ERRATA.
| Page | 19 | line 15 | for is read are |
| — | 35 | — 7 — | for principle read principles |
| — | 42 | — 11 — | for take read takes |
| — | 68 | Table 5 — | for 5,88 read 15,88 |
| — | 94 | — 4 — | for 1¹/₁₂ read ¹/₁₂. |
| — | 95 | — 4 — | for 37 read 30,7 |
| — | 96 | — 3 — | for 38 read ¹/₃₈ |
| — | 105 | — 9 — | for exactitude read exactness |
| — | 129 | — 21 — | for 41 read 4,1 |
| — | 132 | — 4 — | for into read in |
| — | 143 | — 13 — | for 25 read ,25 |
| — | 186 | — 15 — | for by read from |
| — | 208 | last line — | for abstracted read attracted |
| — | 238 | — 5 — | for gas read oxide |
| — | 259 | — 4 — | for 12 read 2 |
| — | 283 | — 4 — | for potash read iron |
| — | 315 | — 14 — | dele in |
| — | 409 | — 15 — | for respiration read expiration |
| — | 464 | — 10 — | for latter end read end |
| — | 543 | — 3 — | for exhalation read inhalation. |
| A few literal errors are left to the reader’s correction. | |||
N. B. The term ignited is sometimes used to signify any temperature equal to or above a red heat, whether applied to solids, fluids, or aëriform substances.
The reasons for the use of the terms nitrogene and nitrous oxide, are given in Mr. Nicholson’s Journal for January.
Speedily will be Published
OBSERVATIONS on the External and Internal Use of
NITROUS ACID.
Demonstrating its PERMANENT EFFICACY in
VENEREAL COMPLAINTS;
And extending its use to other dangerous
and painful Diseases.
COMMUNICATED
By various Practitioners in Europe and Asia.
TO
THOMAS BEDDOES, M. D.
Of the Publisher may be had, price 1s. 6d.
NOTICE of OBSERVATIONS
AT THE PNEUMATIC INSTITUTION,
By THOMAS BEDDOES, M. D.
This Notice contains some trials of nitrous oxide by healthy persons, not in the present work, and some cases of palsy successfully treated by that gas.
Printed by Biggs and Cottle, St. Augustine’s Back.
Footnotes:
[1] A short account of this discovery has been given in Dr. Beddoes’s Notice of some Observations made at the Pneumatic Institution, and in Mr. Nicholson’s Phil. Journal for May and December 1799.
[2] Cavendish, Priestley, Black, Lavoisier, Scheele, Kirwan, Guyton, Berthollet, &c.
[3] Phil. Trans. v. 78, p. 270.
[4] Phil. Trans. v. 75 p. 381.
[5] Elem. Kerr’s Trans. page 76, and 216, and Mem. des Sav. Etrang. tom. 7, page 629.
[6] Ingenhouz sur les Vegetaux, pag. 205. De la Metherie. Essai sur differens Airs, pag. 252.
[7] Annales de Chimie, tome 28, p. 168.
[8] Experiments and Observations, Vol. iii. last edition, page 105, &c.
[9] When copper is dissolved in dilute nitrous acid, certain quantities of nitrogene are generally produced, likewise the nitrous gas carries off in solution some nitrous acid.
[10] This airholder, considered as a pneumatic instrument, is of greater importance, and capable of a more extensive application than any other. It was invented by Mr. W. Clayfield, and in its form is analogous to Mr. Watt’s hydraulic bellows, consisting of a glass bell playing under the pressure of the atmosphere, in a space between two cylinders filled with mercury. A particular account of it will be given in the [appendix].
[11] This absorption will be hereafter particularly treated of.
[12] Annales de Chimie. Tome xviii. page 139.
[13] A table of the specific gravities of these gases, and other gases, hereafter to be mentioned, reduced to a barometrical and thermometrical standard, will be given in the [appendix].
[14] 40 measures, exposed to solution of potash, gave an absorption of not quite a quarter of a measure: hence it contained an inconsiderable quantity of carbonic acid.
[15] Traité Elementaire.
[16] Essai sur le phlogistique, page 30.
[17] The diminution of the specific gravity of the gas from the quantity of nitrogene evolved in his experiment, probably destroyed, in some measure, the source of error from the nitrous acid carried over.
[18] Experiment I.
[19] That no greater contraction took place depended on the solution of the nitrous acid formed in the nitrous gas; a phænomenon to be explained hereafter.
[20] I judged it expedient always to ascertain the quantity of air in the stop-cocks by weight, as it was impossible to join them so as to have always an equal capacity. The upper tubes of the two stop-cocks not joined, contained nearly an inch and half.
[21] That is, by the solution of ammonia, and air.
[22] The following is an account of the increase and diminution of weight of the globe, as it was noted in the journal.
| Globe filled with common air | gr. 2066,5 |
| After exhaustion | 2034,5 |
| After introduction of nitrous gas, 82 cubic inches | 2064,25 |
| After the accidental admission of common air | 2067,25 |
| After the admission of oxygene | 2091,75 |
| —— —— 41 grains of water | 2133,25 |
| —— —— 51 cubic inches of air | 2149,75 |
| Taken out 54 grains of solution | 2095,75 |
| Introduced 13 grains of ammoniacal solution | 2109,25 |
| After introduction of common air | 2106,5 |
[23] Decimals are omitted, because the excess of the two first numbers is exactly corrected by the deficiency of the last.
[24] As is evident from the superabundant quantity of oxygene thrown into the globe.
[25] The weight of the acid poured into the cylinder being known, its specific gravity was known from the space it occupied in the phial. The weight of water being likewise known, the specific gravity of the solution, when the common temperature was produced, was given by the condensation.
[26] That is, such as it exists in the aëriform state at 55°. From the strong affinity of nitrous acid for water, we may suppose that this acid gas contains a larger proportion of it than the other gases.
