, one atom of
each, and form a precipitate which would fall together, were no other
compound present, as I found, and Scheele before me; but if sulphate of
lime be present, each compound atom of lime and alumine, unites with
one of sulphate of lime, and the whole descends together, forming a
subsulphate resembling that of alum, only two atoms of lime are found
as substitutes for two atoms of alumine. This subsalt is very little
soluble in water.
According to this view, if 2 atoms of alum were decomposed, 4 atoms of
subsulphate would be formed, each consisting of 1 acid, 2 lime, and
1 alumine; also 2 compound atoms of potash and alumine, and 6 atoms
sulphate of lime. But in the final arrangement, it would seem, that 2
atoms of sulphate of lime are again decomposed, and sulphate of potash
formed, the 2 atoms of lime combining with the 2 of alumine, and then
two more atoms of subsulphate are formed, and the final arrangement is
6 atoms subsulphate precipitated, and 2 atoms sulphate of potash, and 2
sulphate of lime remain in solution.
The facts above stated appear to me to place the constitution of alum
in a clearer point of view than any other I have seen. They make no
difference in the weights of the several elements in 100 grains of the
salt, from what we have given in Vol. 1; only the weight of the atom of
alumine is here taken to be 20 instead of 15, and we have 3 atoms of it
in 1 of alum, instead of 4, as in the former account.
ON THE PRINCIPLES OF THE ATOMIC SYSTEM OF CHEMISTRY.
It is generally allowed that the great objects of the atomic system
are, 1st to determine the relative weights of the simple elements;
and 2d to determine the _number_, and consequently the weight, of
simple elements that enter into combination to form compound elements.
The greatest _desideratum_ at the present time is the exact relative
weight of the element hydrogen. The small weight of 100 cubic inches
of hydrogen gas, the important modifications of that weight by even
very minute quantities of common air and aqueous vapour, and the
difficulties in ascertaining the proportions of air and vapour in
regard to hydrogen, are circumstances sufficient to make one distrust
results obtained by the most expert and scientific operator. The
specific gravity of hydrogen gas was formerly estimated at ⅒ that of
common air; it descended to ¹/₁₂.₅, which is the ratio we adopted
in the Table at the end of Vol. 1. it is now commonly taken to be
¹/₁₄.₅, and whether it may not in the sequel be found to be ¹/₁₆.₅
is more than any one at present, I believe, has sufficient data to
determine. The other factitious gases have mostly undergone some
material alterations in their specific gravities in the last twenty
years, several of which I have no doubt are improvements; but when we
see these specific gravities extended to the 3rd, 4th, and 5th places
of decimals, it appears to me to require a credit far greater than
any one of us is entitled to. In the mean time, it may be thought a
fortunate circumstance, that the weight of common air has undergone
no change for the last thirty or forty years; 100 cubic inches bring
estimated to weigh 30.5 grains at the temperature of 60°, and pressure
of 30 inches of mercury: (whether this is exclusive of the moisture I
do not recollect.) It is also a fortunate circumstance, (provided it be
correct) that this weight is nearly free from decimal figures. I may
be allowed to add, that according to my experience, the weight of 100
cubic inches of air is more nearly 31 grains than 30.5. I apprehend
these observations are sufficient to shew that something more remains
to be done before we obtain a tolerably correct table of the specific
gravities of gases; the importance of this object can not be too highly
estimated.
The combinations of gases in equal volumes, and in multiple volumes, is
naturally connected with this subject. The cases of this kind, or at
least approximations to them, frequently occur; but no principle has
yet been suggested to account for the phenomena; till that is done I
think we ought to investigate the facts with great care, and not suffer
ourselves to be led to adopt these analogies till some reason can be
discovered for them.
The 2d object of the atomic theory, namely that of investigating the
_number_ of atoms in the respective compounds, appears to me to have
been little understood, even by some who have undertaken to expound the
principles of the theory.
When two bodies, A and B, combine in multiple proportions; for
instance, 10 parts of A combine with 7 of B, to form one compound, and
with 14 to form another, we are directed by some authors to take the
smallest combining proportion of one body as representative of the
elementary particle or atom of that body. Now it must be obvious to
any one of common reflection, that such a rule will be more frequently
wrong than right. For, by the above rule, we must consider the first
of the combinations as containing 1 atom of B, and the second as
containing 2 atoms of B, with 1 atom or more of A; whereas it is
equally probable by the same rule, that the compounds may be 2 atoms
of A to 1 of B, and 1 atom of A to 1 of B respectively; for, the
proportions being 10 A to 7 B, (or, which is the same ratio, 20 A to 14
B,) and 10 A to 14 B; it is clear by the rule, that when the numbers
are thus stated, we must consider the former combination as composed
of 2 atoms of A, and the latter of 1 atom of A, united to 1 or more of
B. Thus there would be an _equal_ chance for right or wrong. But it is
possible that 10 of A, and 7 of B, may correspond to 1 atom A, and 2
atoms B; and then 10 of A, and 14 of B, must represent 1 atom A, and 4
atoms B. Thus it appears the rule will be more frequently wrong than
right.
