1. That of hydrogene for nitrogene, producing ammoniac.2. That of oxygene for nitrous gas, producing nitric acid.3. That of the hydrogene of ammoniac for the oxygene of nitric acid.4. That of the nitrogene of ammoniac for the nitrous gas of nitric acid.
1. That of hydrogene for nitrogene, producing ammoniac.
2. That of oxygene for nitrous gas, producing nitric acid.
3. That of the hydrogene of ammoniac for the oxygene of nitric acid.
4. That of the nitrogene of ammoniac for the nitrous gas of nitric acid.
At temperatures below 300°, the salt, from the equilibrium between these affinities, preserves its existence.
Now when its temperature is raised to 400°, the attractions ofhydrogene for nitrogene,[90]and of nitrous gas for oxygene,[91]are diminished; whilst the attraction of hydrogene for oxygene[92]is increased; and perhaps that of nitrogene for nitrous gas.
Hence the former equilibrium of affinity is destroyed, and a new one produced.
The hydrogene of the ammoniac combines with the oxygene of the nitric acid to generate water; and the nitrogene of the ammoniac enters into combination with the nitrous gas to form nitrous oxide: and the water and nitrous oxide produced, most probably exist in binary combination in the aëriform state, at the temperature of the decomposition.
But when a heat above 800° is applied to nitrate of ammoniac, the attractions of nitrogene and hydrogene for each other, and of oxygenefor nitrous gas,[93]are still more diminished; whilst that of nitrogene for nitrous gas is destroyed, and that of hydrogene for oxygene increased to a great extent: likewise a new attraction takes place; that of nitrous gas for nitric acid, to form nitrous vapor.[94]Hence a new arrangement of principles is rapidly produced; the nitrogene of ammoniac having no affinity for any of the single principles at this temperature, enters into no binary compound: the oxygene of the nitric acid forms water with the hydrogene, and the nitrous gas combines with the nitric acid to form nitrous vapor. All these substances most probably exist in combination at the temperature of their production; and at a lower temperature, assume the forms of nitrous acid, nitrous gas, nitrogene, and water.
I have avoided entering into any discussions concerning the light and heat produced in this process; because these phænomena cannot be reasoned upon as isolated facts, and their relation to general theory will be treated of hereafter.
X.On the preparation of Nitrous Oxidefor experiments on Respiration.
When compact nitrate of ammoniac is slowly decomposed, the nitrous oxide produced is almost immediately fit for respiration; but as onepart of the salt begins to decompose before the other is rendered fluid, a considerable loss is produced by sublimation.
For the production of large quantities of nitrous oxide, fibrous nitrate of ammoniac should be employed. This salt undergoes no decomposition till the greater part of its water is evaporated, and in consequence at the commencement of that process, is uniformly heated.
The gas produced from fibrous nitrate, must be suffered to rest at least for an hour after its generation. At the end of this time it is generally fit for respiration. If examined before, it will be found to contain more or less of a white vapor, which has a disagreeable acidulous taste, and strongly irritates the fauces and lungs. This vapor, most probably, consists of acid nitrate of ammoniac and water, which were dissolved by the gas at the temperature of its production, and afterwards slowly precipitated.
It is found in less quantity when compact nitrate is employed, because more salt is sublimed in this process, which being rapidly precipitated, carries with it the acid and water.
Whatever salt is employed, the last portions of gas produced, generally contain less vapor, and may in consequence be respired sooner than the first.
The nitrate of ammoniac should never be decomposed in a metallic vessel,[95]nor the gas produced suffered to come in contact with any metallic surface; for in this case the free nitric acid will be decomposed, and in consequence, a certain quantity of nitrous gas produced.
The apparatus that has been generally employed in the medical pneumatic institution, for the production of nitrous oxide, consists
1. Of a glass retort, of the capacity of two or three quarts, orificed at the top, and furnished with a ground stopper.2. Of a glass tube, conical for the purpose of receiving the neck of the retort; about ,4 inches wide in the narrowest part, 4 feet long, curved at the extremity, so as to be capable of introduction into an airholder, and inclosed bytin plate to preserve it from injury.3. Of airholders of Mr. Watt’s invention, filled with water saturated with nitrous oxide.4. Of a common air-furnace, provided with dampers for the regulation of the heat.
1. Of a glass retort, of the capacity of two or three quarts, orificed at the top, and furnished with a ground stopper.
2. Of a glass tube, conical for the purpose of receiving the neck of the retort; about ,4 inches wide in the narrowest part, 4 feet long, curved at the extremity, so as to be capable of introduction into an airholder, and inclosed bytin plate to preserve it from injury.
3. Of airholders of Mr. Watt’s invention, filled with water saturated with nitrous oxide.
4. Of a common air-furnace, provided with dampers for the regulation of the heat.
The retort, after the insertion of the salt, is connected with the tube, carefully luted, and exposed to the heat of the furnace, on a convenient stand. The temperature is never suffered to be above 500°. After the decomposition has proceeded for about a minute, so that the gas evolved from the tube enlarges the flame of a taper, the curved end is inserted into the airholder, and the nitrous oxide preserved.
The water thrown out of the airholders in consequence of the introduction of the gas, is preserved in a vessel adapted for the purpose, and employed to fill them again; for if common water was to be employed in every experiment, a great loss of gas would be produced from absorption.
A pound of fibrous nitrate of ammoniac, decomposed at a heat not above 500°, produces nearly 5 cubic feet of gas; whilst from a pound of compact nitrate of ammoniac, rarely more than 4,25 cubic feet can be collected.
For the production of nitrous oxide in quantities not exceeding 20 quarts, a mode still more simple than that I have just described may be employed. The salt may be decomposed by the heat of an argands lamp, or a common fire, in a tubulated glass retort, of 20 or 30 cubic inches in capacity, furnished with a long neck, curved at the extremity; and the gas received in small airholders.