[27] This appearance will be explained hereafter.
[28] This phænomenon will be particularly explained hereafter.
[29] The outline only of this apparatus is given here, as far as was necessary to make the experiment intelligible; a detailed account of it, and of its general application, will be given in the [appendix].
[30] That is, from nitrous acid and mercury.
[31] A pale acid of 1.52, by being converted into yellow acid, became nearly of specific gravity 15,1.
[32] It is impossible to ascertain the quantity of gas absorbed to more than a quarter of a cubic inch, as the first portions of nitrous gas thrown into the graduated cylinder are combined with the oxygene of the common air in it, to form nitrous acid, and hence the slight excess of weight.
[33] In a letter to me, dated Oct. 28, 1799, after giving an account of some experiments on the phlogistication of nitric acid by heat and light, he says, “It was from an attentive examination of the manner in which the nitric acid was phlogisticated in these experiments, that I was confirmed in the suspicion I had long before entertained, of the real difference between the nitrous and nitric acids. It is not enough to shew that in the nitrous acid, (that is, the nitric holding nitrous gas in solution), the proportion of oxygene in the whole compound is less than that entering into the composition of the nitric acid, and that it is therefore less oxygenated. By the same mode of reasoning we might prove that water, by absorbing carbonic acid gas, became less oxygenated, which is absurd. Should any one attempt to prove (which will be necessary to substantiate the generally received doctrine) that the oxygene of the nitrous gas combines with the oxygene of the acid, and the nitrogene, in like manner, so that the resulting acid, when nitrous gas is absorbed by nitric acid, is a binary combination of oxygene and nitrogene, he would find it somewhat more difficult than he at first imagined; it appears to me impossible. It is much more consonant with experiment to suppose that nitrous acid is nothing more than nitric acid holding nitrous gas in solution, which might in conformity to the principles of the French nomenclature, be called nitrate of nitrogene. The difficulty, and in some cases the impossibility, of forming nitrites, arises from the weak affinity which nitrous gas has for nitric acid, compared with that of other substances; and the decomposition of nitrous acid (that is, nitrate of nitrogene) by an alkaline or metallic substance, is perfectly analogous to the decomposition of any other nitrate, the nitrous gas being displaced by the superior affinity of the alkali for the acid.
“Agreeable to this theory, the salts denominated nitrites are in fact triple salts, or ternary combinations of nitric acid, nitrous gas, and salifiable bases.”
This theory is perfectly new to me. Other Chemists to whom I have mentioned it, have likewise considered it as new. Yet in a subsequent letter Mr. Thomson mentions that he had been told of the belief of a similar opinion among the French Chemists.
[34] In some experiments made on the nitrites of potash, and of ammoniac, before I was well acquainted with the composition of nitric acid, I found that a light olive-colored acid of 1,28, was capable of being saturated by weak solutions of potash and ammoniac, without losing any nitrous gas; but after the evaporation of the neutralised solution, at very low temperatures, the salts in all their properties resembled nitrates.
[35] As is evident from the curious appearance of the dark green spherules, repulsive both to water, and light green acid.
[36] That is, undecompounded.
[37] The existence of these bodies will be hereafter proved.
[38] The blue green acid is not homogeneal in its composition, it is composed of the blue green spherules and the bright green acid. The blue green spherules are of greater specific gravity than the dark green acid, probably because they contain little or no water.
[39] The composition of the acids thus marked, is given from calculations.
[40] Nitrous gas contains 44,05 Nitrogene, and 55,95 Oxygene, as has been said before.
[41] A great portion of it, of course, dissolved in the water with the nitrous acid carried over.
[42] Their changes of volume, corresponding to changes of temperature, most probably, are likewise different.
[43] Probably in the ratio of the square of the quantity of water united to it.
[44] The quantities of Oxygene and Nitrogene in any solution, may be thus found—— Let A = the true acid, X the oxygene, and Y the nitrogene.
Then
| 238 A | A | ||
| X = | ——— | and Y = | ——— |
| 239 | 239 |
[45] Experiments and Observations; last edition, vol. 1, page 384.
[46] Nitrous gas, holding in solution nitrous acid, is more readily absorbed by water than when in its pure form, from being presented to it in a more condensed state in the green acid, formed by the contact of water and nitrous vapor.
[47] Mem. des Savans Etrangers, v. xi. 226. Vide Kirwan sur le phlogistique pag. 110.
[48] In this experiment, as well as in the last, some of the mixture was thrown into the jar undecompounded.
[49] To detach the potash from the carbonic acid.
[50] This nitrogene contained a little nitrous gas, as it gave red fumes when exposed to the air. The free nitrous acid was decomposed by the mercury, as it was not covered with water.
[51] Essay on phlogiston.
[52] Dr. Priestley says, “Having filled a phial containing exactly the quantity of four pennyweights of water, with strong, pale, yellow spirit of nitre, with its mouth quite close to the top of a large receiver standing in water, I carefully drew out almost all the common air, and then filled it with nitrous air; and as this was absorbed, I kept putting in more and more, till in less than two days it had completely absorbed 130 ounce measures. Presently after this process began, the surface of the acid assumed a deep orange color, and when 20 or 30 ounce measures of air were absorbed, it became green at the top: this green descended lower and lower, till it reached the bottom of the phial. Towards the end of the process, the evaporation was perceived to be very great, and when I took it out, the quantity was found to have diminished to one half. Also it had become, by means of this process, and the evaporation together, exceeding weak, and was rather blue than green.”
Experiments and Observations, vol. 1, p. 384. Last edition.
[53] See Mr. Keir’s excellent observations on this subject. Chem. Dict. Art. Acid.
[54] Irish Transactions, vol. 4, p. 34.
[55] Addit. Obs. pag. 74.
[56] Additional Observations, page 70.
[57] Elements, pag. 103, Kerr’s Translation.
