Part 7

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 the absorption 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 was finished, 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.

[100] That is, sulphate of iron containing oxide of iron, in the first degree of oxygenation.

A small quantity of caustic potash, much more than was sufficient to decompose the sulphate of iron, was now introduced. A rapid diminution took 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, and consist 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.

[101] That is, carbon, or oxide of diamond.

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 the decomposition 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.

[102] That is, blue prussiate of iron.

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 was rapidly 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, _apparently_ filled 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 with almost 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.

[103] No luminous appearance is produced when phosphorus is introduced into _pure_ nitrous gas. It has been often observed, that phosphorus is luminous in nitrous gas, that has not been long in contact with water after its production. This phænomenon, I suspect, depends either on the decomposition of the nitric acid held in solution by the nitrous gas; or on the combination of the phosphorus with oxygene loosely adhering to the binary aëriform compound of nitric acid and nitrous gas. I have not yet examined if nitrous gas can be converted into nitrous oxide by long exposure to heated phosphorus: it appears, however, very probable.

[104] Perhaps this fact has been noticed before; I have not, however, met with it in any chemical work.

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 between the 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.

[105] This mode of inflaming bodies in gases, not capable of supporting combustion at low temperatures, will be particularly described hereafter.

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 not discolored. 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, it appears 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 of nitrous 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]

[106] Elements English Trans. edit. i. pag. 216.

[107] Experiments and Observations, Vol. II. pag. 40, 2d. Ed.

The difference between this account and mine is very great indeed; but I have already, in Division 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]

[108] He says, “On a observé, (depuis qu’on travaille sur le pureté de l’air) que le gaz nitreux, secoué avec l’eau, en souffre une diminution de volume. Quelques physiciens attribuent ce changement à une vraie absorption, à une dissolution du gaz nitreux dans l’eau; d’autres à l’air contenu dans les interstices de tous les fluides. Le cit. Vanbreda, à Delft, a fait des recherches très-exactes sur l’influence des eaux de pluie et de puit, sur les nombres eudiométriques; et les belles expériences du cit. Hassenfratz, sur l’abondance d’oxygène, contenue dans les eaux de neige et de pluie, sont supposer que l’air des interstices de l’eau joue un rôle important dans l’absorption du gaz nitreux. En comparant ces effets avec les phénomènes observé dans la decomposition du sulfate de fer, nous supposâmes, le cit. Tassaert et moi, que le simple contact du gaz nitreux avec l’eau distillée pourroit bien causer une décomposition de ce dernier. Nous examinâmes soigneusement une petite quantité d’eau distillée, secouée avec beaucoup de gas nitreux trés-pur, et nous trouvâmes, au moyen de la terre calcaire, et l’acide muriatique, qu’il s’y forme du _nitrate d’ammoniaque_. L’eau se décompose en cette opération, par un double affinité de l’oxygene pour le gaz nitreux, et de l’hydrogène pour l’azote; il se forme de l’acide nitrique et de l’_ammoniaque_; et, quoique la quantité du dernier paroisse trop petite pour en évaluer exactment la quantité, son existence cependant se manifeste, (à ne pas sans douter) par le dégagement des vapeurs, qui blanchissent dans la proximité de l’acide muriatique. Voilá un fait bien frappant que la composition d’une substance alcaline par le contact d’une acide, et de l’eau.”

Annales de Chimie, t. xxviii. pag. 153.

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.

[109] Which was certainly as free from air as it ever can be obtained.

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.

[110] Dr. Priestley found distilled water, saturated with nitrous air, to acquire an astringent taste and pungent smell. In some unboiled impregnated pump water, I once thought that I perceived a subacid taste; but it was extremely slight, and probably owing to nitrous acid formed by the union of the oxygene of the common air in the water, with some of the nitrous gas.

_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 solution of 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.

[111] As carbonic acid and ammoniac are both products of animalisation, is it not probable that our common waters particularly those in, and near towns and cities, contain carbonate of ammoniac? If so, this salt will always exist in them after distillation. In the experiments on carbonate of ammoniac, to which I have often alluded, I found, in distilling a solution of this salt in water, that before half of the water had passed into the recipient, the carbonate of ammoniac had sublimed; so that the distilled solution was much stronger than before, whilst the water remaining in the retort was tasteless. Will this supposition at all explain Humbolt’s mistake?

VI. _Of the absorption of Nitrous Gas by Water 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 as unity. 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.

[112] The water still being unity.

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 atmospheric air contained in the water; and from the disengagement of the nitrogene of this air, arises an increased residuum. _c._ _d._