Thus, if the pleasurable effects, or medical properties of the nitrous oxide, should ever make it an article of general request, it may be procured with much less time, labor, and expence,[96]than most of the luxuries, or even necessaries, of life.
EXPERIMENTS and OBSERVATIONS on the COMPOSITION of NITROUS GAS, and on its ABSORPTION by different bodies.
I.Preliminaries.
Inmy account of the composition of nitric acid, inDivision I. I gave an estimation of the quantities of oxygene and nitrogene combined in nitrous gas: I shall now detail the experiments on which that estimation is founded.
At an early period of my researches relating to nitrous oxide, from the observation of the phænomena taking place during the production of this substance, I had concluded, that the common opinion with regard to the composition of nitrous gas, was very distant from the truth. I had indeed analysed nitrous gas, by converting it into nitrous oxide,before I attempted to ascertain its composition by immediately separating the constituent principles from each other: and my first hopes of the possibility of effecting this, were derived from Dr. Priestley’s experiments on the combustion of pyrophorus in nitrous gas, and on the changes effected in it, by heated iron and charcoal.
This great philosopher found, that pyrophorus placed in contact with nitrous gas, burnt with great vividness, whilst the gas was diminished in volume to about one half, which generally consisted of nitrogene and nitrous oxide. He likewise found, iron heated by a lens in nitrous gas, increased in weight, whilst the gas was diminished about ½, and converted into nitrogene.[97]
He heated common charcoal, and charcoal of copper,[98]in nitrous gas by a lens. When common charcoal was employed, the gas was neither increased or diminished in bulk, but wholly converted into nitrogene; when charcoal of copper was used, the volume was a little increased, and the gas remaining consisted of ⁵/₇ nitrogene, and ²/₇ carbonic acid.
In his experiments on the iron and pyrophyrus, the nitrous gas was evidently decomposed. From the great quantity of nitrogene produced in those on the charcoal, it seems likely that both the common charcoal,[99]and the charcoal of copper employed contained atmospherical air, which being dispelled by the heat of the lens, was decomposed by the nitrous gas: indeed, till I made the following experiment, I suspected that the carbonic acid produced, when the charcoal of copper was employed, arose from a decomposition of the nitrous acid, formed in this way.
I introduced a piece of well-burnt charcoal, which could hardly have weighed the eighth of a grain, whilst red hot, under a cylinder filled with mercury, and admitted to it half a cubic inch of nitrous gas. A slight absorption took place.
The sun being very bright, I kept the charcoal in the focus of a small lens for near a quarter of an hour. At the end of this time the gas occupied a space nearly as before the experiment, and a very minute portion of the charcoal had been consumed. On introducing into the cylinder a small quantity of solution of strontian, a white precipitation was perceived, and the gas slowly diminished to aboutthree tenths of a cubic inch. To these three tenths a little common air was admitted, when very slight red fumes were perceived.
This experiment convinced me, that the attraction of charcoal for the oxygene of nitrous gas, at high temperatures, was sufficiently strong to effect a slow decomposition of it.
To be more accurately acquainted with this decomposition, and to learn the quantities of carbonic acid and nitrogene produced from a known quantity of nitrous gas, I proceeded in the following manner.
II.Analysis of Nitrous Gas by Charcoal.
A quantity of nitrous gas was procured in a water apparatus, from the decomposition of nitrous acid by mercury. A portion of it was transferred to the mercurial trough. After the mercury and the jar had been dried by bibulous paper, 40 measures of this portion were agitated in a solution of sulphate of iron. The gas remaining after theabsorption was complete, filled about a measure and half; so that the nitrous gas contained nearly ¹/₂₆ nitrogene.
Thermometer being 53°, a small piece of well-burnt charcoal, the weight of which could hardly have equalled a quarter of a grain, was introduced ignited, into a small cylinder filled with mercury, graduated to,10 grain measures; to this, 16 measures, equal to 160 grain m. of nitrous gas, were admitted. An absorption of about one measure and half took place. When the focus of a lens was thrown on the charcoal, a slight increase of the gas was produced, from the emission of that which had been absorbed.
After the process had been carried on for about a half an hour, the charcoal evidently began to fume, and to consume very slowly, though no alteration in the volume of the gas was observed.
The sun not constantly shining, the progress of the experiment was now and then stopped: but taking the whole time, the focus could not have been applied to it for less than four hours. When the process wasfinished, the gas was increased in bulk nearly three quarters of a measure.
A drop of water was introduced into the cylinder, by means of a small glass tube, on the supposition that the carbonic acid, and nitrogene, might be capable of holding in solution, more water than that contained in the nitrous gas decomposed; but no alteration of volume took place.
When 20 grain measures of solution of pale green[100]sulphate of iron were introduced into the cylinder, they became rather yellower than before, but not dark at the edges, as is always the case when nitrous gas is present. On agitation, a diminution of nearly half a measure was produced, doubtless from the absorption of some of the carbonic acid by the solution.
A small quantity of caustic potash, much more than was sufficient to decompose the sulphate of iron, was now introduced. A rapid diminutiontook place, and the gas remaining filled about 8 measures. This gas was agitated for some time over water, but no absorption took place. Two measures of it were then transferred into a detonating cylinder with two measures of oxygene. The electric spark was puffed through them, but no diminution was produced. Hence it was nitrogene, mingled with no ascertainable quantity of hydrogene: consequently little or no water could have been decomposed in the process.
Now supposing, for the greater ease of calculation, each of the measures employed, cubic inches.
16 of nitrous gas—¹/₂₆ = 15,4 were decomposed, and these weigh, making the necessary corrections, 5,2; but 7,4 nitrogene were produced, and these weigh about 2,2. So that reasoning from the relative specific gravities of nitrous gas and nitrogene, 5,2 grains of nitrous gas will be composed of 3 oxygene, and 2,2 nitrogene.