[58] Mem. Acad. 1787.
[59] As well as oxygene and nitrogene, Mr. Watt’s experiments prove that much phlogisticated nitrous acid is produced.
[60] Journal de Physique, 1786. Tom. 2, pag. 176.
[61] Though the tube had never been used, and was apparently clean and dry on the inside, it must have contained something in the form of dust, capable of furnishing either hydrocarbonate, or charcoal.
[62] Journal de Physique, 1786, t. 2, 177.
[63] Phil. Trans. vol. 79, page 294.
[64] Vol. 2, page 398.
[65] Ammoniac generated at a temperature above that of the atmosphere, always deposits ammoniacal solution during its reduction to the common temperature.
[66] By the introduction of aëriform ammoniac into the exhausted globe.
[67] Additional Observations, page 107.
[68] It is necessary in these experiments, that the greatest care be observed in the introduction and extraction of the capillary tube. If it is introduced dry, there will be a source of error from the moisture adhering to it when taken out. I therefore always wetted it before its introduction, and took care that no more fluid adhered to it after the experiment, than before.
[69] Previous to those experiments, I had made a number of others on the combination of ammoniac with water.—My design was, to ascertain the diminution of specific gravity for every three grains of ammoniac absorbed; but this I found impossible. The capillary tube, when taken out of the phial, always carried with it a minute portion of the solution, which partially evaporated before it could be again introduced; and thus the sources of error increased in proportion to the number of examinations.
[70] The expansion from increase of temperature is probably great in proportion to the quantity of ammoniac in the solution.
[71] From the combination.
[72] I had before proved that at this temperature the salt neither decomposed nor sublimed.
[73] A particular account of the experiments from which these facts were deduced, was printed in September, and will appear in the first volume of the Researches.
[74] And which will be published, with an account of its perfect decomposition at a high temperature, in the Researches.
[75] When nitrous gas exists in neutro-saline solutions, they are always colored more or less intensely, from yellow to olive, in proportion to the quantity combined with them.
[76] Hence a nitrate of ammoniac with excess of acid, when exposed to heat, first becomes yellow, and then white.
[77] The accounts given by different chemists of the composition of nitrate of ammoniac, are extremely discordant; they have been chiefly deduced from decompositions of carbonate of ammoniac (the varieties of which have been heretofore unknown) by nitrous acids of unknown degrees of nitration. Hence they are particularly erroneous with regard to the alkaline part. Wenzel supposes it to be 32 per cent, and Kirwan 24. Addit. Observ. pag. 120.
[78] Mem. Par. 1783. See Irish Trans. vol. 4.
[79] Addit. Obs. pag. 120.
[80] Two measures of air dispelled from this water by boiling, mingled with 2 of nitrous gas, diminished to 2,4 nearly.
[81] Experiments and Observations, vol. 2, pag. 89. Last Edition.
[82] A minute quantity, however, must have been absorbed, and given out again when the charcoal was heated.
[83] Strong solution of ammoniac has no attraction for nitrous oxide.
[84] The gas was examined by those tests in order to prove that no water had been decomposed.
[85] See the curious paper of this excellent philosopher, on the combustion of the diamond, in which he proves that charcoal is, in fact, oxide of diamond. Annales de Chimie, xxxi.
[86] This was actually the case; for on examining the conducting tube the day after the experiment, some minute crystals of prismatic nitrate of ammoniac were perceived in it.
[87] Owing part of their weight to an unknown quantity of water.
[88] Mem. de Paris. 1785, and Journal de Physique, 1786, page 175.
[89] The absorption of nitrous gas by sulphate of iron, &c. will be treated of in the next division.
[90] As is evident from the decomposition of ammoniac by heat.
[91] Nitric acid is phlogisticated by heat, as appears from Dr. Priestley’s experiments. Vol. 3, p. 26.
[92] As is evident from the increase of temperature required for the formation of water.
[93] For ammoniac and nitrous oxide are both decomposed at the red heat, and oxygene given out from nitric acid when it is passed through a heated tube.
[94] Whenever nitrous acid is produced at high temperatures, it is always highly phlogisticated, provided it has not been long in contact with oxygene. When Dr. Priestley passed nitric acid through a tube heated red, he procured much oxygene, and phlogisticated acid; and the water in the apparatus employed was fully impregnated with nitrous air. Hence it would appear, that heat diminishes the attraction between oxygene and nitrous gas, and increases the affinity of nitrous gas for nitrous acid. Mr. James Thomson, whose theory of the Nitrous Acid I have already mentioned, from some experiments on the phlogistication of Nitric Acid by heat, which he has communicated to me, concludes with great justness, that a portion of the acid is always completely decomposed in this process: the oxygene liberated, and the nitrous gas combined with the remaining acid.
[95] Except it be gold or platina.
[96] A pound of nitrate of ammoniac costs about 5s. 10d. This pound, properly decomposed, produces rather more than 34 moderate doses of air; so that the expence of a dose is about 2d. What fluid stimulus can be procured at so cheap a rate?
[97] Experiments and Observations, vol. II. pag. 50. Last Edition.
[98] That is, charcoal produced by the decomposition of spirits of wine. Vol. II. pag. 39.
[99] Dr. Priestley says, “having heated iron in nitrous air, I proceeded to heat in the same air, a piece of charcoal not long after it had been subjected to a strong heat covered with sand. The sun not shining immediately, after the charcoal was introduced into the vessel of air, through the mercury by which it was confined, part of the air was absorbed; but on heating the charcoal, the quantity was increased. Having continued the progress as long as I thought necessary, I examined the air and found it to be about as much as the original quantity of nitrous air; but it was all phlogisticated air extinguishing a candle and having no mixture of fixed air in it.”—Experiments and Observations, Vol. II, page 39.
[100] That is, sulphate of iron containing oxide of iron, in the first degree of oxygenation.
