Part 19

_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.