But 8,7 of carbonic acid were produced, which weigh 4,1 grains, andconsist of 2,9 oxygene, and 1,2 charcoal.[101]Consequently, drawing conclusions from the quantity of carbonic acid formed, 5,2 grains of nitrous gas will consist of 2,9 oxygene, and 2,3 nitrogene.
The difference in these estimations is much less than could have been expected; and taking the mean proportions, it would be inferred from them, that 100 grains of nitrous gas, contain 56,5 oxygene, and 43,5 nitrogene.
I repeated this experiment with results not very different, except that the increase of volume was rather greater, and that more unabsorbable gas remained; which probably depended on the decomposition of a minute quantity of water, that had adhered to the charcoal in passing through the mercury.
As nitrous gas is decomposable into nitrous acid, and nitrogene, by the electric spark; it occurred to me, that a certain quantity of nitrous acid might have been possibly produced, in the experiments on thedecomposition of nitrous gas, by the intensely ignited charcoal. To ascertain this circumstance, I introduced into 12 measures of nitrous gas, a small piece of charcoal which had been just reddened. The sun being very bright, the focus of the lens was kept on it for rather more than an hour and quarter. In the middle of the process it began to fume and to sparkle, as if in combustion. In three quarters of an hour, the gas was increased rather more than half a measure; but no alteration of volume took place afterwards.
The mercury was not white on the top as is usually the case when nitrous acid is produced. On introducing into the cylinder a little pale green sulphate of iron, and then adding prussiate of potash, a white precipitate only was produced. Now, if the minutest quantity of nitric acid had been formed, it would have been decomposed by the pale green oxide of iron, and hence, a visible quantity of prussian blue[102]produced, as will be fully explained hereafter.
III.Analysis of Nitrous Gas by Pyrophorus.
I placed some newly made pyrophorus, about as much as would fill a quarter of a cubic inch, in a jar filled with dry mercury, and introduced to it, four cubic inches of nitrous gas, procured from mercury and nitric acid.
It instantly took fire and burnt with great vividness for some moments.
After the combustion had ceased, the gas was diminished about three quarters of a cubic inch. The remainder was not examined; for the diminution appeared to go on for some time, after; in an half hour, when it was compleat, it was to 2 cubic inches. A taper, introduced into these, burnt with an enlarged flame, blue at the edges; from whence it appeared, that they were composed of nitrogene and nitrous oxide.
I now introduced about half a cubic inch of pyrophorus to two cubic inches of nitrous gas; the combustion took place, and the gas wasrapidly diminished to one half; and on suffering it to remain five minutes to one third nearly; which extinguished flame.
Suspecting that this great diminution was owing to the absorption of some of the nitrogene formed, by the charcoal of the pyrophorus, I carefully made a quantity of pyrophorus; employing more than two thirds of alumn, to one third of sugar.
To rather more than half of a cubic inch of this, two cubic inches of nitrous gas, which contained about ¹/₄₀ nitrogene, were admitted. After the combustion, the gas remaining,apparentlyfilled a space equal to 1,2 cubic inches; but, as on account of the burnt pyrophyrus in the jar, it was impossible to ascertain the volume with nicety, it was carefully and wholly transferred into another jar. It filled a space equal to 1,15 cubic inches nearly.
When water was admitted to this gas no absorption took place. It underwent no diminution with nitrous gas, and a taper plunged into it was instantly extinguished. We may consequently conclude that it was nitrogene.
Now 2 cubic inches of nitrous gas weigh,686 grains, and 1,1 of nitrogene—,05, the quantity previously contained in the gas = to 1,05, 3,19. Hence,686 of nitrous gas would be composed of,367 oxygene, and ,319 nitrogene; and 100 grains would contain 53,4 oxygene, and 46,6 nitrogene.
IV.Additional observations on the combustion of bodies in Nitrous Gas,and on its Composition.
Though phosphorus may be fused, and even sublimed, in nitrous gas, without producing the slightest luminous appearance,[103]yet when it is introduced into it in a state of active inflammation, it burns withalmost as much vividness as in oxygene.[104]Hence it is evident, that at the heat of ignition, phosphorus is capable of attracting the oxygene from the nitrogene of nitrous gas.
I attempted to analise nitrous gas, by introducing into a known quantity of it, confined by mercury, phosphorus, in a vessel containing a minute quantity of oxygene.[105]The phosphorus was inflamed with an ignited iron wire, by which, at the moment of the combustion, the vessel containing it was raised from the mercury into the nitrous gas. But after making in this way, five of six unsuccessful experiments, I desisted. When the communication betweenthe vessels was made before the oxygene was nearly combined with the phosphorus, nitrous acid was formed, which instantly destroyed the combustion; when, on the contrary, the phosphorus was suffered to consume almost the whole of the oxygene, it was not sufficiently ignited when introduced, to decompose the nitrous gas.
In one experiment, indeed, the phosphorus burnt for a moment in the nitrous gas; the diminution however was slight, and not more than ¼ of it was decomposed.
Sulphur, introduced in a state of vivid inflammation, into nitrous gas, was instantly extinguished.
I passed a strong electric shock through equal parts of hydrogene and nitrous gas, confined by mercury in a detonating tube; but no inflammation, or perceptible diminution, was produced.
19,2 grain measures of hydrogene were fired by the electric shock, with 10 of nitrous oxide, and 6 of nitrous gas; the diminution was to 17; and pale green sulphate of iron admitted to the residuum, was notdiscolored. Consequently the nitrous gas was decomposed by the hydrogene, and as will be hereafter more clearly understood, nearly as much nitrogene furnished by it, as would have been produced from half the quantity of nitrous oxide.
Suspecting that phosphorated hydrogene might inflame with nitrous gas, I passed the electric spark through 1 measure of phosphorated hydrogene, and 4 of nitrous gas; but no diminution was perceptible. I likewise passed the electric spark through 1 of nitrous gas, with 2 of phosphorated hydrogene, without inflammation.