[101] That is, carbon, or oxide of diamond.
[102] That is, blue prussiate of iron.
[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.
[105] This mode of inflaming bodies in gases, not capable of supporting combustion at low temperatures, will be particularly described hereafter.
[106] Elements English Trans. edit. i. pag. 216.
[107] Experiments and Observations, Vol. II. pag. 40, 2d. Ed.
[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.
[109] Which was certainly as free from air as it ever can be obtained.
[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.
[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?
[112] The water still being unity.
[113] He says “100 parties de gaz nitreux, (à 0.14 d’azote) secouées avec l’eau distillée, récemment cuite, diminuent en volume de 0.11, ou 0.12. Ce même gaz, en contact avec l’eau de puits, ne perd que 0.02. La cause de cette différence de 0.9, ou 0.10, ne doit pas être attribuée ni à l’impurité de l’air atmosphérique, contenu dans les interstices de l’eau, ni à la décomposition de cette eau même. Elle n’est qu’apparente; car l’acide nitrique, qui se forme par le contact du gaz nitreux avec l’eau de puits, en décompose le carbonate de chaux. Il se dégage de l’acide carbonique, qui, en augmentant le volume du residu, rend l’absorption du gaz nitreux moins sensible. Pour déterminer la quantité de cet acide carbonique, je lavai le résidu avec de l’eau de chaux. Dans un grand nombre d’expériences, le volume diminua de 0.09, ou 0.07. Il faut en conduire que l’eau de puits absorbe réellement 9 + 2, ou 7 + 2 parties de gas nitreux, c’est-à-dire, à peu-près la même quantité que l’eau distillée.”
Annales De Chimie, xxviii. pag. 154.
[114] Nicholson’s Phil. Jour. No. 1, p. 453.
[115] I have been able to make these observations on the sulphates of iron, most of them after Proust.
[116] Annales de Chimie, vol. xxviii. pag. 182.
[117] [Division IV. Section 5.]
[118] [Division II. Section 1].
[119] No precipitation takes place during the conversion of solution of green sulphate into red; and the acid appears saturated.
[120] Division II, Section 6.
[121] According to the estimation in the equation, 6.5 of dry green sulphate of iron contain 4.1 green oxide of iron, and 2.4 of Kirwan’s real sulphuric acid; and 8.1 red sulphate of iron, contain 2.4 acid, and 5.7 red oxide of iron.
[122] The muddy green color produced in a solution of red sulphate of iron agitated in nitrous gas, depended upon impurities in the mercury. I have since found, that when the solution is completely oxygenated, the diminution is barely perceptible.
[123] Perhaps the liberation of nitrous gas from the solution takes place at a lower temperature than its decomposition. I have always observed that the quantity of yellow precipitate is greater when the solution is rapidly made to boil. Were it possible to heat it to a certain temperature at once, probably a compleat decomposition would take place.
[124] Annales de Chimie. T. 38, pag. 187.
[125] Annales de Chimie, xxiii. pag. 85; or Nicholson’s Phil. Journal vol. i. pag. 45.
[126] Probably by giving them oxygene; whereas the green muriate and sulphate blacken animal substances; most likely by abstracting from them oxygene.
[127] The existence of green nitrate was not suspected by Proust.
[128] In this process nitrous oxide is sometimes given out, as will be seen hereafter.
[129] Hence we learn why no nitrous gas is disengaged when impregnated solution of sulphate of iron is decomposed by prussiate of potash, as in Div. IV. Sec. vii.
[130] In both of these solutions the metal is at its minimum of oxydation. The absorption of a small quantity of nitrous gas by white vitriol was observed by Priestley.
[131] Humbolt, who is the first philosopher that has applied the solution of sulphate of iron to ascertain the purity of nitrous gas, asserts that he uniformly found nitrous gas obtained from solution of copper in nitrous acid, to contain from six tenths to one tenth nitrogene.
Annales de Chimie, vol. xxviii. pag. 147.
[132] Vol. ii. pag. 55.
[133] Phil. Trans. vol. lxxvi. pag. 133.
[134] Journal de Physique, tom. xliii. 323.
[135] That is, alumn containing sulphate of potash.
[136] The production of ammoniac in this process was observed by Kirwan and Austin.
[137] Solution of sulphure of strontian, or barytes, should be used. During the conversion of nitrous gas into nitrous oxide by those bodies, a thin film is deposited on the surface of the solution. This film examined, is found to consist of sulphur and sulphate. Possibly the nitrous gas is wholly decomposed by the hydrogene of the sulphurated hydrogene in the solution, whilst the sulphate is produced from water decompounded by the sulphur to form more gas for the saturation of the hydro-sulphure.
[138] As was first observed by Priestley and Austin, and as I have proved by many experiments.
[139] As I have found by experiment.
[140] As was observed by Milner. Nitrous gas passed over heated zinc, or tin, I doubt not will be found converted into nitrous oxide.
[141] Annales de Chimie, xxxii. p. 3.
[142] The decomposition and recomposition of water, in this process, are analogous to some of the phænomena observed by the ingenious Mrs. Fulhame.
[143] From one of Dr. Priestley’s experiments, it appears that hydrogene gas is sometimes disengaged during the solution of iron in very dilute nitric acid by heat. This phænomenon has never occurred to me.
[144] As was discovered by Priestley, and the Dutch Chemists.
[145] Such as the leaves, bark, and wood, of trees.
[146] As I have observed after Priestley.
[147] As was discovered by Priestly.
[148] This deep color depended, in some measure, upon the nitro-muriatic vapor suspended in it. I have since observed that it is more intense in proportion as the heat employed for the production of the gas has been stronger. The natural color of the peculiar gas is deep yellow.