It is necessary not only to consider the combinations of A with B,
but also those of A with C, D, E, &c.; as well as those of B with
C, D, &c., before we can have good reason to be satisfied with our
determinations as to the _number_ of atoms which enter into the various
compounds. Elements formed of azote and oxygen appear to contain
portions of oxygen, as the numbers 1, 2, 3, 4, 5, successively, so
as to make it highly improbable that the combinations can be effected
in any other than one of two ways. But in deciding which of those two
we ought to adopt, we have to examine not only the compositions and
decompositions of the several compounds, of these two elements, but
also compounds which each of them forms with other bodies. I have spent
much time and labour upon these compounds, and upon others of the
primary elements carbone, hydrogen, oxygen, and azote, which appear to
me to be of the greatest importance in the atomic system; but it will
be seen that I am not satisfied on this head, either by my own labour
or that of others, chiefly through the want of an accurate knowledge of
combining proportions.
NEW TABLE OF THE RELATIVE WEIGHTS OF ATOMS.
At the close of the last volume, the weights of several principal
chemical elements or atoms were given; but as several additions and
alterations have been educed from subsequent experience, it has been
judged expedient to present a reformed table of weights.
SIMPLE ELEMENTS.
Weights.
Hydrogen 1
Azote 5±, or 10?
Carbone 5.4
Oxygen 7
Phosphorus 9
Sulphur 13, or 14
Calcium 17?
Sodium 21
Arsenic 21
Molybdenum 21, or 42?
Cerium 22?
Iron 25
Manganese 25
Nickel 26
Zinc 29
Tellurium 29, or 58?
Chromium 32
Potassium 35
Cobalt 37
Strontium 39
Antimony 40
Iridium 42
Palladium 50
Uranium 50, or 100?
Tin 52
Copper 56, or 28?
Rhodium 56
Titanium 59?
Gold 60±
Barium 61
Bismuth 62
Platina 73
Tungsten 84, or 42?
Silver 90
Lead 90
Columbium 107? 121?
Mercury 167, or 84?
SIMPLE OR COMPOUND?
Weights.
Fluoric Acid 10? 15?
Magnesia 17
Alumine 20
Glucine 23? 34?
Lime 24
Oxymuriatic Acid
(chlorine) 29, or 30
Muriatic Acid} 30, or 31
Gas}
Zircone 45
Silex 45?
Yttria 53? 36? 18?
COMPOUND ELEMENTS.
Weights.
Ammonia 6? 12? 13?
Olefiant Gas 6.4? 12.8?
Carburetted Hydrogen
or Pond Gas 7.4
Water 8
Phosphuretted Hydrogen 10
Nitrous Gas 12, or 24?
Carbonic Oxide 12.4
Sulphuretted Hydrogen 15
Deutoxide of Hydrogen 15
Nitrous Oxide 17
Nitrous Acid 19, or 38?
Carbonic Acid 19.4
Sulphurous Oxide 21
Phosphoric Acid 23
Sulphurous Acid 28
Protoxide of Arsenic 28
Soda 28
Hydrate of Lime 32
Protoxide of Iron 32
Protoxide of Manganese 32
Protoxide of Nickel 33
Sulphuric Acid 35
Sulphuret of Arsenic (native) 35
Hydrate of Soda 36
Oxide of Zinc 36
Carbonate of Magnesia 36.4
Protosulphuret of Iron 39
Deutoxide of Manganese 39
Oxide of Chromium 39
Muriate of Magnesia 39
Protosulphuret of Nickel 40
Protosulphuret of Lime 41
Carbonate of Lime 43.4
Protoxide of Cobalt 44
Strontites 46
Muriate of Lime 46
Chromic Acid 46
Protoxide of Antimony 47
Carbonate of Soda 47.4
Hydrate of Potash 50
Muriate of Soda 50
Sulphate of Magnesia 52
Sulphuret of Antimony 54
Sulphate of Alumine (simple) 55
Oxide of Palladium 57
Sulphate of Lime 59
Protoxide of Tin 59
Carbonate of Potash 61.4
Hydrosulphuret of Antimony 62
Nitrate of Magnesia 62
Sulphate of Soda 63
Protoxide of Copper 63
Muriate of Potash 64
Deutoxide of Tin 66
Protosulphuret of Tin 66
Oxide of Gold 67
Barytes 68
Muriate of Lime 69
Oxide of Bismuth 69
Deutoxide of Copper 70
Nitrate of Soda 73
Sulphuret of Gold 74
Protosulphuret of Bismuth 76
Sulphate of Potash 77
Oxide of Platina 80?