Perhaps if I had tried many other different proportions of the gases, I should have at last discovered one, in which they would have inflamed; for, as will be seen hereafter, nitrous oxide cannot be decomposed by the compound combustible gases, except definite quantities are employed.
From Dr. Priestley’s experiments on iron and pyrophorus, and from the experiments I have detailed, on charcoal, phosphorus, and hydrogene, itappears that at certain temperatures, nitrous gas is decomposable by most of the combustible bodies: even the extinction of sulphur, when introduced into it in a state of inflammation, depends perhaps, on the smaller quantity of heat produced by the combustion of this body, than that of most others.
The analysis of nitrous gas by charcoal, as affording data for determining immediately the quantities of oxygene and nitrogene, ought to be considered as most accurate; and correcting it by mean calculations derived from the decomposition of nitrous gas by pyrophorus and hydrogene, and its conversion into nitrous oxide, a process to be described hereafter, we may conclude, that 100 grains of nitrous gas are composed of 55,95 oxygene, and 44,05 nitrogene; or taking away decimals, of 56 oxygene, and 44 nitrogene.
This estimation will agree very well with the mean proportions that would be given from Dr. Priestley’s experiments on the decomposition ofnitrous gas by iron; but as he never ascertained the purity of his nitrous gas,[106]and probably employed different kinds in different experiments, it is impossible to fix on any one, from which accurate conclusions can be drawn.
Lavoisier’s estimation of the quantities of oxygene and nitrogene entering into the composition of nitrous gas, has been generally adopted. He supposes 64 parts of nitrous gas to be composed of 43½ of oxygene, and 20½ of nitrogene.[107]
The difference between this account and mine is very great indeed; but I have already, inDivision 1st, pointed out sources of error in the experiments of this great man, on the decomposition of nitre by charcoal; which experiments were fundamental, both to his accounts of the constitution of nitrous acid, and nitrous gas.
V.Of the absorption of Nitrous Gas by Water.
Amongst the properties of nitrous gas noticed by its great discoverer, is that of absorbability by water.
In exposing nitrous air to distilled water, Dr. Priestley found a diminution of the volume of gas, nearly equal to one tenth of the bulk of the water; and by boiling the water thus impregnated, he procured again a certain portion of the nitrous gas.
Humbolt, in his paper on eudiometry, mentions the diminution of nitrous gas by water. This diminution, he supposes to arise from the decomposition of a portion of the nitrous gas, by the water, and the consequent formation of nitrate of ammoniac.[108]
I confess, that even before the following experiments were made, I was but little inclined to adopt this opinion: the small diminution of nitrous gas by water, and the uniform limits of this diminution, rendered it extremely improbable.
a.To ascertain the quantity of nitrous gas absorbable by pure water, and the limits of absorption, I introduced into a glass retort about 5 ounces of water, which had been previously boiled for some hours. The neck of the retort was inverted in mercury, and the water made to boil. After a third of it had been distilled, so that no air could possibly remain in the retort, the remainder was driven over, and condensed in an inverted jar filled with mercury. To three cubic inches of this water,[109]confined in a cylinder graduated to,05 cubic inches, 5 cubic inches of nitrous gas, containing nearly one thirtieth nitrogene, were introduced.
After agitation for near an hour, rather more than ⁴/₂₀ of a cubic inch appeared to be absorbed; but though the process was continued for near two hours longer, no further diminution took place.
The remaining gas was introduced into a tube graduated to,02 cubic inches. It measured ¹⁴/₅₀; hence ¹¹/₅₀ had been absorbed.
Consequently, 100 cubic inches of pure water are capable of absorbing 11,8 of nitrous gas. In the water thus impregnated with nitrous gas I could distinguish no peculiar taste;[110]it did not at all alter the color of blue cabbage juice.
b.To determine if the absorption of nitrous gas was owing, to a decomposition of it by the water, as Humbolt has supposed, or to a simple solution; I procured some nitrous gas from nitrous acid and mercury, containing about one seventieth nitrogene. ,5 cubic inches of it, mingled with ,25, of oxygene, from sulphuric acid and manganese left a residuum of,03. 5 cubic inches more were introduced to 3 of water, procured in the same manner as in the last experiment, in the same cylinder.After the diminution was complete, the cylinder was transferred in a small vessel containing mercury, into a water bath, and nearly covered by the water.
As the bath was heated, small globules of gas were given out from the impregnated water, and when it began to boil, the production of gas was still more rapid. After an hour’s ebullition, the volume of heated gas was equal to 1,4 cubic inches nearly.
The cylinder was now taken out of the bath, and quickly rendered cool by being placed in a water apparatus. At the common temperature the gas occupied, as nearly as possible, the space of,5 cubic inches: these,5 mingled with,25 of oxygene, of the same kind as that employed before, left a residuum nearly equal to,03.
From this experiment, which was repeated with nearly the same results, it is evident,
1. That nitrous gas is not decomposable by pure water.2. That the diminution of volume of nitrous gas placed in contact with water, is owing to a simple solutionof it in that fluid.3. That at the temperature of 212°, nitrous gas is incapable of remaining in combination with water.
1. That nitrous gas is not decomposable by pure water.
2. That the diminution of volume of nitrous gas placed in contact with water, is owing to a simple solutionof it in that fluid.