[149] The decomposition of aëriform nitrous acid by mercury, was first noted by Priestley; vol. iii. pag. 101. This decomposition I have often had occasion to observe. In reading Humbolt’s paper on eudiometry, Annales de Chimie, xxviii, pag. 150, I was not a little surprised to find that he takes no notice of this fact. He seems to suppose that nitrous acid can remain aëriform, and even be condensed, in contact with mercury, without alteration. He says, “In mingling 100 parts of atmospheric air with 100 of nitrous air, the air immediately became red, but all the acid produced remained aëriform; and after eighteen hours some drops only of acid were formed, which swam upon themercury.”
[150] Lavoisier has said concerning aqua regia, “In solutions of metals in this acid, as in all other acids, the metals are first oxydated, by attracting a part of the oxygene from the compound radical. This occasions the disengagement of a particular species of gas not hitherto described, which may be called nitro-muriatic gas. It has a very disagreeable smell, and is fatal to animal life when respired; it attacks iron, and causes it to rust; it is absorbed in considerable quantities by water.” Elem. Eng. 237.
[151] I have no doubt but that the gas procured from the solution of gold in aqua regia, is analogous to that produced from platina.
Some very uncommon circumstances are attendant on the solution of platina:
1st. The immense quantity of acid required for the solution of a minute quantity of platina.
2d. The great quantity of gas produced during the solution of this minute quantity.
3d. The intense red color of the solution, and its perfectly acid properties after it ceases to act upon the metal.
[152] For if nitrous oxide had been formed, it would have been decomposed by the hydrogene.
[153] Experiments and observations, vol. ii. pag. 81.
[154] The experiments of Berthollet have clearly proved the perfect acidity of this substance.
[155] The Dutch chemists have asserted, that mixture with ammoniac prevents the absorption of nitrous oxide by water, either wholly or partially. Journal de Physique, t. xliii. part ii. pag. 327. It is difficult to account for their mistake.
[156] Sulphureous acid saturates more potash than sulphuric acid, so that most probably during the conversion of sulphite of potash into sulphate, portions of sulphureous acid are disengaged.
[157] Hence we learn that sulphite of potash, when strongly heated, does not decompose nitrous oxide, even in the nascent state.
[158] See the excellent memoir of Fourcroy and Vauquelin on the sulphureous acid, and its combinations. Annales de Chimie, ii, 54. Or Nicholson’s Phil. Journal, vol. i, pag. 313.
[159] Unless the sum of affinity of the potash, oil, nitrous oxide, and earths, should be inch as to enable the nitrous oxide to combine with the earth, whilst the oil and alkali remained in combination, & c.
[160] For when a little of the mixed salt was introduced into a solution of sulphurated hydrogene, globules of gas were given out during the solution.
[161] Carbonate of ammoniac formed at a high temperature, containing near 60 per cent alkali, and capable of combining with small quantities of acids without giving out its carbonic acid. Of this salt a particular account will be given in the experiments on the ammoniacal salts, which I have often mentioned in the course of this work.
[162] It may not be amiss to mention some appearances taking place in the decomposition of nitrous gas by sulphurated hydrogene, though it is useless to theorise concerning them. The sulphur deposited is at first yellow; as the process proceeds, it becomes white, and in some instances I have suspected a diminution of it.
[163] Predisposing affinity, the existence of which at first consideration it is difficult to admit, may be easily accounted for by supposing the attractions of the simple principles of compound substances. And this doctrine will apply in all instances where the constitution of bodies is known. Predisposing affinity ought not to be considered as the affinity of non-existing bodies for each other; but as the mutual affinity of their simple principles, disposing them to assume new arrangements.
[164] See the above mentioned elaborate memoir of Fourcroy and Vauquelin.
[165] The different persons who have respired nitrous oxide have, as will be seen hereafter, given different accounts of the taste; the greater number have called it sweet, some metallic. One of my friends, in a letter to me dated Nov. 13, 1799, containing a detail of some experiments made on the respiration of nitrous oxide, at Birmingham, denotes the taste of it by the term “sweetish faintly acidulous.” To me the taste both of the gas and of its solution in water, has always appeared faintly sweetish.
[166] Section 2.
[167] Vol. ii. pag. 91.
[168] Journal de Physique, tom. xliii, part ii. pag. 330. They effected the same change by passing it through a heated tube. Dr. Priestley had published an account of similar experiments more than two years before.
[169] On the one hand, it decomposes ammoniac into hydrogene and nitrogene, whilst on the other, it converts free oxygene and nitrogene into nitrous acid. It likewise converts nitrous gas into nitrous acid and nitrogene. Till we are more accurately acquainted with the nature of heat, light, and electricity, we shall probably be unable to explain these phænomena.
[170] Vol. ii. pag. 83.
[171] Journal de Physique, tom. xliii. part 2, pag. 331. They supposed it to consist of about 37,5 oxygene, and 62,5 nitrogene. The nearness of this account to the truth is singular, when we consider that they were neither acquainted with the specific gravity of nitrous oxide, nor with the production of nitrous acid in this experiment.
[172] Experiments on the detonation of nitrous oxide with phosphorus in this way require great attention. The detonating jar should be very conical; the nitrous oxide employed should never equal more than one eighth of the capacity of the jar. The wire for the inflammation must be very thick, and curved so as to be easily introduced into the jar. When ignited, it must be instantaneously passed through the heated mercury into the jar.
Perhaps the electric spark might be advantageously applied for detonating phosphoric vapor with nitrous oxide.
[173] It will be seen hereafter that these bodies are easily inflamed in nitrous oxide.
[174] Phosphorus burnt feebly with a white flame in a mixture of 4 nitrogene and 1 nitrous oxide.
[175] Journal de Physique, xliii. 328.
[176] In this experiment, as in the last, dense white vapor was produced.
[177] [Res. I. Div. III. S. II.]
[178] Journal de Physique, xliii. 334.
[179] As is proved by the decomposition of oxide of iron and sulphuric acid by charcoal, at that temperature.