Nitrate of Potash 87
Carbonate of Barytes 87
Muriate of Barytes 90
Oxide of Silver 97
Protoxide of Lead 97
Minium 98
Sulphate of Barytes 103
Deutoxide of Lead 104
Protosulphurets of
Lead and Silver 104
Nitrate of Barytes 113
Protoxide of Mercury 174?
Deutoxide of Mercury 181?
Protosulphuret of Mercury 181
Alum 277
ADDENDA.
STEEL.--Since writing the article at page 214, I have had an
opportunity of analysing the crystalline steel, formed by Mr.
Macintosh’s process of cementation by means of coal gas. I dissolved
21 grains of this steel in sulphuric acid, with only a very slight
excess of acid. The whole was dissolved except about ⅒ of a grain of
silvery-like particles. The gas obtained amounted to 29.6 cubic inches.
It yielded no trace of carbonic acid. When fired with oxygen it yielded
3 per cent. upon the volume of hydrogen of carbonic acid; and this
arose, as I ascertained, from the hydrogen containing 3 per cent of
carburetted hydrogen gas: it contained no carbonic oxide. Supposing the
carbone to have been combined with the iron, it would amount only to
about ⅝ of a grain, to 100 grains of iron. Whether such a quantity can
be deemed an essential or an accidental ingredient of steel, may be a
subject of consideration.
_By a mistake of the Printer, the following paragraphs were omitted
after page 308._
EXAMPLE.
According to the following values of the different specific gravities,
(of the accuracy of some of which there may be doubts) and referring
to my essay on oil gas (Manchester Memoirs, Vol. 4, new series, page
79,) we may take the oil gas, which, when the incombustible portion was
abstracted would be nearly .812 sp. gravity, and
100 pure gas give 152 carb. acid and take 248 oxygen;
Here _w_ = 100, _a_ = 152, _g_ = 248, _S_ = 1.458, ∫ = .555, _c_ = .972
_s_ = .0694 and _C_ = .812. The value of _u_ reduces to the following
form;
_u_ = 4.7916_a_ - 1⅔_g_ + 1.875_w_ - 6_C__w_
-------------------------------------------- = 24.5
.625
hydrogen per cent. of pure combustible gas.
Hence we have 75.5 volumes left for the 3 other ingredients = _w_ of
the formula; and abstracting 12 + from the oxygen on account of the
hydrogen, _g_ = 236, and _a_ = 152 as above.
Whence _x_ = Superolefiant = 38¼
_y_ = Carb. hydrg. = 30.2
and _z_ = Carb. oxide = 7+
-----
75.5
These results differ considerably from those deduced in the above
essay; probably in part from errors in the above estimates of the
specific gravities of one or more of the gases.
EXPANSION OF LIQUIDS BY HEAT.
I am not aware of any particular labour that has recently been given
to the enquiry how far pure liquids accord with each other in the law
which I announced as derived from the experiments on water and mercury,
and corroborated by those upon several other liquids. See Vol. 1, Table
of temperature, page 14; also page 36, and following.
Perhaps all liquids should be considered as _pure_ that are subject to
uniform congelation at certain temperatures on the one hand, and on the
other are capable of being distilled by heat without any alteration in
their constitution. Water and mercury will rank in the first place;
alcohol of .82 specific gravity and ether of .72; concentrated
sulphuric acid; nitric acid of 1.42 specific gravity: naphtha and oil
of turpentine, &c. will probably be thought to claim the next place.
It is desirable that the temperatures at which these liquids congeal
should be ascertained; also whether any decomposition is effected by
the operation. If these expand proportionally to a scale of square
numbers for certain given equal or unequal intervals of temperature,
it may point out something relative to the collocation of the ultimate
particles in liquids. The apparent coincidence of this rate of
expansion in liquids, with the geometrical progressive force of steams
or vapours creates an additional interest. It may be that most or all
of these supposed relations are accidental, and only approximative
like that of the rate of expansion of air and mercury, between the
temperatures of -40° and 212°; but I cannot think this probable. Even
should they be only approximations, they are of sufficient utility to
be kept in view.