3. That at the temperature of 212°, nitrous gas is incapable of remaining in combination with water.
Humbolt’s opinion relating to the decomposition of nitrous gas by water, is founded upon the disengagement of vapor from distilled water impregnated with nitrous gas, by means of lime, which became white in the proximity of the muriatic acid. But this is a very imperfect, and fallacious test, of the presence of ammoniac. I have this day, April 2, 1800, heated 4 cubic inches of distilled water, impregnated with nitrous gas, with caustic lime; the vapor certainly became a little whiter when held over a vessel containing muriatic acid; but the vapor of distilled water produced precisely the same appearance,[111]which was owing, most likely, to the combination of the acid with the aqueous vapor. Indeed, when I added a particle of nitrate of ammoniac, which might have equalled one twentieth of a grain, to the lime and impregnated water, the increased whiteness of the vapor was but barely perceptible, though this quantity of nitrate of ammoniac is much more considerable than that which could have been formed, even supposing the nitrous gas decomposed.
VI.Of the absorption of Nitrous Gas byWater of different kinds.
In agitating nitrous gas over spring water, the diminution rarely amounts to more than one thirtieth, the volume of water being taken asunity. I at first suspected that this great differcnce in the quantity of gas absorbed by spring water, and pure water, depended on carbonic acid contained in the last, diminishing the attraction of it for nitrous gas: but by long boiling a quantity of spring water confined by mercury, I obtained from it about one twentieth of its bulk of air, which gave nearly the same diminution with nitrous gas, as atmospheric air.
This fact induced me to refer the difference of diminution to the decomposition of the atmospheric air held in solution by the water, the oxygene of which I supposed to be converted into nitric acid, by the nitrous gas, whilst the nitrogene was liberated; and hence the increased residuum.
a.I exposed to pure water, that is, water procured by distillation under mercury, nitrous gas, containing a known quantity of nitrogene. After the absorption was complete, I found the same quantity of nitrogene in the residuum, as was contained in a volume of gas equal to the whole quantity employed.
b.Spring water boiled for some hours, and suffered to cool under mercury, absorbed a quantity of nitrous gas equal to one thirteenth of its bulk; which is not much less than that absorbed by pure water.
c.I exposed to spring water, 10 measures of nitrous gas; the composition of which had been accurately ascertained; the diminution was one twenty-eighth, the volume of water being taken as unity. On placing the residuum in contact with solution of sulphate of iron, the nitrogene remaining was nearly one twentieth more than had been contained by the gas before its exposure to water.
d.Distilled water was saturated with common air, by being agitated for some time in the atmosphere. Nitrous gas placed in contact with this water, underwent a diminution of ¹/₁₈; the volume of water being unity. The gas remaining after the absorption contained about one twenty-seventh nitrogene more than before.
e.Nitrous gas exposed to water combined with about one fourth of its volume of carbonic acid, diminished to ¹/₃₂[112]nearly. The remainder contained little or no superabundant nitrogene.
From these observations it appears, that the different degrees of diminution of nitrous gas by different kinds of water, may depend upon various causes.
1. Less nitrous gas will be absorbed by water holding in solution earthy salts, than by pure water; and in this case the diminution of the attraction of water for nitrous gas will probably be in the ratio of the quantities of salt combined with it.a.b.
2. The apparent diminution of nitrous gas in water, holding in solution atmospheric air, will be less than in pure water, though the absolute diminution will be greater; for the same portion will be absorbed, whilst another portion is combined with the oxygene of the atmosphericair contained in the water; and from the disengagement of the nitrogene of this air, arises an increased residuum.c.d.
3. Probably in waters containing nitrogene, hydrogene, and other gases, absorbable only to a slight extent, the apparent diminution will be less, on account of the disengagement of those gases from the water, by the stronger affinity of nitrous gas for that fluid.
4. In water containing carbonic acid, and probably some other acid gases, the diminution will be small in proportion to the quantity of gas contained in the water: the affinity of this fluid for nitrous gas being diminished by its greater affinity for the substance combined with it.e.
The different diminution of nitrous gas when agitated in different kinds of water, has been long observed by experimenters on the constituent parts of the atmosphere, and various solutions have been given of the phænomenon; the most singular is that of Humbolt.[113]He supposes that the apparent diminution of nitrous gas is less in spring water than distilled water, on account of the decomposition of the carbonate of lime contained in the spring water, by the nitrous acid formed from the contact of nitrous gas with the water; the carbonic acid disengaged from this decomposition increasing the residuum.
This opinion may be confuted without even reference to my observations.It is, indeed, altogether unworthy of a philosopher, generally acute and ingenious. He seems to have forgotten that carbonic acid is absorbable by water.
VII.Of the absorption of Nitrous Gas, by solutionof pale green Sulphate of Iron.
a.The discovery of the exact difference between the sulphates of iron, is owing to Proust.[114]According to the ingenious researches of this chemist, there exist two varieties of sulphate of iron, the green and the red. The oxide in the green sulphate contains ²⁷/₁₀₀ oxygen. This salt, when pure, is insoluble in spirit of wine; its solution in water is of a pale green color; it is not altered by the gallic acid, and affords a white precipitate with alkaline prussiates.
The red sulphate of iron is soluble in alcohol and uncrystalizable; its oxide contains ⁴⁸/₁₀₀ oxygene. It forms a black precipitate with the gallic acid, and with the alkaline prussiates, a blue one.
The common sulphates of iron generally consist of combinations of these two varieties in different proportions.
The green sulphate may be converted into the red by oxygenated muriatic acid or nitric acid. The common sulphate may be converted into green sulphate, by agitation in contact with sulphurated hydrogene.
The green sulphate has a strong affinity for oxygene, it attracts it from the atmosphere, from oxygenated marine acid, and nitric acid. The alkalies precipitate from it a pale green oxide, which if exposed to the atmosphere, rapidly becomes yellow red.
The red sulphate of iron has no affinity for oxygene, and when decomposed by the alkalies, gives a red precipitate, which undergoes no alteration when exposed to the atmosphere.[115]
b.The absorption of nitrous gas by a solution of sulphate ofiron, was long ago discovered by Priestley. During this absorption, he remarked a change of color in the solution, analogous to that produced by the mixture of it with nitric acid.
This chemical fact has been lately applied by Humbolt, to the discovery of the nitrogene generally mingled with nitrous gas.