[180] Hydrogene at or about the red heat, appears to attract oxygene stronger than phosphorus. See Dr. Priestley’s experiments, vol. i. page 262.
[181] That attraction must be called chemical, which enables bodies of different specific gravities to unite in such a manner as to produce a compound, in every part of which the constituents are found in the same proportions to each other. Atmospheric air, examined after having been at perfect rest in closed vessels, for a great length of time, contains in every part the same proportions of oxygene and nitrogene; whereas if no affinity existed between these principles, following the laws of specific gravity, they ought to separate; the oxygene forming the inferior, the nitrogene the superior stratum.
The supposition of the chemical composition of atmospheric air, has been advanced by many philosophers. The two first evidences have been often noticed.
[182] For it is unalterable by those bodies which are capable of attracting oxygene from nitrous gas and nitrous acid, at common temperatures.
[183] See the curious experiments of Rosier, Journal de Physique, 1786, vol. 1, pag. 419.
[184] As appears from the experiments of Dr. Beddoes; likewise those of Mr. Watt.
[185] As appears from the experiments of Lavoisier and Dr. Beddoes; and as will be seen hereafter.
[186] The colour of common venous blood, examined in this way, resembles that of the paint called by colour-men red ochre; that of blood saturated with nitrous oxide, approaches to the tinge of lake.
[187] Small birds suffer much from cold when introduced into gases through water. In this experiment, the goldfinch was immediately inserted into a large mouthed phial, filled with the gases, and opened in the atmosphere.
[188] I use the popular name. This fish is very common in every part of England; it is nearly of the same size and color as the minnow, and is distinguished from it by two small bony excresences at the origin of the belly. It is extremely susceptible.
[189] A priori I expected that fishes, like amphibious animals would have been very quickly destroyed by the action of nitrous oxide.
[190] The hydrocarbonate employed, was procured from alcohol, by means of sulphuric acid. This gas contains more carbon, than hydrocarbonate from water and charcoal.
[191] The curious fact of the reddening of venous blood by hydrocarbonate, was discovered by Dr. Beddoes.
[192] By lungs, I mean in this place, all the internal organs of respiration.
[193] Because these products are formed during the respiration of common air.
[194] Annales de Chimie, vol. 1, page 279.
[195] This is only an imperfect approximation; the ratio of the increase of expansibility of gases to the increase of temperature, has not yet been ascertained. It is probable that the expansibility of gases is altered by their mixture.
[196] For there is no reason to suppose the production of nitrogene.
[197] This capacity is most probably below the medium, my chest is narrow, measuring in circumference, but 29 inches, and my neck rather long and slender.
[198] Dr. Goodwyn in his excellent work on the connexion of life with respiration, has detailed some experiments on the capacity of the lungs after natural expiration. He makes the medium capacity about 109 cubic inches, which agrees very well with my estimation.—page 27.
[199] The oxygene as we have before noticed, most probably wholly existed in the residual gas.
[200] When they are agitated, a greater proportion of nitrous gas is absorbed, condensed in the nitric acid by the water; and to find the oxygene,
| (50 - m) | (50 - m) | |
| x = | ———— or | ———— |
| (3,4) | (3,5) |
[201] The diminution of air by single inspirations, was particularly noticed by Dr. Goodwyn.
[202] Dr. Priestley found that it likewise became florid at the surface when covered by milk; but that it underwent little or no alteration of color under water and most other fluids.—Vol. 3. p. 372.
[203] There are many analogous decompositions. Dr. Priestley noticed (and I have often made the observation) that green oxide of iron, or the precipitate from pale green sulphate of iron by caustic alkali, became red at the surface, when covered by a thick stratum of water. In my experiments on the green muriate and sulphate of iron, I observed that part of some dark oxide of iron which was at the bottom of a trough of water 9 inches deep, became red at the surface nearly in the same time as another portion of the same precipitation that was exposed to the atmosphere. This oxygenation must depend upon the decomposition of atmospheric air constantly dissolved by the water.
[204] Dr. Mitchill attempted to prove from some phænomena connected with contagious diseases, that dephlogisticated nitrous gas which he called oxide of septon, was the principle of contagion, and capable of producing the most terrible effects when respired by animals in the minutest quantities or even when applied to the skin or muscular fibre.
[205] I did not attempt to experiment upon animals, because they die nearly in equal times in non-respirable gases, and gases incapable of supporting life and possessed of no action on the venous blood.
[206] Dr. Beddoes has given some account of this experiment, in his Notice of some observations made at the Medical Pneumatic Institution. It was noticed in Mr. Nicholson’s Phil. Journal for May 1799.
[207] Mild physical pleasure is perhaps always destructive to action. Almost all our powerful voluntary actions, arise either from hope, fear, or desire; and the most powerful from desire, which is an emotion produced by the coalescence of hope or ideal pleasure with physical pain.
[208] Pure hydrogene has been often respired by different Philosophers, particularly by Scheele, Fontana, and the adventurous and unfortunate Rosier.
[209] I believe it had never been breathed before by any individual, in a state so little diluted.
[210] I ought to observe, that between eight and ten, I took by the advice of Dr. Beddoes, two or three doses of diluted nitric acid.
[211] By whatever cause the exhaustion of organs is produced, pain is almost uniformly connected with their returning health. Pain is rarely ever perceived in limbs debilitated by fatigue till after they have been for some hours at rest. Pain is uniformly connected with the recovery from the debility induced by typhus, often with the recovery from that produced by the stimulation of opium and alcohol.
[212] Carbonic acid is produced in this way in a high state of purity, and with great readiness.
[213] Carbonic acid possesses no action on arterial blood. Hence perhaps, its slight effects when breathed mingled with large quantities of common air. Its effects are very marked upon venous blood! If it were thrown forcibly into the lungs of animals, the momentary application of it to the pulmonary venous blood would probably destroy life.