_FINIS._
_Printed by the Executors of S. Russell_
BOOKS, ESSAYS, &c.,
_PUBLISHED BY THE SAME AUTHOR._
METEOROLOGICAL OBSERVATIONS AND ESSAYS. 4_s._ 8vo. 1793.
ELEMENTS OF ENGLISH GRAMMAR: or, a new System of Grammatical
Instruction, for the use of Schools and Academies.
2_s._ 6_d._ 12mo. 1801.
☞_A few Copies of these Works may still be had of the
London Booksellers._
A NEW SYSTEM OF CHEMICAL PHILOSOPHY.
Part I. of Vol. I. 7_s._ 8vo. 1808.
Published by G. Wilson, Bookseller, Essex Street, Strand, London.
_ESSAYS, by the same, in the Memoirs of the Literary
and Philosophical Society, Manchester._
VOL. 5. PART 1.--Extraordinary facts relating
to the vision of colours.
PART 2.--Experiments and observations to
determine whether the quantity of rain and dew is equal
to the quantity of water carried off by the rivers, and
raised by evaporation; with an enquiry into the origin
of springs.
Experiments and observations on the power of fluids, to
conduct heat, with reference to Count Rumford’s seventh
essay on the same subject.
Experiments and observations on the heat and cold
produced by the mechanical condensation and rarefaction
of air.
Experimental essays on the constitution of mixed
gases; on the force of steam or vapour from water and
other liquids, in different temperatures, both in a
Torricellian vacuum, and in air; on evaporation; and on
the expansion of gases by heat.
Meteorological observations made at Manchester,
from 1793 to 1801.
VOL. 1. _Second series._--Experimental enquiry
into the proportions of the several gases or
elastic fluids constituting the atmosphere.
On the tendency of elastic fluids to diffusion through each
other.
On the absorption of gases by water and other liquids.
Remarks on Mr. Gough’s two essays on the doctrine of mixed
gases; and on Professor Schmidt’s experiments on the
expansion of dry and moist air by heat.
VOL. 2. On respiration and animal heat.
VOL. 3. Experiments and observations on phosphoric
acid and on the salts denominated phosphates.
Experiments and observations on the combinations of
carbonic acid and ammonia.
Remarks tending to facilitate the analysis of spring
and mineral waters.
Memoir on sulphuric ether.
Observations on the barometer, thermometer, and rain,
at Manchester, from 1794 to 1818 inclusive.
VOL. 4. On oil, and the gases obtained from it by heat.
Observations in Meteorology, particularly with regard to the
dew-point, or quantity of vapour in the atmosphere; made
on the mountains in the North of England.
On the saline impregnation of the rain which fell during
the late storm, December 5th, 1822--with an appendix
to the same.
On the nature and properties of indigo, with directions for
the valuation of different samples.
_In the Philosophical Transactions of the Royal Society._
On the Constitution of the Atmosphere.--1826.
_In Mr. Nicholson’s Philosophical Journal._
VOL. 5. (Quarto) On the constitution of mixed
elastic fluids, and the atmosphere.--1801.
VOL. 3. (Octavo) On the theory of mixed gases.
5. On the zero of temperature.
6. Correction of a mistake in Dr. Kirwan’s essay on
the state of vapour in the atmosphere.
8. On chemical affinity as applied to atmospheric air.
9. Observations on Mr. Gough’s strictures on the theory
of mixed gases.
10. Facts tending to decide at what point of temperature
water possesses the greatest density.
12. Remarks on Count Rumford’s experiments on the max.
density of water.
13 & 14. On the max. density of water in reference to
Dr. Hope’s experiments.
28. On the signification of the word _particle_
as used by chemists.
29. Observations on Dr. Bostock’s review of the
atomic principles of chemistry.
_In Dr. Thomson’s Annals of Philosophy._
VOL 1 & 2. On oxymuriate of lime.--1813.
3. Remarks on the essay of Dr. Berzelius, on the cause of
chemical proportions.
7. Vindication of the theory of the absorption of gases by
water, against the conclusions of M. De Saussure.
9 & 10. On the chemical compounds of azote and oxygen, and
on ammonia.
11. On phosphuretted hydrogen.
12. On the combustion of alcohol, by the lamp without flame.
On the _vis viva_.
_In Phillips’s Annals of Philosophy._
VOL. 10. (new series). On the analysis of atmospheric air
by hydrogen.
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