Vauquelin and Humbolt have published a memoir, on the causes of the absorption[116]of nitrous gas by solution of sulphate of iron. They saturated an ounce and half of sulphate of iron in solution, with 180 cubic inches of nitrous gas.
Thus impregnated it strongly reddened tincture of turnsoyle; when mingled with sulphuric acid, gave nitric acid vapor; and saturated with potash, ammoniacal vapor.
By analysis, it produced as much ammoniac as that contained in 4 grains of ammoniacal muriate, and a quantity of nitric acid equal to thatexisting in 17 grains of nitre. Hence they concluded, that the nitrous gas and a portion of the water of the solution, had mutually decomposed each other; the oxygene of the water combining with the oxygene and a portion of the nitrogene of nitrous gas to form nitric acid; and its hydrogene uniting with the remaining nitrogene, to generate ammoniac.
They have taken no notice of the nature of the sulphate of iron employed, which was most probably the common or mixed sulphate; nor of the attraction of the oxide of iron in this substance for oxygene.
c.Before I was acquainted with the observations of Proust, the common facts relating to the oxygenation of vitriol of iron induced me to suppose, that the attraction of this substance for oxygene was in some way connected with the process of absorption. The comparison of the experiments of Humbolt and Vauquelin, with the observations of Proust, enabled me to discover the true nature of the process.
I procured a solution of red sulphate of iron, by passing oxygenatedmuriatic acid through a solution of common sulphate of iron, till it gave only a red precipitate, when mingled with caustic potash. To nitrous gas confined by mercury, a small quantity of this solution was introduced. On agitation, its color altered to muddy green; but the absorption that took place was extremely trifling: in half an hour it did not amount to,2, the volume of the solution being unity, when it had nearly regained the yellow color.
I now obtained a solution of green sulphate of iron, by dissolving iron filings in diluted sulphuric acid. The solution was agitated in contact with sulphurated hydrogene, and afterwards boiled; when it gave a white precipitate with prussiate of potash.
A small quantity of this solution agitated in nitrous gas, quickly became of an olive brown, and the gas was diminished with great rapidity; in two minutes, a quantity equal to four times the volume of the solution, had been absorbed.
These facts convinced me that the solubility of nitrous gas in commonsulphate of iron, chiefly depended upon the pale green sulphate contained by it; and that the attraction of one of the constituents of this substance, the green oxide of iron, for oxygene, was one of the causes of the phænomenon.
d.Green sulphate of iron rapidly decomposes nitric acid. It was consequently difficult to conceive how any affinities existing between nitrous gas, water, and green sulphate of iron, could produce the nitric acid found in the experiments of Vauquelin and Humbolt.
To ascertain if the presence of a great quantity of water destroyed the power of green sulphate of iron to decompose nitric acid, I introduced into a cubic inch of solution of green sulphate of iron, two drops of concentrated nitric acid.
The solution assumed a very light olive color; prussiate of potash mingled with a little of it, gave a dark green precipitate. Hence the nitric acid had been evidently decomposed. As no nitrous gas was givenout, which is always the case when nitric acid is poured on crystalised sulphate of iron, I suspected that a compleat decomposition of the acid had taken place; but when the solution was heated, a few minute globules of gas were liberated, and it gradually became slightly clouded.
Having often remarked that no precipitation is ever produced during the conversion of green sulphate of iron into red, by oxygenated muriatic acid, or concentrated nitric acid, I could refer the cloudiness to no other cause than to the formation of ammoniac.
To ascertain if this substance had been produced, a quantity of slacked caustic lime was thrown into the solution. On the application of heat, the ammoniacal smell was distinctly perceptible, and the vapor held over orange nitrous acid, gave dense white fumes.
e.When I considered this fact of the decomposition of nitric acid and water by the solution of green sulphate of iron, and the change of color effected in it by the absorption of nitrous gas, exactly analogous to that produced by the decomposition of nitric acid;I was induced to believe that the nitric acid found in the analysis of Vauquelin and Humbolt, had been formed by the combination of some of the nitrous gas thrown into the solution with the oxygene of the atmosphere: and that the absorbability of nitrous gas, by solution of green sulphate of iron, was owing to a decomposition produced by the combination of its oxygene with the green oxide of iron, and of its nitrogene with the hydrogene disengaged from water, decompounded at the same time.
To ascertain this, I procured a quantity of nitrous gas: it was suffered to remain in contact with water for some hours after its production. Transferred to the mercurial apparatus, it gave no white vapor when placed in contact with solution of ammoniac; and consequently held no nitric acid in solution.
Into a graduated jar filled with mercury, a cubic inch of concentrated solution of pure green sulphate of iron was introduced, and 7 cubic inches of nitrous gas admitted to it. The solution immediately becamedark olive at the edges, and on agitation this color was diffused through it. In 3 minutes, when near 5¾ cubic inches had been absorbed, the diminution ceased. The solution was now of a bright olive brown, and transparent at the edges. After it had rested for a quarter of an hour, no farther absorption was observed; the color was the same, and no precipitation could be perceived. A little of it was thrown into a small glass tube, under the mercury, and examined in the atmosphere. Its taste was rather more astringent than that of solution of green sulphate; it did not at all alter the color of red cabbage juice. When a little of it was poured on the mercury, it soon lost its color, its taste became acid, and it quickly reddened cabbage juice, even rendered green by an alkali.
To the solution remaining in the mercurial jar, a small quantity of prussiate of potash was introduced, to ascertain if any red sulphate of iron had been formed; but instead of the production of either a blue, or a white precipitate, the whole of the solution became opaque, and chocolate colored.
