Part 1

Transcriber’s Notes:

Underscores “_” before and after a word or phrase indicate _italics_ in the original text. Equal signs “=” before and after a word or phrase indicate =bold= in the original text. Small capitals have been converted to SOLID capitals. Footnotes have been moved so they do not break up paragraphs. Old or antiquated spellings have been preserved. Typographical and punctuation errors have been silently corrected.

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.