[214] In a conversation with Mr. Watt, relating to the powers of gases, that excellent philosopher told me he had for some time entertained a suspicion, that the effects attributed to oxygene produced from manganese by heat, in some measure depended upon nitrous acid suspended in the gas, formed during ignition by the union of some of the oxygene of the manganese with nitrogene likewise condensed in it.
In the course of experiments on nitrous acid, detailed in [Research I]. made in September, October, and December, 1799, I several times experienced a severe oppression on the chest and difficulty of respiration, not unanalogous to that produced by oxygene, but much more violent, from breathing an atmosphere loaded with nitrous acid vapour. This fact seemed to confirm Mr. Watt’s suspicion. I confess, however, that I have never been able to detect any smell of nitrous acid, either by means of my own organs or those of others, during the production of oxygene; when the gas is suffered to pass into the atmosphere. The oxygene breathed in the experiments detailed in the text, had been for some days in contact with water.
[215] In the same manner as the debility from intoxication by two bottles of wine is increased by a third.
[216] I ought to observe that my usual drink is water, that I had been little accustomed to take wine or spirits, and had never been compleatly intoxicated but once before in the course of my life. This will account for the powerful effects of a single bottle of wine.
[217] The plan of this box was communicated by Mr. Watt. An account of it will be detailed in the Researches.
[218] The nitrous oxide was too diluted to act much; it was mingled with near 32 times its bulk of atmospheric air.
[219] In all these experiments after the first minute, my cheeks became purple.
[220] Physical pleasure and pain generally occur connected with a compound impression, i. e. an organ and some object. When the idea left by the compound impression, is called up by being linked accidentally to some other idea or impression, no recurrence, or the slightest possible, of the pleasure or pain in any form will take place. But when the compound impression itself exists without the physical pleasure or pain, it will awaken ideal or intellectual pleasure or pain, i. e. hope or fear. So that physical pleasure and pain are to hope and fear, what impressions are to ideas. For instance, assuming no accidental association, the child does not fear the fire before he is burnt. When he puts his finger to the fire he feels the physical pain of burning, which is connected with a visible compound impression, the fire and his finger. Now when the compound idea of the fire and his finger, left by the compound impression are called up by his mother, saying, “You have burnt your finger,” nothing like fear or the pain of burning is connected with it. But when the finger is brought near the fire, i. e. when the compound impression again exists, the ideal pain of burning or the passion of fear is awakened, and it becomes connected with those very actions which removed the finger from the fire.
[221] Notice of some Observations made at the Medical Pneumatic Institution.
[222] In some of these experiments, hearing was rendered more acute.
[223] Dr. Mitchill (an American Chemist) has erroneously supposed its full admission to the lungs, in its concentrated state, to be incompatible with animal life, and that in a more diluted form it operates as a principal agent in the production of contagious diseases, &c. This gratuitous position is thus unqualifiedly affirmed. “If a full inspiration of gaseous oxyd be made, there will be a sudden extinction of life; and this accordingly accounts for the fact related by Russel (History of Aleppo, p. 232.) and confirmed by other observers, of many persons falling down dead suddenly, when struck with the contagion of the plague.”
Vide Remarks on the Gaseous Oxyd of Azote, by Samuel Latham Mitchill, M. D.
[224] In the former experiments, Mr. Southey generally respired six quarts, now he is unable to consume two.
In an experiment made since this paper was drawn up, the effect was rather pleasurable.
[225] The doses in these experiments were from five to seven quarts.
[226] Of the facts on which Brown founded his law of indirect debility, no prudent man will lose sight either in practising or studying medicine. They are incontrovertible.—And our new facts may doubtless be conciliated to the Brunonian doctrine.
But to suppose that the expenditure of a quality or a substance or a spirit, and its renewal or accumulation are the general principles of animal phænomena, seems to me a grievous and baneful error. I believe it often happens that excitement and excitability increase, and that they oftener decrease together;—In short, without generalizing in a manner, of which Brown and similar theorists had no conception, our notions of the living world will in my opinion, continue to be as confused as the elements are said to have been in chaos. On some future occasion, I may presume to point out the region through which I imagine the path to wind, that will lead the observers of some distant generation to a point, whence they may enjoy a view of the subtle, busy and intricate movements of the organic creation as clear as Newton obtained of the movements of the heavenly masses.
[227] After writing this, I was present when an invalid, in whose foot the gout, after much wandering, had at last fixed, breathed 12 quarts of oxygene gas. While breathing, he eagerly pointed to the inflamed leg; and afterwards said he had felt in it a new sensation, somewhat like tension.—I never had seen oxygene respired where there was so much local inflammation.
June 18. After four quarts of oxygene with 6 of nitrous oxide and then 6 of nitrous oxide alone, violent itching of the wounds made by the leech; and redness and tumour.—Both had healed, and I did not expect to feel any thing more from them.—I tried this again with two doses of nitrous oxide—The yellow halo round one wound changed to crimson, and there was so much stinging and swelling that I feared suppuration.—Absorption here was rapid.
[228] See Dr. Beddoes’s Considerations, part 1. page 26. His observations in the note in the last section, will likewise apply here.—Is not healthy living action dependant upon a certain equilibrium between the principles supplied to the blood by the pulmonary veins from respiration and by the lymphatics from absorption? Does not sensibility more immediately depend upon respiration? Deprive an animal under stimulation, of air, and it instantly dies; probably if absorption could be prevented, it would likewise speedily die. It would be curious to try whether intoxication from fermented liquors cannot be prevented by breathing during their operation, an atmosphere deprived of part of its oxygene.
[229] Sublime emotion with regard to natural objects, is generally produced by the connection of the pleasure of beauty with the passion of fear.
[230] The immortal Hartley has demonstrated that all our motions are originally automatic, and generally produced by the action of tangible things on the muscular fibre.
The common actions of adults may be distinguished into two kinds; voluntary actions, and mixed automatic actions. The first are produced by ideas, or by ideas connected with passions. The second by impression, or by pleasure and pain.
In voluntary action, regular associations of ideas and muscular motions exist: as when a chemist performs a pre-conceived experiment.
In mixed automatic actions, the simple motions produced by impression are connected with series of motions formerly voluntary, but now produced without the intervention of ideas: as when a person accustomed to play on the harpsichord, from accidentally striking a key, is induced to perform the series of motions which produce a well-remembered tune.
Evidently the muscular actions produced by nitrous oxide are mixed automatic motions.
[231] See R. IV. Div. I. page 478.
[232] R. IV. Div. I. page 467.
[233] That of Brown modified by his disciples.
[234] Supposing the increase or diminution of living action when produced by different agents, uniform, similar and differing only in degree; it would follow, that certain mixtures of hydrocarbonate and nitrous oxide, or hydrogene and nitrous oxide, ought to be capable of supporting the life of animals for a much longer time than pure nitrous oxide. From the experiments in [Res. III. Div. I]. it appears however, that this is not the case.
It would seem, that in life, a variety of different corpuscular changes are capable of producing phænomena apparently similar; so that in the science of living action, we are incapable of reasoning concerning causes from effects.
[235] Annales de Chimie, 100; and Mr. Tilloch’s Phil. Magazine. 24.
[236] I regret much that I could not procure Dr. Menzies’s observations on Respiration, while I was making the experiments on the capacity of the lungs: they would probably have saved me some labor.
[237] If loosely combined carbon exists in venous blood, hydrogene may probably dissolve a portion of it when respired and become slightly carbonated. At least there is as much probability in the supposition that carbon in loose affinity may combine with hydrogene at 98° as that it may combine with oxygene.
[238] Dr. Beddoes has since favoured me with the following account of these facts.
“Mr. Humboldt (ueber die gereizte Faser I. 473, 1797) quotes part of a letter from Dr. Ash, in which it is said that if two finely polished plates of homogeneous zinc be moistened and laid together, little effect follows—but if zinc and silver be tried in the same way, the whole surface of the silver will be covered with oxydated zinc. Lead and quicksilver act as powerfully on each other, and so do iron and copper.—Mr. Humboldt (p. 474) says that, in repeating this experiment, he saw air-bubbles ascend, which he supposes to have been hydrogene gas from the decomposition of water—When he placed zinc simply on moist glass, the same phænomena took place, but more slowly and later. The quantity of oxyd of zinc upon the glass alone was in 20 hours to that on the silver as one to three.
In a very ingenious but obscurely written tract by Mr. Ritter, entitled, Evidence that the galvanic action exists in organic nature, 8vo. Jena, 1800—The author observes, that the care of Dr. Ash and Mr. Humboldt that the metals should touch each other in as many points as possible was superfluous, even if we could grant that two metallic plates might be made by polishing, to touch in a number of points. To shew that it was sufficient if by touching in one point only they should form a compleat galvanic circle, he dropped a single drop of distilled water upon the bust of a large silver coin. A piece of pure zinc was placed with its one end on the edge of the coin, while the other was supported by a bit of glass. The drop of water was neither in contact with the glass nor with the point at which the metals touched. The materials were left in this situation for four hours at the temperature of 68°. On taking them apart, the water had become quite milky and had half disappeared; and Mr. Ritter actually separated a quantity of white oxide that had been produced in the experiment.
The pieces of metal were cleaned and laid together in the same manner, only that now a piece of paper was put between the metals at their former point of contact. In four hours first, and afterwards in ten, a faint ring of oxide only had been produced of which the quantity could not be estimated, nor could it be separated. In this case, the zinc had scarce lost any thing of its splendour; in the former it had been corroded. In many repetitions of the experiment, he found that far more oxide was formed when the metals touched, than when they were separated to the slightest distance by an insolating body, even air.
On exposing these apparatuses with somewhat more water to a considerable heat for four minutes, the water in the interrupted circle continued quite clear, while that in the other had become milk-white.
The same phænomena were presented by other pairs of metals in a degree proportional to their galvanic activity; viz. by zinc and molybdæna, zinc and bismuth, zinc and copper, as also with tin and silver, tin and molybdæna, and lead and silver. The experiment with tin was particularly decisive, for when in contact with no other metal it was scarcely at all oxydated by water, though oxydation took place when tin was brought into contact with silver, and both were connected at the other end by a drop of water—What therefore took place in Dr. Ash’s experiment, arose from an aggregation of galvanic circles of different forms.
By the foregoing experiments, concludes Mr. Ritter, which though capable of the most various modifications, uniformly coincide in their main result, it is abundantly proved that galvanic circles can be formed of merely inorganic bodies, by whose completion there is produced an action which ceases when the circle is opened. The manner in which this has been shewn, proves also that this action can effectuate sensible modifications in organic bodies; and the process by which these modifications have been effected, made it evident that they were not consequences of a momentary action of the circle, but of an action that is kept up while the circle remains entire; for the process which brought this action under the cognizance of the senses went on, while the circle was unbroken, and its figure not brought back to that of a line.
It is scarce necessary to observe that the experiments here quoted, are far from being the only ones on which the above conclusions rest.”
T. B.
[239] Possibly a ratio exists between the solubility of gases in water, and the solubility of water in gases. It is probable from Mr. Wm. Henry’s curious experiments on the muriatic acid, that the absolute quantity of water in many gases, may be ascertained by means of its decomposition by the electric spark.
Transcriber’s Notes:
The cover image was created by the transcriber, and is in the public domain.
Ancient spellings were not corrected.
Typographical and punctuation errors have been silently corrected.
The text usually uses a comma to designate a decimal point, although a period is used in some instances.
The changes mentioned in the ERRATA have been applied to the text.