Surprised at this appearance, I was at first induced to suppose, that the ammoniac formed by the nitrogene of the nitrous gas and the hydrogene of the water, had been sufficient to precipitate from the sulphuric acid, the red oxide of iron produced, and that the color of the mixture was owing to this precipitation. To dissolve any uncombined oxide that might exist in the solution, I added a very minute quantity of diluted sulphuric acid; but little alteration of color was produced. Hence, evidently, no red oxide had been formed.
This unexpected result obliged me to theorise a second time, by supposing that nitrate of ammoniac had been produced, which by combining with the white prussiate of iron, generated a new combination. But on mingling together green sulphate of iron, prussiate of potash, and nitrate of ammoniac in the atmosphere, the mixture remained perfectly white.
To ascertain if any nitric acid existed, combined with any of the bases, in the impregnated solution, I introduced into it an equal bulkof diluted sulphuric acid: it became rather paler; but no green or blue tinge was produced.
That the prussic acid had not been decomposed, was evident from the bright green produced, when less than a grain of dilute nitric acid was admitted into the solution.
f.From these experiments it was evident, that no red sulphate of iron, or nitric acid, and consequently no ammoniac, had been produced after the absorption of nitrous gas by green sulphate of iron. And when I compared them with the observations of Priestley, who had expelled by heat a minute quantity of nitrous gas from an impregnated solution of common sulphate of iron, and who found common air phlogisticated by standing in contact with it, I began to suspect that nitrous gas was simply dissolved in the solution, without undergoing decomposition.
g.To determine more accurately the nature of the process, I introduced into a mercurial cylinder 410 grains of solution of greensulphate of iron, occupying a space nearly equal to a cubic inch and quarter; it was saturated with nitrous gas, by absorbing 8 cubic inches. This saturated solution exhibited the same appearance as the last; and after remaining near an hour untouched, had evidently deposited no oxide of iron, nor gained any acid properties.
Into a small mattrass filled with mercury, having a tight stopper with a curved tube adapted to it, the greater part of this solution was introduced; judging from the capacity of the mattrass, about 50 grains of it might have been lost. To prevent common air from coming in contact with the solution, the stopper was introduced into the mattrass under the mercury; the curved tube connected with a graduated cylinder filled with that substance; and the mattrass brought over the side of the mercurial trough. But in spite of these precautions a large globule of common air got into the top of the mattrass, from the curvature of the tube. When the heat of a spirit lamp was applied to the solution, it gave out gas with great rapidity, and gradually lost its color. When5 cubic inches were collected it became perfectly pale green, whilst a yellow red precipitate was deposited on the bottom of the mattrass.
On pouring a little of the clear solution into prussiate of potash, it gave only white prussiate of iron.
But on introducing a particle of sulphuric acid into the solution, sufficient to dissolve some of the red precipitate, and then pouring a little of it into a solution of prussiate of potash, it gave a fine blue prussiate of iron.
Hence the red precipitate was evidently red yellow oxide of iron.
I now examined the gas, suspecting that it was nitrous oxide. On mingling a little of it with atmospheric air, it gave red vapor, and diminished. Solution of sulphate of iron introduced to the remainder, almost wholly absorbed it: the small residual globule of nitrogene could not equal one thirtieth of a cubic inch.
Consequently it was nitrous gas, nearly pure.
Caustic potash was now introduced into the solution, till all the oxide of iron was precipitated. The solution, when heated, gave a strongsmell of ammoniac, and dense white fumes when held over muriatic acid. It was kept at the heat of ebullition till the evaporation had been nearly compleated. Sulphuric acid poured upon the residuum gave no yellow fumes, or nitric acid vapor in any way perceptible; even when heated and made to boil, there was no indication of the production of any vapor, except that of the sulphuric acid.
h.This experiment, compared with the others, seemed almost to prove, that nitrous gas combined with solution of pale green sulphate of iron, at the common temperature, without decomposition; and that when the impregnated solution was heated, the greater portion of gas was disengaged, whilst the remainder was decompounded by the green oxide of iron; which attracted at the same time oxygene from the water and the nitrous gas; whilst their other constituent principles, hydrogene and nitrogene, entered into union as ammoniac.
Whilst, however, I was reasoning upon this singular chemical change,as affording presumptive proofs in favor of the exertion of simple affinities by the constituent parts of compound substances, a doubt concerning the decomposition of the nitrous gas occurred to me. As near as I could guess at the quantity of nitrous gas contained by the impregnated solution, at least ¾ of it must have been expelled undecompounded.
More than a quarter of a cubic inch of common air had been present in the mattrass: the oxygene of this common air must have combined with the nitrous gas, to form nitric acid. Might not this nitric acid have been decomposed, and furnished oxygene to the red oxide of iron, and nitrogene to the small quantity of ammoniac found in the solution, as ind?
i.I now introduced to a solution of green sulphate confined by mercury, nitrous gas, perfectly free from nitric acid. When the solution was saturated, a portion of it was introduced into a small mattrass filled with dry mercury, in the mercurial trough. The curvedtube was closed by a small cork at the top, and filled with nitrous gas; it was then adapted to the mattrass, which was raised from the trough, and the solution thus effectually preserved from the contact of the atmosphere.
When the heat of a spirit lamp was applied to the mattrass, it began to give out gas with great rapidity. After some time the solution lost its dark color, and became turbid. When the production of nitrous gas had ceased, it was suffered to cool. A copious red precipitate had fallen down; which, examined by the same tests as in the last experiment, proved to be red oxide of iron.
The solution treated with lime, as before, gave ammoniac; but with sulphuric acid, not the slightest indications of nitric acid.
k.Having thus procured full evidence of the decomposition of nitrous gas in the heated solution, in order to gain a more accurate acquaintance with the affinities exerted, I endeavoured to ascertain the quantity of nitrous gas decomposed by a given solution, under known circumstances.
Into a cylinder of the capacity of 20 cubic inches, inverted in mercury, 1150 grains of solution of green sulphate of iron, of specific gravity 1,4, were introduced. Nitrous gas was admitted to it, and after some time 21 cubic inches were absorbed.
The impregnated solution was thrown into a mattrass, in the same manner as in the last experiment, and the same precautions taken to preserve it from the contact of atmospheric air. A quantity was lost during the process of transferring, which, reasoning from the space occupied in the mattrass by the remaining portion, as determined by experiment afterwards, must have amounted nearly to 240 grains.
The curved tube from the mattrass was now made to communicate with the mercurial airholder. By the application of heat 12,5 cubic inches of nitrous gas were collected, after the common temperature had been restored to the mattrass; which was suffered to remain in communication with the conducting tube.
The solution was now pale green, that is, of its natural color, and a considerable quantity of red oxide of iron had been deposited.
Solid caustic potash was introduced into it, till all the green oxide of iron had been precipitated, and till the solution rendered green, red cabbage juice.
A tube was now accurately connected with the mattrass, bent, and introduced into a small quantity of diluted sulphuric acid. Nearly half of the fluid in it was slowly distilled into the sulphuric acid, by the heat of a spirit lamp. The impregnated acid evaporated at a heat above 212°, and gave a small quantity of crystalised salt, which barely amounted to two grains and quarter: it had every property of sulphate of ammoniac. Sulphuric acid in excess was poured on the residuum, and the whole distilled by a heat not exceeding 300°, into a small quantity of water. This water, after the process, tasted strongly of sulphuric acid; it had no peculiar odor. Tin thrown into it when heated, was not perceptibly oxydated; mingled with strontitic lime water, it gave acopious white precipitate, and after the precipitation became almost tasteless. Hence it evidently contained no nitric acid.
The 12,5 cubic inches of undecompounded gas that came over were examined; and accounting for the small quantity of common air previously contained in the airholder, must have been almost pure.
l.Now supposing 927 grains of the impregnated solution (including the weight of the nitrous gas), to have been operated upon, this must have contained about 16,7 cubic inches of nitrous gas. But 12,5 cubic inches escaped undecompounded: hence 4,2 were decomposed; and these weigh 1,44 grains, and are composed of,8 oxygene, and,64 nitrogene.[117]
Consequently, the nitrous gas must have furnished,8 of oxygene to the green oxide of iron.
But,64 of nitrogene require,15 of hydrogene to form,79 of ammoniac:[118]consequently 1 of water was decompounded, and this furnished,85 of oxygene to the green oxide of iron.
The green oxide of iron contains ²⁷/₁₀₀ oxygene; the red ⁴⁸/₁₀₀. But the whole quantity of oxygene supplied from the water and nitrous gas is 0,8 + 0,85 = 1,65; and calculating on the difference of the composition of the red and green oxide of iron, 5,7 grains of red oxide must have been deposited, and consequently these would saturate as much acid as,79 grains of ammoniac, or 4,1 grains of green oxide of iron.[119]
And supposing the ammoniac in sulphate of ammoniac to be to the acid as 1 is to 3,[120]3.2 grains of sulphate of ammoniac must have been formed, containing about 2,4 grains acid; and then 6,5 grains of green sulphate of iron must have been decomposed.
Hence we gain the following equation:
Though the estimation of the quantities in this equation must not be considered as strictly accurate, on account of the degree of uncertainty that remains concerning the exact numerical expression of the quantities of the constituents of water, ammoniac, and the other compound bodies employed; yet as founded on a simple quantity, that is, the nitrous gas decomposed, it cannot be very distant from the truth.
The sulphate of ammoniac given by experiment, is considerably less than that which was really produced; much of it was probably carried off during the evaporation of the superabundant acid.
The conclusions that may be drawn from this experiment, afford a striking instance of the importance of the application of the science of quantity to the chemical changes: for the data being one chemical fact, the decomposition of a given quantity of nitrous gas by known agents; the composition of nitrous gas, of water, ammoniac, the oxides of iron, and sulphate of ammoniac; we are able not only to determine the quantities of the simple constituents that have entered into new arrangements, but likewise the composition of two compound bodies, the green and red sulphates of iron.[121]
m.Though from the experiments ineit appeared that no decomposition of nitrous gas had been produced during or even after its absorption by solution of sulphate of iron at the common temperature;yet a suspicion that it might take place slowly, and that indications of it might be given by deposition, induced me to examine minutely two impregnated solutions, one of which had been at rest, confined by mercury, for 19 hours, and the other for 27. In neither of them could I discover any deposition, or alteration of color, which might denote a change.
Two cubic inches of oxygene were admitted to half a cubic inch of one of these solutions. The oxygene was slowly absorbed, and the solution gradually lost its color.
To ascertain if during the conversion of the nitrous gas held in solution by sulphate of iron, into nitric acid, by the oxygene of the atmosphere at the common temperature, any water was decomposed; I suffered an impregnated solution, weighing nearly two ounces, to remain in contact with the atmosphere at 57°-62°, till it was become perfectly pale. It then had a strong acid taste, effervesced with carbonate of potash, and gave a blue precipitate with prussiate of potash.—It wassaturated with quicklime, and heated: slight indications of the presence of ammoniac were perceived.
As in this experiment the nitric acid had been most probably decomposed by the green oxide of iron, as inf, I sent oxygenated muriatic acid through an impregnated solution, till all the green oxide of iron was converted into red, and all the nitrous gas into nitric acid.
This solution saturated with potash, and heated, gave no ammoniacal smell.
From these experiments we may conclude,
1st. That solution of red sulphate of iron has little or no affinity for nitrous gas[122]; and that solution of common sulphate absorbs nitrous gas only in proportion as it contains green sulphate.
2dly. That solutions of green sulphate of iron dissolve nitrous gas in quantities proportionable to their concentration, without effecting anydecomposition of it at common temperatures. And the solubility of nitrous gas in solution of green sulphate, may be supposed to depend on an equilibrium of affinity, produced by the following simple attractions: