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CULAR THEORY,
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SIMPKIN. AMEDEO AVOGADRO. HAMILTON.) OF THE UNIVERSITY OF IFOR EDINBURGH : WILLIAM F. (1808-1811. LTD. . 18 : TEVIOT PLACE. KENT. JOSEPH-LOUIS AND GAY-LUSSAC. MARSHALL. LONDON 1893. CLAY. 4. & CO. FOUNDATIONS OF THE MOLECULAR THEORY COMPRISING PAPERS AND EXTRACTS BY JOHN DALTON.(gfemfiic fu6 (geprtnfe ($o.

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although he does not point this out in his paper. but that he is legitimately forced to reject this assumption. JL papers here reprinted in chronological order serve to exhibit the historical development of the idea of a connection existing between the number of particles in different gases and the volume they occupy. 1814). conceiving no distinction between the atom and the molecule of an element.PREFACE. since that paper contains no advance on the views of Avogadro published three years earlier. W. Dalton. perceives the necessity. and teaches how to reconcile them by distinguishing between the atom and the molecule of an elementary gas. 43-86. where the French always clumsy and occasionally obscure. finally. especially so is Avogadro's paper. theory and Gay-Lussac's data. It will be seen that Dalton from the first entertains the notion that equal volumes of different gases may contain the same number of ultimate particles at equal temperature and pressure. however. its author simply drawing the same conclusions from the same premises. It has npt been thought necessary to reprint the letter of Ampere to Berthollet (Annales de Chimie. J. accepts both Dalton's experiments. and characteristically concludes by doubting the accuracy of Gay-Lussac's Avogadro. The bably be found more in the case of English version of the French originals will profaithful than elegant. 90. Gay-Lussac's important experimental work on the combining volumes of gases then shows the necessity of a simple relation between the ultimate particles of gases and their volumes. .

.

each surrounded with an atmosphere of heat. probably. EXTRACTS FROM A NEW SYSTEM OF CHEMICAL PHILOSOPHY. No two elastic fluids. repelling each other through the medium of those atmospheres. must be the same under the same pressure It is and temperature. therefore. having the same weight as the two original measures . PART BY JOHN DALTON. I. (pp. Suppose. they would form nearly two measures of nitrous gas. but the number of ultimate particles could at most be one half of that before the union. (1808). and in a state of equili- .) 3. have the same number of particles. evident the number of ultimate : particles or mole- cules in a given weight or volume of one gas is not the same as in another for. either in the same volume or the same weight. tides of all The quantity of heat belonging to the ultimate parelastic fluids.FOUNDATIONS OF THE MOLECULAR THEORY. i. and could be instantly united chemically. a given volume of any elastic fluid to be constituted of particles. 70-72. then. I. if equal measures of azotic and oxygenous gases were mixed.

will take place. I . is this. is demonstrated. as it appears to me. the space it occupies in the state of a pure elastic fluid . proposition. heat query the change that would take place The only consequence of this last supposition ? answer that can be given.) my present views on the which are somewhat different from what they were when the theory was announced. to ascertain whether the atoms or I By the size or volume of an ultimate particle. in ished. in this sense the bulk of the particle signifies the bulk of the supposed impenetrable nucleus. my enquiries into necessary. and the external pressure will therefore effect a proportionate condensation in the volume of air neither an increase nor diminution in the quantity of heat around : each molecule. as many have. or as it may now be called. the nature of elastic In prosecuting fluids. perience has diffused. or around the whole. (pp. that by some sudden change each molecule of air was endued with a stronger . mixed gases. Hence the truth of the supposition. brium under the pressure of a constant force. 187-189. also at the temperature of the surrounding bodies suppose further. pressure. I had a confused idea. such as the earth's atmosphere. The particles will condense their respective atmospheres of heat. in consequence of the fresh lights which succeeding exI shall now proceed mixed to give subject of gases. II. if ultimate particles of the different gases are of the same size or volume in like circumstances of temperature and soon perceived it was possible. by which their mutual repulsion will be diminaffinity for . together with that of its surrounding repulsive atmoAt the time I formed the theory of sphere of heat.6 Dalton. I mean in this place.

: every species of pure elastic fluid has its particles globular and all of a size . that we had no data from which But from a train of reasonthe question could be solved. ing. .New System of Chemical Philosophy. that the particles of elastic fluids are all of the same size . the pressure That and temperature being the same. I became con- vinced that different gases have not their particles of the same size and that the following may be adopted as a : maxim. at this time. or if not. till some reason appears to the contrary namely. 7 suppose. but that no two species agree in the size of their particles. that a given volume of oxygenous gas contains just as many particles as the same volume of hydrogenous . similar to that exhibited at page 71.

expands substances. while Similarly. QUEST O ANCES. and it the cause which modifies their special properties. BY M. but the dilata- solids have hitherto presented no only those of elastic fluids which are regularity. II. and which no longer follow any regular law. (1809). and that the contraction of volume which they experience on combination also follows a * Memoires de la Societe d'Arcueil. there- tions of liquids and and it is fore. 2. GAY-LUSSAC. liquid. whether in the solid. pp. heat it would be equal all for all elastic fluids. that bodies under similar At least. the effects of which are regular. by showing that these substances combine amongst themselves in very simple proportions. The same pressure applied to all solid or liquid substances would produce a diminution of volume differing in each case. . as in gases. it is conditions obey simple and regular laws. MEMOIR ON THE COMBINATION OF GASEOUS SUBSTANCES WITH EACH OTHER.Gay-Lussac.* '. or gaseous appear to be modified by this force (so variable in its intensity). Read before the Philomathic Society ^\st December 1808. my intention to make known some new properties in gases. appears that it is only when the attraction is entirely destroyed. equal and independent of the nature of each gas. possess properties which are independent of the force of cohesion but they also possess others which state. . The attraction of the molecules in solids and liquids is. 207-234.

two. Such is the state of the * Dalton has been led to this idea by systematic considerations . one atom of the one unites with one. idea advanced by several very distinguished chemists that we are perhaps not far removed from the time when we shall be able to submit the bulk of chemical phenomena to calculation. M.Combination of Gaseous Substances. three. 213. or Dalton has advanced the idea that compounds of two bodies are formed in such a way that elasticity.* It would follow from this mode of looking at compounds that they are formed in constant proportions. 9 I hope by this means to give a proof of an regular law. and one much are formed in discussed amongst chemists. p. insolubility. the existence of intermediate bodies being excluded. It is a very important question in itself. is of opinion that the metals are susceptible of only two degrees of oxidation. 6. he has seen himself forced to entertain principles contrary to physics in order to reduce to two oxides all those which the same metal sometimes away by presents. on the other hand reasoning from general considerations and his own ex- periments variable special that compounds such as proportions. but led this seductive theory. Berthollet has already strongly opposed it in the Introduction he has written to Thomson's Chemistry. and one may see from his work. or more atoms of the other. M. are always formed in very unless they are determined by crystallisation. Proust. who appears first to have fixed his attention on this subject. a minimum and a maximum . Berthollet thinks. . that his researches have no connection with mine. but M. to ascertain if compounds all sorts of proportions. A New System of Chemical Philosophy. Lastly. and from that of Thomson. and in this respect Dalton's theory would resemble that of M. Vol. Proust. and we shall see that in reality it is not entirely exact. causes.

It may. the first gas will then be in excess with regard to the second. I prepared fluoboric. and there will result a salt with excess of base. If carbonic gas is brought into contact with ammonia gas. composed of 100 of fluoboric gas and 200 of ammonia gas. which M. now proceed it is still very far from hope that the facts which I facts which had entirely escaped . I have made the following experiments. and the other gas is then passed in. there is always formed a sub-carbonate composed of 100 parts of carbonic gas and 200 of ammonia equal volumes of gas. but I to set forth. whether one or other of gas. from the exact ratio of TOO of oxygen to 200 of hydrogen. however. Thenard and I particular gas which we obtained with vitreous boracic acid. by passing it sometimes first. and that the salt formed is neutral. we begin by first putting the ammonia gas into the and then admitting the fluoboric gas in single bubbles. But if tube.* muriatic. and made them combine successively with ammonia 100 parts of muriatic gas saturate precisely 100 parts of ammonia gas.] . Berhave given the name of fluoboric gas to that by distilling pure fluoride of lime * M. When the acidt gas is put first into the graduated tube. be proved that neutral carbonate of ammonia would be composed of each of these components. and carbonic gases.io question receiving Gay-Lussac. sometimes second into the tube. on the contrary. unites in two proportions with ammonia gas. it is found that equal volumes of the two condense. Suspecting. will contribute to its elucidation. M. t ["Alkaline" in the original. Fluoboric gas. and the salt which is formed from them is perfectly neutral. the notice of chemists. now under its discussion solution. the gases is in excess. Humboldt and I had determined for the proportions of water. that other gases might also combine in simple ratios.

Accordingly. and from this we that if all acids and all alkalis could be obtained in the gaseous state.34 parts by weight of carbonic gas and 26. Now. 28.Combination of Gaseous Substances. 100. and since we can only obtain it through the intervention of water. It is much form of ammonia may suspect gas equal to their own . obtained by passing carbonic gas into the sub-carbonate.81 of carbonic acid. and that the ammonia can only exist through the medium of water. if we suppose it to be composed from their of equal volumes of its components. carbonic acids take exactly their and two take twice very remarkable to see acids so different from one another neutralise a volume to sub-salts. contains by weight 71.66 of ammonia gas. we find that it known specific gravity. 1 1 who has analysed this salt. whether we obtain a neutral salt or a sub-salt. fluoboric. that muriatic. found that it was composed of 73. If the neutral carbonate of by the mixture of of one gas as of the other would be absorbed . as much come neutral carbonate of the elasticity of the carbonic acid. we must conclude that it is the affinity of this liquid which competes with that of the ammonia to over- ammonia could be formed carbonic gas and ammonia gas. and own volume of ammonia that the last Thus we may conclude gas to form neutral as salts. their elements combine in simple ratios which may be considered as limits to their proportions.19 of ammonia. neutrality would result from the combination of equal volumes of acid and alkali. if we accept the specific gravity of f X OF THE (UNI V ^ .0 a proportion differing only slightly from the preceding. thollet. It is not less remarkable that.

0 Muriatic acid. Berthollet 100 of ammonia. allowance having been for the water contained in muriatic acid. we contains sub-carbonate of ammonia Ammonia.3 43. 100. muriatic.81 TOO.00 and the neutral carbonate Ammonia. we must only take three-fourths of the density acid. muriatic acid determined by those of carbonic gas and and Arago. we composed of find that M.65 100. some * fresh proofs. muriatic gas contains one-fourth As its weight of water. easy from the preceding results to ascertain the and carbonic since acids. 254.0 Carbonic acid.6 28. oo Ammonia. made We might even now conclude that gases combine with each other in very simple ratios but I shall still give .19 71.7 a proportion very far from that of M. 100. for these three gases saturate the volume of ammonia gas.0 Carbonic acid. 100. find that In the same way. 213 of acid.OO It is ratios of the capacity of fluoboric. 160. Biot and myself. 127.02 100.35 61. for that of real muriatic . their relative capacities will same be inversely as their densities.98 56.1 2 Gay-Lussac. Biot dry muriate of ammonia is 38.* and ammonia given by MM.

Combination of Gaseous Substances.

1

3

According to the experiments of M. Amedee Berthollet,

ammonia

is

composed of
100 of nitrogen,

300 of hydrogen,
by volume. I have found
sulphuric acid
is

of the Societe d'Arcueil) that composed of
(ist vol.

100 of sulphurous

gas,

50 of oxygen

gas.

When a mixture of 50 parts of oxygen and 100 of carbonic oxide- (formed by the distillation of oxide of zinc with strongly calcined charcoal) is inflamed, these two
gases are destroyed and their place taken by 100 parts of carbonic acid gas. Consequently carbonic acid may

be considered

as being

composed of

100 of carbonic oxide gas,

50 of oxygen gas. from the analysis of various compounds of Davy, nitrogen with oxygen, has found the following proportions

by weight

:

Nitrogen.

Oxygen.

Nitrous oxide Nitrous gas Nitric acid
-

-

-

63.30
44.05 29.50

36.70
55.95

-

-

70.50

Reducing these proportions to volumes
Nitrogen.

we

find
Oxygen.

Nitrous oxide

-

-

100 100

49.5

Nitrous gas Nitric acid

108.9

100

204.7

and the last of these proportions differ only from 100 to 50, and 100 to 200 it is only the slightly second which diverges somewhat from 100 to 100. The difference, however, is not very great, and is such as we might expect in experiments of this sort; and I have
first
;

The

assured myself that

it

is

actually

nil.

On

burning the

14

Gay-Lussac.

in 100 parts by there remained over exactly 50 gas, parts of nitrogen, the weight of which, deducted from that of the nitrous gas (determined with great care by M.

new combustible substance from potash

volume of nitrous

Berard at Arcueil), yields as result that this gas is composed of equal parts by volume of nitrogen and oxygen. We may then admit the following numbers for the proportions by volume of the compounds of nitrogen with

oxygen

:

Nitrogen.

Oxygen.

Nitrous oxide

-

100 100
100

Nitrous gas Nitric acid

50 100

200

From my experiments, which those of M. Chenevix, oxygenated
posed by weight of

very little from muriatic acid * is comdiffer

Oxygen

-

22.92 77.08

Muriatic acid

Converting these quantities into volumes, we find that

oxygenated muriatic acid
Muriatic gas

is
-

formed of
300.0
103.2
-

Oxygen gas
a proportion very nearly Muriatic gas

-

Oxygen gas
*

300 ioof

[Chlorine.]

f In the proportion by weight of oxygenated muriatic acid, the muriatic acid is supposed to be free from water, whilst in the proportion by volume it is supposed to be combined with a fourth of its weight of water, which, since the reading of this paper, M. Thenard and I have proved to be absolutely necessary for its existBut since the simple ratio of 300 of acid ence in the gaseous state. to loo of oxygen cannot be due to chance, we must conclude that water by combining with dry muriatic acid to form ordinary muriatic We should be acid does not sensibly change its specific gravity. led to the same conclusion from the consideration that the specific

Combination of Gaseous Substances.

1

5

Thus it appears evident to me that gases always combine in the simplest proportions when they act on one another ; and we have seen in reality in all the preceding
examples that the
i

ratio of

combination

is i

to

i, i

to

2,

or

very important to observe that in considering there is no simple and finite relation between the weights
to 3.
It is

elements of any one
a second

compound it is only when compound between the same elements
;

there

is

that the
is

new proportion
multiple of the

of the element that has been added
first

a

Gases, on the contrary, in quantity. whatever proportions they may combine, always give rise to compounds whose elements by volume are multiples
of each other.
only, however, do gases combine in very simple proportions, as we have just seen, but the apparent con-

Not

volume which they experience on combination has also a simple relation to the volume of the gases, or at least to that of one of them.
traction of
I

have

said, following

M.

Berthollet, that 100 parts of

carbonic oxide gas, prepared by distilling oxide of zinc and strongly calcined charcoal, produce 100 parts of car-

bonic gas on combining with 50 of oxygen. It follows from this that the apparent contraction of the two gases
is

The

volume of oxygen gas added. of carbonic gas is thus equal to that of cardensity bonic oxide gas plus half the density of oxygen gas ; or, conversely, the density of carbonic oxide gas is equal to
precisely equal to the
that

of carbonic

gas,

minus half that of oxygen

gas.

Accordingly, taking the density of air as unity,

we

find

gravity of oxygenated muriatic acid, which from our experiments contains no water, is exactly the same as that obtained by adding the

density of oxygen gas to three times that of muriatic gas, and taking M. Thenard and I have also found that oxygenhalf of this sum.

ated muriatic gas contains precisely half
that
it

its

volume of oxygen, and
of hydrogen.

can destroy in consequence

its

own volume

j
x.

OF THE

^w

(XJNIVERSITTT) S OF

265.. and Richter.62 of oxygen.265. acid. and carbonic oxide of 42. sulphurous gas weighs 2. it takes 150 parts to produce sulphuric fact. tne density of air being taken as unity. we find that if sulphur ta\kes 100 parts of oxygen to produce sulphurous acid. is composed of 100 parts by weight of sulphur and 138 of oxygen.10359 there will remain 2. or 1. 6 3359 oxygen. Bucholz. consequently oxygen gas doubles its volume on forming carbonic oxide gas with carbon.9569 experimentally determined by Cruickshanks. this quantity contains 3. Consequently the weight of a certain quantity of sulphuric acid should be the same as that of 2 parts of sulphurous acid and i of oxygen gas. and i of oxygen gas. besides. Klaproth. As a matter of we find that sulphuric acid. it is easy to calculate the proportion In this way we find that carbonic gas composed of 27. We know. according to Kirwan. the density of carbonic oxide gas to be 0.38 of carbon. according to the experi- ments of MM. .9678. 72. and so does carbonic gas on being passed over red-hot charcoal. Pursuing a similar course. and the density of the latter is well known.1 6 Gay-Lussac. 57. instead of 0. On the other hand sulphuric acid is composed of 2 parts by volume of sulphurous gas.e. P^ us I 10 359 = - seeing that. 2 x 2. Since oxygen produces an equal volume of carbonic gas.26653 of oxygen.99 of carbon. and if we subtract from it 1.01 of oxygen. i. of is its elements.16294 for the weight of oxygen in 2 parts of sulphurous acid. But from the proportion of 100 of sulphur to 138 of 5'. that a given volume of oxygen produces an equal volume of carbonic acid .08147 for the weight of oxygen contained in i part.

as appears probable. 92.* it would be necessary to the density of sulphurous gas. and that 50 have still to be added to convert it into sulphuric acid.0 of oxygen. I have * In order to remove these differences make new experiments on found. as sulphurous gas can be used to analyse sulphuretted if its proportions are well known. we adopting the preceding proportions for sulphuric allow. find that this acid is composed of we should 100. able conditions. from 1. on heating cinnabar in oxygen gas. 95. that 100 of sulphur- ous gas contain 100 of oxygen gas. But acid. and on the union of sulphurous gas with ammonia gas.00 of sulphur. on the direct union of oxygen gas with sulphur to see if there is contraction. which could only be made in presence of water. would be 2.02 of oxygen. especially the last. instead of 2. on the same suppositions. that 100 parts It also appeared as of this gas only produce 93 of sulphurous gas. hydrogen gas. if less sulphurous gas than ammonia gas was necessary to form a But as these experiments were not made under suitneutral salt. B . Its specific gravity calculated and referred to that of air. if. necessary. we shall obtain for the proportions in sulphurous acid 100. intend to repeat them and determine exactly all the conditions This is all the more before drawing any conclusion from them. only experiences a diminution of a fiftieth of its volume. and this would probably be nil if the data I have employed were more exact.Combination of Gaseous Substances. the sulphurous gas decomposing and precipitating I sulphur immediately on being mixed with the ammonia gas. On this last supposition. 17 Now as this last quantity only differs by 2 per cent.2650 as Kirwan found directly.10359. which represents the weight of i part of oxygen gas.30314. it must be concluded that oxygen gas. using Kirwan's value for the specific gravity of sulphurous gas. in combining with sulphur to form sulphurous gas. it is true.00 of sulphur.

and 102 parts of nitrogen remain. would be very nearly equal in volume to the nitrous oxide employed. that the apparent contraction is precisely equal to the volume of oxygen gas added. and exactly 250 parts of nitrogen remain.0 of oxygen. But it is easy to show. and a little of the latter gas which has escaped The residue. Since the latter is composed. Consequently phosphorus should take up twice as much state into oxygen to become phosphorous acid. it follows that phosphorous acid should contain i oo. water and phosphoric acid are formed. seeing that both have nearly the same specific gravity.52092.61414. on passing the electric spark combustion. including that quantity which is almost always mixed with the hydrogen. while that given by Davy is 1. calculated on this hypothesis. from some of Davy's . Phosphorus is very closely connected with sulphur. according to Rose. In the first case. through a mixture of 100 parts of phosphuretted hydrogen and 250 of nitrous oxide.0 of phosphorus. of 114.5 of nitrous oxide the hydrogen is destroyed. is 1.0 of oxygen.o of phosphorus.1 8 Gay-Lussac. another evident proof that the apparent contraction of the elements of nitrous oxide is equal to the whole volume . We experiments. after making all corrections. and 100 of oxygen gas to form nitrous gas. as to pass from this phosphoric acid. Similarly. the contraction is a little greater than the volume of oxygen added for the specific gravity of nitrous oxide. have seen that 100 parts of nitrogen gas take 50 parts of oxygen gas to form nitrous oxide. 100. On passing the electric spark through a mixture of 100 parts of hydrogen and 97. 76.

we of 10 to find instead of this a ratio 1 6. Assuming that the contraction of volume of the two gases is only equal to the whole volume of oxygen added. we find only 1488 for the volume occupied by water when it is converted into steam . Saussure found that the density of water vapour is to that of air as 10 is to 14. while that determined directly is 1. that it is composed of equal parts of oxygen and nitrogen. we should have 1700.5. gas appears. but that calculated from the ratio 10 to 16 is much more in harmony with the results of experiment. but I shall mention several circumstances that render it very probable. This difference. Trales found by direct experiment that the ratio of the density of watervapour to air is 10 to 14. but adopting the ratio of 10 to 1 6.6. its gravity referred to that of air should be 1. is 1. calculated on the assumption of the ratio 10 to 14. it has a very strong analogy in favour. The apparent contraction of the elements of nitrous If we admit. a volume 1728 times as great. is a little greater than the observed refraction. we do know. Ammonia gas is composed of three parts by volume of . and the authority of a physicist so distinguished as Saussure.Combination of Gaseous Substances. These.52092. the refraction of water-vapour. .038. secondly. Finally. adopting Saussure's ratio. its Firstly. from the experiments of Watt. are the considerations which go to make the ratio 10 to 1 6 very probable. Now. 19 specific From this circumstance. as I have shown. although we do not know very exactly the volume occupied by water on passing into the elastic state. we find that its density. i. calculated on the assumption that there is no contraction. of oxygen added. on the other hand. M. then..e. that a cubic inch of water produces nearly a cubic foot of steam. to be nil. instead of 10 to 14 thirdly. would seem to be enough to make us reject the assumption I have just made.036.

volume of the I nitrogen. see. Admitting that the apparent contraction of the two gases is half the whole volume. we shall see them vanish entirely. It follows from this that in all the muriates.2O Gay-Lussac. we find 2. Recalling the great law of chemical affinity. that is the gas should be lighter than oxygen. or rather with the volume of one of them.596. that the apparent contraction of its elements is precisely half the total volume. have already proved that oxygenated muriatic gas is composed of 300 parts of muriatic gas and 100 of oxygen gas. if we pass oxygenated muriatic gas over copper. But if we suppose the apparent contraction to be half of the whole volume. from these various examples. and a little oxide of copper is precipitated. by this almost perfect concordance. it is difficult to conceive why carbonic oxide Indeed. would be the same for carbonates and fluorides.594 for the to air Thus it is proved. and its density compared is 0. as in oxygenated muriatic acid. that the contraction experienced by two gases on combination is We in almost exact relation with their volume.468 for its I have also assured density. because the metals. . and it is probable that. or rather double the density. myself by several experiments that the proportions of its elements are such that it forms neutral salts with the For example. we find 0. and by experiment 2.470. on undertaking new researches. the acid It reduced to volume is thrice the oxygen. there is formed a slightly acid green muriate. then. exist Only very slight differences between the densities of compounds obtained by calculation and those given by experiment. hydrogen and one of nitrogen. that every combination involves an approximation of the elementary molecules. salt cannot be obtained perfectly neutral. the acids of which have for equal volumes the same saturation capacity as muriatic acid.

and we might cite several gaseous combinations. may stand with these suppositions. we should conclude. by assuming.Combination of Gaseous Substances. although there is not only no diminution of volume. and that the affinity which unites its elements is very being formed relation Nevertheless. the constituent molecules of which would be brought very close together. there is no nitrous oxide and oxygen. Berthollet to assume the existence of hydrogen in this gas. make make that supposition for carbonic acid. as a truth founded on 'a OF THE UNIVERsi'i . we may also carbonic oxide. 21 principal reason which has led M. and that the apparent condensation would then be equal to the whole volume of the gaseous carbon.Otherwise it would be necessary to suppose that if carbon were in the gaseous state it would combine in equal volumes (or in any other proportion) with oxygen. for instance. But if we powerful. if we admitted an immediate between the condensation of the elements and the condensation of volume. contrary to experiment. there would be dilatation. we must admit. We know too that carbonic gas represents an exactly equal volume of oxygen. but even a for example. for 100 parts of nitrous oxide and 50 of oxygen would produce 200 of nitrous gas. Such. from supposing that the approximation of the elementary molecules is represented in gases by the diminution of volume which they suffer on combination. is dilatation. and in the second. This supposition is not always true. or from In the first case. which serve to make it conceivable that oxygen can proonly duce a compound lighter than itself by combining with a it However solid substance. 100 parts of gaseous carbon would produce 100 this it for parts of the gas on combining with 50 parts of oxygen. that there is no condensation. and thus explain its low But it seems to me that the difficulty arises density. diminution of volume. whether we consider as directly from nitrogen and oxygen. it nitrous gas.

it is sufficient to convert the oxygen into volumes and also the combustible. For example. and as we know the proportion of oxygen taken up by each com- bustible substance in the solid or liquid state. i . i to J. that the condensation of the molecules of two combining substances. mercury is susceptible of two degrees we may compare the first one to nitrous oxide. according to MM.40. 100 parts of mercury absorb 4. under the condition that its vapour shall be equal to the volume of oxygen. of mercury reduced to vapour should therefore occupy of oxidation. which reduced to These TOO parts gas would occupy a space of 8.to 2.. in particular of two gases. observation that the gaseous combustibles comis bine with oxygen in the simple ratios of i to i. viz. all combustible substances to be in the gaseous state. since great the other The we often see that whilst one is very very small or even nil. Fourcroy and Thenard. I shall not discuss more of these determinations.22 great Gay-L ussac. as the experiments of which I have just given an account lead me to the discussion of these two opinions.16. or else double or half this value. or else half. or at least to approxi- For if we suppose closely to that determination. or twice as much. has no immediate relation to the condensation of volume. and I shall conclude besides easy to multiply them. 12. Now. and to the gaseous state assumes a volume 961 times as great. number of observations.01 greater than that that the metal on passing from the liquid because they are only based on analogies. the density of mercury vapour We is thence conclude that of oxygen. . and twice the space.20. it is this Memoir by examining if compounds are formed in con- stant or variable proportions. can lead us to determine the density of the vapours of combustible substances. 16. a mate specified volume of each would absorb an equal volume of oxygen.

or with a greater tions number. on the other hand. that combinaare formed from atom to atom. We must first of all admit. or with two. all of which glass. alloys.] 2.] . whatever their number and ratio may be. which tend to produce compounds in fixed proportions. apart insolubility. and t that the sub-carbonate of Wollaston. therefore. p. favour. Berthollet. 23 According to Dalton's ingenious idea. p. But M. The numerous results I have brought forward in this Memoir are also very favourable to the theory. chemical action is exercised indefinitely in a continuous ( manner between the molecules of substances. f [See Alembic Club Reprints. are compounds with very on the variable proportions. potash contains. it is easy to reconcile them. 41. insists principally identity of the force duces chemical compounds and solutions. cites in proof of his opinion the acid sulphates. No. with M. But then we must admit at the same time that. Thomson * has found that super-oxalate of potash contains twice as much is necessary to saturate the alkali. and he which pro-| a large . that facts Each of number of these two opinions in its has. who thinks that combinations are made continuously. No. and elasticity.Combination of Gaseous Substances. mixtures of various liquids. but although they are apparently utterly opposed. 2. Thomson and Wollaston have indeed described experiments which appear to confirm this theory. the various compounds which two substances can form would be produced by the union of one molecule of the one with one molecule of the other. but always without intermediate compounds. Berthollet. chemical action from * [See Alembic Club Reprints. 35. and that 'in general we can obtain compounds with very variable proportions. cohesion. twice as much alkali as is necessary to acid as saturate the acid.

or at most 3. unless these proportions are deter- mined by special circumstances. and they form a new proof that it is only in the gaseous state that sub- stances are in the laws. the other is i. and give rise in general to compounds with very variable proportions. and this The might perhaps be the true manner of determining it. and that compounds are thus produced which In this way we reconcile the separate out more easily. nor when we consider weights. they would salts. contraction of volume suffered by gases on combination is also very simply related to the volume of one of them. I have shown in this Memoir that the compounds of gaseous substances with each other are always formed in very simple ratios. or 2. Conclusion. exerted more powerfully when the elements are in simple ratios or in multiple proportions among themselves. and this property likewise is peculiar to The apparent gaseous substances. . and it is probable that if all acids and alkalies were in the elastic state. all combine in equal volumes to produce neutral capacity of saturation of acids and alkalies measured by volume would then be the same. so that representing one of the terms by unity. two opinions. and maintain the great chemical law. that whenever two substances are in presence of each other they act in their sphere of activity according to their masses. These ratios by volume are not observed with solid or liquid substances. It is same circumstances and obey regular remarkable to see that ammonia gas neutralises exactly its own volume of gaseous acids.24 is Gay-Lussac.

BY JOHN DALTON. 25 3. . as i to 2. 555~559-) observations on nitric acid. to 3. and abandoned as untenable . which. In fact. or in measures some simple relation one to another. Gay Lussac could not but see (page 188. is the nature of the combinations below No answer is given to 3. as he has revived the notion. though inadequacy. constituted of equal measures of azote and oxygen. Gay He contends that one measure of oxygenous gas unites to two measures of nitrous gas to form nitric acid. have been made by Lussac. (1810). according to Gay Lussac. PART II. this what. in the 2d vol. Now I have shewn that i measure of oxygen may be combined with 1. of nitrous gas ? but the opinion is founded upon an hypothesis that all elastic fluids that have i combine in equal measures. or with any intermediate quantity whatever. then. Nitrous gas is. of this work) that a similar hypothesis had been entertained by me. and to three measures to form nitrous acid. except universal. : and above . according to circumstances. of the Memoires d'Arcueil. his notion of measures is \ analogous to mine of atoms and if it could be proved that all elastic fluids have the same number of atoms in the same volume. when com- I do not doubt but he soon see its .3 of nitrous gas. SOME and the other com- pounds of azote and oxygen. which he seems to allow 2. EXTRACT FROM A NEW SYSTEM OF CHEMICAL PHILOSOPHY. two hypotheses would be the same. pp. j &c. Part i. 3. I shall make a few will observations upon it. and his applies only to elastic 2. the | that mine is fluids. however. 3. or with 3. 2 to &c. (Appendix. or numbers that are as i.New System of Chemical Philosophy.5.

and the particulars of the experiment. occupy the Dalton. and finds them after the rate of TOO azote to 108.05 weight. it may farther i In be added. he shews by burning potassium in nitrous gas. There is another point of view in which this theory of Gay Lussac is unfortunate. when 100 measuresafforded just 50 of azote. must give results wide of the truth. forms 2 of ammonia and i measure . .9 oxygen. Now this will apply to Gay gas for their saturation. in i measure of azote regard to ammonia and nitrous gas with 3 of hydrogen. ammonia is formed of i measure of azote and 3 of hydrogen. that to 3.26 bined. of azote with i of oxygen.5. taking the specific and Arago. require 75 oxygen the hydrogen. forms 2 of nitrous gas : now. instead of 50. azote. hence. made with the most scrupulous attention to accuracy. 75 ox yg en or I0 Here either the theory of Gay Lussac. Lussac's theory in a very direct manner . 120 nitrous gas should contain should contain 62. as hereafter shall appear. Dr. however. But that Davy has overrated the oxygen 12 per cent. in nitrous gas. Davy. it follows.95 oxygen by He converts these into volumes. There is. He quotes Davy. regard to neither is ammonia too. are not This one result is to stand against the mean of three experiments of Davy. for. and 55. and Henry. gives 100 azote to 112 gravities according to Biot it oxygen. according to him. or the experience > ammonia to saturate of Dr. mentioned. who found 44. .. a mistake in this if properly reduced. same volume as when free. . nor is the rate of azote to hydrogen the volume of ammonia doubled by decomposition. and may or may not be more correct. The degree of purity of the nitrous gas. Henry. Henry's of ammonia embraces that of nitrous gas also analysis he finds TOO measures of ammonia require 120 of nitrous . that 100 . condensed into a volume of 2 then. according to the experiments of Berthollet. to which may be added my own.

the most exact experiments i I have ever made. perhaps. but here. and that 100 azote require about 120 oxygen to form nitrous gas. further than the unavoidable errors of experiments might produce . and thus the great chemical law would be preserved. that 100 measures of azote require about 250 hydrogen to form ammonia. my he will perceive that the hydrogen of the former would unite to the oxygen of the latter. namely. leaving no excess of either. is inaccuracy of our experiments. or twice as much . I believe. when they appear to do so. and form water. or with one half as much. The truth is. If Gay Lussac adopt conclusions. but no one of these combinations takes place. it is owing to the In no case.97 hydrogen to oxygen. gave 1. . 27 according to a well established principle in chemistry. i measure of oxygen ought to combine with 3 of hydrogen. than in that of i measure of oxygen to 2 of hydrogen . there a nearer approach to mathematical exactness. that' gases do not unite in equal or exact measures in any one instance .New System of Chemical Philosophy.

MoUcule inttgrante (translated "integral molecule") means molecule in general.] . Molecule elementaire (translated "elementary molecule ") stands for the atom of an elementary substance. AVOGADRO * I. t [Avogadro has been accused of inconsistency in his use of the term " molecule.MASSES OF THE ELEMENTARY MOLECULES OF BODIES. and that when the result of the union is a gas. but is usually applied only to compounds. It must then be admitted that very simple relations also exist between the volumes of gaseous substances and the numbers of simple or compound molecules which form * Journal de Physique. 4. has shown in an interesting de la Societe* d'Arcueil. and on the number of composite molecules which result.28 Avogadro. Memoir (Memoires MGAY-LUSSAC . pp. (1811). BY A. as MoUcule (translated " molecule ") without qualification means in modern chemical phraseology either atom or molecttle. But the quantitative proportions of sub- stances in compounds seem only to depend on the relative number of molecules t which combine. Tome gases always unite in a very simple proportion by volume.) that its components. 58-76. LXXIII. AND THE PROPORTIONS IN WHICH THEY ENTER INTO THESE COMPOUNDS. ESSAY ON A MANNER OF DETERMINING THE RELATIVE. its volume also is very simply related to those of II." but a careful perusal of his paper will show that he uses follows : it with its qualifying adjectives quite consistently. is MoUcule constitiiante (translated "constituent molecule") em- ployed to denote the molecule of an elementary substance.

it would scarcely be possible to conceive that the law regulating the distance of molecules could give in all cases relations so simple as those which the facts just detailed compel us to acknowledge between the volume and the number of molecules. On the other hand. same caloric only results in producing a greater or less con- densation of this quantity around the molecules. and that the greater or less attraction for this. nection. it is true. has proposed a hypothesis directly opposed to ing namely. without the number of molecules contained in a given volume being different. But in our present ignorance of the manner in which this attraction is of the molecules for caloric is exerted. the supposition that the number of integral molecules in any gases is always the same for equal volumes. 29 conis The first hypothesis to present itself in this and apparently even the only admissible one. consequently. without the distance between the molecules varythat their varying attraction for caloric .Relative Masses of Elementary Molecules. that the quantity of caloric is always the for the molecules of all bodies whatsoever in the gaseous state. there of the one nothing to decide us a priori in favour of these hypotheses rather than the other . and. it is very well conceivable that the molecules of gases being at such a distance mutual attraction cannot be exercised. or always proportional to the volumes. and thus varying the distance between the molecules themselves. if we were to suppose that the number of molecules contained in a given volume were different for different gases. and we should rather be inclined to adopt a neutral hypothesis. which would make the distance between the molecules and the quantities of caloric vary according (UNIVERSITY) \'^S . them. Dalton. Indeed. in other words. or. without ing the atmosphere formed by this fluid having any greater extent in the one case than in the other. their may be limited to condensa greater or smaller quantity around them.

For example. ammonia will result from the union of one molecule of nitrogen with three of hydrogen. since the numbers 1. Setting out from this hypothesis. more exactly. and the ratio of the two numbers consequently represents the ratio between the masses of equal volumes of these two gases. nitrous oxide from one molecule of oxygen with two of nitrogen.07321 express the densities of the two gases oxygen and hydrogen compared to that of atmospheric air as unity.10359 an d 0. as 15.074 to i. Gay-Lussac for the elements of ammonia.238. Thus the mass of the molecule of oxygen will be about 15 times that of the molecule of hydrogen. In the same way the mass of the molecule of nitrogen will be to that of hydrogen as 0. that is. to i. it will also represent on our hypothesis the ratio of the masses of their molecules. nitrous gas . On the other hand. nitrous gas. Similarly. is and compound given at once by the ratio of the volumes of the gases that form it. which unknown would appear to be otherwise inexplicable. were it not that the hypothesis we have proposed is based on that simplicity of relation between the volumes of gases on combination. or. relative number compounds for the ratios of the of these molecules masses of the mole- cules are then the same as those of the densities of the different gases at equal temperature the relative number of molecules in a and pressure. it is apparent that we have the means of determining very easily the relative masses of the molecules of substances obtainable in the gaseous in state. nitrous oxide. according to the proportions by volume established by M. and the .3O to Avogadro.96913 to 0. and nitric acid. or more exactly 13.07321. since is we know that the ratio of the in the formation of volumes of hydrogen and oxygen water 2 to i. just laws. it follows that water results from the union of each molecule of oxygen with two molecules of hydrogen. as 13.

or. For instance. There is composed of two or more elementary molecules should have its mass equal to the sum of the masses of these molecules and that in particular. the resulting compound. Gay-Lussac has shown. but are made up of a certain number of these molecules united by attraction to form a single one . the volume of water in the gaseous state is. the number of compound molecules should remain the same as the number of mole. the integral molesplits up into two or more parts (or integral molecules) composed of half. 3 1 from one molecule of nitrogen with one of oxygen. quarter. ing facts of this type in conformity with our hypothesis we suppose. on our hypothesis when a gas combines with two or more times its volume of another gas. namely. the cule which should result .e. what comes to the thing. must have a volume equal to that of the first of these gases. a consideration which appears at first sight to be opposed to the admission of our hypothesis with respect It seems that a molecule to compound substances. the molecules which are at such a distance : from each other that they cannot exercise their mutual action) are not formed of a solitary elementary molecule. in general. this is same of oxygen which enters into it. cules of the first substance. not actually the case. and further. Accordingly. II. twice as great as the volume Now.Relative Masses of Elementary Molecules. presents itself naturally enough that the constituent molecules of any simple gas whatever (i... if gaseous. and nitric acid from one of nitrogen with two of oxygen. that when molecules of another substance unite with the former to form a compound molecule. equal to that of the hydrogen instead of But a means of explainbeing equal to that of the oxygen. if in a compound one molecule of one substance unites with two or more molecules of another substance. as M. &c.

quartermolecules.* On reviewing the various compound gases most generally known. quarter.. which contains equal volumes of nitrogen and oxygen. &c. to number of elementary molecules going stituent form the con- substance. combined with half. &c. that is to say. &c.. two half-molecules of hydrogen. what is posed of a half-molecule of oxygen the same thing. In the volume of ammonia gas is M. &c. but it is possible that in other cases The possithe division might be into four. quadruple. bility of this division of compound molecules might have been conjectured a priori . I only find examples of duplication of the volume relatively to the volume of that one of the constituents which combines with one or more volumes of the other. has a volume equal to the sum of the two constituent gases. or. what comes to the same thing. Gaytwice that of the nitrogen which enters into it. of the second substance) . the number of constituent molecules of the second substance that ought to enter into comfirst molecule of the bination with one constituent molecule of the first sub- stance (or. we know molecule into two . and exactly what is necessary to satisfy the volume of the resulting gas. what it would have been if there had been no splitting-up.32 Avogadro. the integral molecule of water will be comwith one molecule. eight. double that of each of them. Lussac has also shown that the volume of nitrous oxide is equal to that of the nitrogen which forms part of it. would come to Thus. Thus in all these cases there must be a division of the same way. * . and consequently is twice that of the oxygen.. nitrous gas. Finally. We have already seen that the this for water. for example. combined with a number equal to this last of half-molecules. for otherwise the integral molecules of bodies composed of several substances with a relatively large number of molecules. so that the number of integral molecules of the compound becomes double.

on likely relative arbitrary to suppositions in as to the most number of molecules fix endeavoured it ratios compounds. according to the facts. nature had some means of bringing them back to the order of the latter. it is easy to see that the combination really reduces two different molecules to one. Dalton. there is another consideration which would seem to make us admit in some otherwise conceive cases the division in question . has between the masses of the molecules of simple substances. supposing well-founded. 33 have a mass excessive in comparison with the molecules We might therefore imagine that of simple substances. and the facts have pointed out to us the existence of such means. Our hypothesis.* if each compound molecule did not two molecules of the same nature. Besides. the diminution of volume on the combination of gases cannot of one of the gases split up into represent the approximation of their elementary molecules. and that there would be contraction by the whole volume division of the molecule. to assign the magnitude of compound molecules according to the c . puts us in a position to confirm or rectify his results from precise data. M.Relative Masses of Elementary Molecules. GayLussac clearly saw that. III. we cannot imagine that a new attraction could take place between the molecules of one But on the hypothesis of gas and those of the other. such as takes place in the formation of nitrous gas ? Supposing the molecules to remain at such a distance that the mutual attraction of those of each gas could not be exercised. The division of molecules on combination explains to us how these two things may be made inde- pendent of each other. for a real combination how could one between two gaseous substances uniting in equal volumes without condensation. and. above all.

2. 8|. or. but on account of this division it reduced to half. and from the ratio by weight of the two components. according to Dalton's evaluation. precisely the if have. it would follow that the mass of the molecule of oxygen would be to that of hydrogen as 7^ to i nearly. or more exactly 8. 42. which depend partly on the division of molecules entirely unsuspected by this physicist.537. namely. as 6 to i. This on our hypothesis is. No. always supposing that he had not set out from a different value for that of oxygen. so that in this respect Dalton's result approximately correct from the combination of two compensating errors. the error in the mass of the molecule of oxygen. and his neglect of the division of the molecule. volumes of the gaseous compounds.34 Avogadro. p. twice as great. and if he had taken elements same value for the quantities of the * In what follows I shall make use of the exposition of Dalton's ideas given in Thomson's System of Chemistry. as we saw. Dalton supposes that in nitrous gas the combination of nitrogen and oxygen is molecule to molecule we have seen on our hypothesis that this is actually the case. As for the molecule of water. it by Dalton. as 15 to i. that assigned to 0. if there were no division of the molecule into two . molecule to molecule. by the difference in the values for the comis position of water is .] . Thus Dalton supposes* that water is formed by the union of hydrogen and oxygen. [See Alembic Club Reprints. Thus Dalton would have found the same molecular : mass for nitrogen as we of hydrogen to be unity. its ratio mass ought to be roughly expressed by 15 +2= 17 (taking for unity that of hydrogen). as may also be found directly by dividing the density of aqueous vapour 0.625 (Gay-Lussac) by the density of hydrogen This mass only differs from 7. From this.0732.

Relative Masses of Elementary Molecules. partly corrects in this case also the error which would result from his other suppositions. same manner as the facts have given us. In the case of ammonia. he has made it 6 + 5 = 11. He makes it 6 + 2x5 = 1 6.. As according to us it is about - = 14. as ma Y also be deduced directly from the density of ammonia The division of the molecule. by the density of hydrogen. viz. But by supposing the molecule of oxygen to be less than half what we find. his neglect of the division of the molecule again makes his result approach ours. whereas hydrogen we have seen that one molecule of nitrogen unites with three molecules of hydrogen.07321. which does not enter gas. in nitrous gas 35 by weight. the relative number of molecules in nitrous oxide and in nitric acid. into Dalton's calculations.074+ i3-238 2 y diyiding 1. gas itself. whilst according to our method it should be2 obtained by dividing 1. He molecule of ammonia would be us it 5 + 1 = 6: according to should be ^ ^ = 8. Gay-Lussac's value for the density of nitrous oxide. 5 instead regards the molecule of nitrous. the density of nitrous gas according to GayDalton has likewise fixed in the Lussac. or more exactly 15.03636.52092. UNIVERSITY OF THE . According to him the hypothesis entirely at fault. by 0. whilst 13.119. and in the first case the same circumstance has rectified his result for the magnitude of the molecule. he has been obliged to make that of nitrogen also equal to less than half the value of we have assigned to it. Dalton's supposition as to the relative number of molecules in its composition is on our supposes nitrogen and to'be united in it molecule to molecule. or more exactly 8.

leaving the possibility of division out of account. whence it would follow. which on our hypothesis can give us at least conjectural information concerning the relative masses of the molecules and their We may now number in these compounds. that of hydrogen being taken as unity. i. the this last molecule would be 57.542. look at a few more compounds. and compare our results with the suppositions of Dalton. division into two. From Gay-Lussac's experiments (Societe d'Arcueil. and the density of nitrous acid gas would be 4.^6 density of air being taken But it is probable that there is at least another as unity. But this mode of combination can be referred to the preceding simpler forms by considering it as the result of the union of i molecule of oxygen with 3 of nitrous gas. . In nitrous acid we have another compound of two of the substances already spoken of. 5 of oxygen. what comes to the same thing. on our hypothesis. that its molecule should be composed of 3 molecules of nitrogen and volume). IV. which thus already includes the division of some of the molecules acid. All the compounds we have just discussed are produced by the union of one molecule of one of the components with one or more molecules of the other. or. same it appears that this acid is formed from i part by volume of oxygen and 3 of nitrous gas.. of oxygen which enter into that of nitrous Supposing there to be no other division.21267.e. with 3 molecules.36 Avogadro. of 3 parts of nitrogen and 5 of oxygen . and consequently a reduction of the density to half we must wait until this density has been mass of : determined by experiment. each composed of a half-molecule of oxygen and a half-molecule of nitrogen. in which the terms of the ratio between the number of molecules both differ from unity.

of dry sulphuric acid produced. made from the quantity Now it seems almost certain that ordinary sulphur contains hydrogen . and that the density of acid is sul- unity 2. If. or. which must have been con- added verted into water in the operation. instead of 138. namely. a source of error tending to increase the quantity of the radical. and that its specific gravity to weigh in favour assumption.53. that sulphuric acid is com- referred to air as posed of two parts by volume of sulphurous acid gas and one of oxygen. throwing the whole error on the analysis of sulphuric acid. on 'the con- we suppose it exact. instead of 2. we find that in sulphurous acid 100 parts of sulphur take 95. as the result of Gay-Lussac's experiments. Gay-Lussac has shown that if we assume that dry sulphuric acid is composed of 100 parts of sulphur and 138 of oxygen by weight. as the most recent work of chemists has established. and if we admit. diminish the quantity of The determination was oxygen. = 142. and consequently in sulphuric acid 95. I shall therefore . until the density of sulphurous acid gas has been confirmed or rectified by. then the volume of sulphurous acid is nearly equal to that of the oxygen which entered into on it .30314. suppose Kirwan's determination to be exact. fresh experiments.02+^ trary. 37 M. that there must have been in the deter- mination of the composition of sulphuric acid. has therefore been to the true weight of the radical.265 phurous gas (Kirwan's determination). the weight of this hydrogen. One consideration would appear of the first the analysis of sulphuric acid to be follows that sulphurous acid contains 92 of for 100 of sulphur. what is the same thing. and this equality would be exact if the bases If we which the calculation rests were the same.265. oxygen should be 2.Relative Masses of Elementary Molecules.02 of oxygen.

0967. If we adopt this density. ratio as the densities of the gases to The masses in. of these molecules combined. or as 31. instead of 92.e. that the volume of the sulphur as gas is half that of the sulphurous acid. which also contains new experiments on sulphur and phosphorus. and in sulphuric acid 167 instead of 138 . but perhaps this density of sulphurous acid.38 Avogadro. sulphurous acid should be analogous to [Erroneously 92. t In order now to determine the mass of the molecule of the sulphuric radical.51 . leads us to suppose that it is the same in this case also. and consequently also half that of the oxygen with which it combines.323 the density sulphur. is somewhat too low. the mass of the molecule of the sulphuric radical will be to that of One hydrogen as 2.02 in the original. i. On this supposition the density of sulphur gas 47. will be to that of oxygen as 100 to for ^^' 2 2 . of gaseous of the the molecules being according to our hypothesis same which they belong. according to Davy. taking that of air as unity. as we have said. where there is in general a doubling of the volume or halving of the molecule. In it he determines the density of sulphurous acid gas. Accordingly. will form sulphuric acid. it would be necessary to know what proportion by volume this radical in the gaseous state would bear to the oxygen in the formation of sulphurous acid. with two of oxygen. or rather of sulphuric radical. will form sulphurous acid (division of the molecule being left out of account).02 * of oxygen to 100 of sulphur. assume sulphurous acid to be composed of 95. and finds it * to be only 2. which gives new force to the above considerations.323 to 0. we find that in sulphurous acid 100 parts by weight of sulphur take in of oxygen. The analogy with other combinations already discussed. or which gives 2.] f This was written before I had seen the Memoir of Davy on oxymuriatic acid. and combined with yet another molecule of oxygen.73 to i. .07321.

will be equal to 31-73 + 2x15. and that its volume cases. by a similar calculation. and its molecule 27. if both were known For example.13. having regard to division. number of no The mole- cule of sulphurous acid. for we do not know whether there is further division of the molecule on * its formation. If. a result only slightly different from Kirwan's. Davy in the density of sulphurous acid gas.. nitric 39 acid.7. half. is I twice that of the gaseous radical.0645. must assume that suppose the molecule of sulphur to be nearly twice as great. As we know. that of hydrogen being taken as unity. viz. He finds nearly the same mass.9862. viz. As for the molecule of sulphuric acid. sulphuric acid having analogue amongst the nitrogen compounds. supposing Davy's determination for sulexactly. we this gas is the product of the union of one mole- cule of the radical with two at least of hydrogen..074 Qr ^^ ^ wQuld algo be obtained directly by dividing the density 2. as in so many other say at least with two molecules of hydrogen.4. as we its own volume of hydrogen combined with sulphur) is composed of one molecule of sulphur and one of hydrogen. which his experiments make equal to 1. with its regard to the relative molecules of constituents. Davy. This could be decided by the comparison of the specific gravities of sulphuretted hydrogen and sulphurous acid gas.Relative Masses of Elementary Molecules. ordinary sulphur were composed of one molecule of sulphuric radical and one of hydrogen. the density of the sulphuric radical would be 1. sulphuretted hydrogen would be composed of three molecules of hydrogen and one of radical. its quantity also must be added. 13. fixes it at about because he supposes the molecule of oxygen to be equal to about half our molecule. . using Dalton's hypothesis with respect to water. has made the same supposinumber of molecules of oxygen and radical in From his determination of the sulphurous and sulphuric acids. for instance. for if there were hydrogen already in ordinary sulphur. as known experiments on this substance indicate. or not* tions as to the relative Memoir alluded to. by taking as his starting-point the density of sulphuretted hydrogen. it cannot be determined. and by assuming that this gas (which contains. 13.265 f sulphurous acid gas by that of hydrogen gas.

08. There ought to be a little more oxygen in it if we suppose that phosphorus. bears to mass of the oxygen molecule a ratio which approaches that presented by these two substances on our hypothesis. to for according Gay-Lussac's results the quantities of oxygen in these two acids i for a given quantity of radical. ij. On this assumption we may calculate approximately the mass of the molecule of the phosphoric radical. but on the supposition of three molecules of hydrogen.4O Avogadro. that phosphoric acid contains about 115 parts by weight of oxygen to 100 of phosphorus. are represented by and Besides. the molecule of the sulphuric radical. Dalton had supposed that sulphuric acid was composed of two molecules of oxygen to one of radical. so that the If the exact density of sulformer would be reduced to 26. that of hydrogen being taken as unity . his value for the Phosphorus has so much analogy with sulphur that we might apparently assume that phosphoric acid also is composed of three molecules of oxygen to one of radical. and it is only by chance that the mass 15 which he assigns to it. As an approximation like sulphur. and phosphorous acid of only two of oxygen to one of radical. would be 27. . in his determina- tion of the molecule he set out from a wrong value for the composition of sulphuric acid. it would confirm by that means one or other of these hypotheses but we : are not sufficiently agreed about these densities to be able to draw any conclusion in this respect from the determinations hitherto existing.08. Rose found by a method analogous to that which had been employed for sulphuric acid. contains hydrogen. and sulphurous acid of one molecule of oxygen to one of sulphur. These two assumptions are incompatible. phuretted hydrogen to be exact. 27. phurous acid gas confirmed one or other of these results. on the supposition of only two molecules of hydrogen.08 would still be the sum of one molecule of radical and one of hydrogen.

5 for the molecule of phosphorus. UNIVERSITY) ^/ . and by still taking the molecule of oxygen nearly half ours. instead in Davy has adopted the same suppositions number of molecules of oxygen and radical * as ourselves for the of 38. he finds 16. if we admit that the volume element. Further experiments will clear up this point. as in several combinations of that sort. . f P . instead of 120 as we have assumed. /<&&> THE ^ \ OF LIBM^. hypotheses analogous to those he had made for sulphurous and sulphuric acids but since he used different values for the elements of these acids by weight. and thus bring the quantity of oxygen up to 120.give about 33 on our evaluation of the molecule of oxygen. which would .Relative Masses of Elementary Molecules. of carbon. between these molecules he has fixed that of phosphorus as 8. phorous and phosphoric acids.. 41 can make this increase in the same proportion as we have seen holds good for sulphuric acid in accordance with the specific gravity of sulphurous acid. which does not bear the same ratio to his determination of the molecule of sulphur as ought to exist. as the quantity of oxygen in phosphoric acid. volume of carbonic acid is equal to that of the oxygen which enters into it. that of hydrogen Dalton also has adopted for phosbeing taken as unity. and that conphosphorous and phosphoric acids . that of carbon. it will be necessary to suppose that this volume is the half of that of the oxygen With which it combines. i.* Let us now see what conjecture we may form as to the mass of the molecule of a substance which plays in nature a far greater part than sulphur or phosphorus. which forms the other is doubled by the division of its molecules into two. supposed gaseous.e. As it is certain that the namely. then. We then find we from our hypotheses that the mass of the molecule of the phosphoric radical is about 38. he arrived at a determination of the molecule of phosphorus. according to us. : hydrogen being unity. 136 to 100 of phosphorus. The difference arises from Davy having taken from his own experiments 34 parts to 25.

whereas one would be inclined to attribute the solidity of its aggregation at the highest temperatures to a higher molecular mass. and consequently a molecular mass. should have an extremely large nevertheless gaseous at a temperature smaller. according to other known examples. from the proportion by weight between the oxygen and the carbon. Mercury. Oxygenated muriatic acid gas has a density. and the mass of its molecule 11. one difficulty in this supposition. might avoid this difficulty by assuming a division of the molecule into four. as is observed and phosphoric radicals. There is. But such a composition would not be analogous to that of the other acids and.36 with respect to hydrogen.832 with respect to that of air as unity. or even into eight. which as we shall see further is molecule. to however. infinitely on. and is therefore analogous to sulphurous and phosphorous acids. but also on some other unknown property of substances. lower than would be necessary to vaporise iron. that the density of carbon as gas would be 0. tion or not of the gaseous state does not appear to depend solely on the magnitude of the molecule. accord- In this case we find ing to the preceding suppositions. which is almost equal to that of the solid sulphuric radical. Thus we see sulphurous acid in the form of a gas at the ordinary temperature and pressure of the atmosphere notwith- standing its large molecule. for we give the molecule of carbon a mass less than that of nitrogen and oxygen. still more considerable.42 Avogadro. the molecule of carbon twice or four times as great as that we have just fixed. on the formation of carbonic acid for in that way we should have in the case of the sulphuric We . the assump. besides. is the molecule of which Thus there is nothing to prevent us from regarding carbonic acid to be com- . sequently carbonic acid results from the union of one molecule of carbon and two of oxygen.

although the last- .Relative Masses of Elementary Molecules. The mass ii. Assuming the values indicated for the mass of the molecule of carbon and the density of its gas. as to the mass of its molecule .22 11. can leave no doubt. but the latest experiments of Davy upon it. Gay-Lussac and Thenard. of equal parts by volume of carbon gas and oxygen gas . Amongst still the simple non-metallic substances there is one of which we have to speak.07321 - V. the mass of the molecule of oxygen according to us. and even the earlier experiments of MM.4.36 is to 15. and phosphoric acids. 36 and that of carbonic oxide will +2 2 of the molecule of carbonic acid will be x 15.36. and has consequently been led to attribute to carbon a molecule equal to 4. and the molecule of carbon to have a mass expressed by 11.36+15. 43 posed in the manner indicated above. carbonic oxide will be formed.96782 0. Gay-Lussac. with subsequent halving all in perfect analogy to nitrous gas.074 1. being naturally gaseous. force us to depart from ideas hitherto received.074 = 1 = 0. Dalton has made the same supposition as we have done regarding the composition of carbonic acid. according to the experiments of M. on our principles. and its volume will be equal to the sum of the volumes of its constituents it will accordingly be formed of carbon and oxygen united molecule to mole: cule. which is almost in the same ratio to his value for that of oxygen as 11.5*96 be 3. sulphuric. This substance. and therefore analogous to nitric.

9.272.44 A vogadro. from other considerations. according to our hypothesis. the mass that These two estimates differ very little from Davy himself. 33. the density of oxymuriatic gas should be 2. should be 1.91. Accordingly the density of muriatic acid gas. 74-5 =32.278 according MM. fore. with halving of the molecule. and hydrogen. viz. this gives for its molecule referred to that of hydrogen as unity.82. both of Gay-Lussac and Thenard. . density of oxymuriatic acid according to MM. adopting the density of hydrogen determined by MM. calculating from that given above for to the experiments of oxymuriatic gas. the acid. and the mass of its molecule 33. ideas. of which we have already tion of equal volumes of oxymuriatic gas and that its volume is equal to their sum.470 referred to atmospheric The air as unity . Gay-Lussac and Thenard is 2. had so many examples.74. Biot and Arago. Should we prefer to adopt this value. of oxygenated muriatic acid. we must now hydrogen. that muriatic acid gas is formed by the combina- This means. that muriatic acid is formed of these two substances united molecule to molecule. Biot and Gay-Lussac. According to Davy 100 English cubic inches of oxymuriatic gas weigh 74. and of experiments Davy. If we suppose this last determination to be exact. it is 1.27. named chemists have attempted to ance with these This is explain them in accordthe substance hitherto known by oxymuriatic posed. therethat we shall apply our principles regarding com- binations to these two substances. and an equal volume of hydrogen gas This would give for the molecule of the former 2. It follows from the assigns to this substance. 32..5 grains.483. or In the present state of our knowledge regard this substance as still undecomit name and muriatic acid as a compound of It is in with accordance with this theory.

It follows from the experiments of different chemists.18 VI.16 of oxygen. and the mass of its molecule. viz. Let us now apply our hypothesis to some metallic substances. would be double what they are on the preceding hypothesis. in the formation of absorb 4. and 17. and that in mercuric oxide one molecule of mercury combines with two of oxygen. supposed gaseous. is analogous to nitrous oxide.*. accord100 cubic inches of that gas weigh 39 33. mercuric oxide..32. mass of the molecule of oxymuriatic acid. 26 \ for the first. oxygen united molecule to molecule but some reasons lead me to think that it is mercurous oxide which represents this last case. drawn from other metals. and 362 for the Then In this assumption I am supported by analogies second. viz.07321 specific gravity of the muriatic acid gas ing to which grains. 1 81 taking as unity that of hydrogen. for that of muriatic acid. which would give 13. Supposing this to be the case.25 as its density taking that of air as unity. and particularly from iron. the density of mercury gas ought to be to that of oxygen as 100 to 8. which contains twice should be formed of mercury and . is combined in it with half its volume of oxygen gas. that the mercury. and for the mass of the molecule of mercury On as this supposition much oxygen. by Davy. the mass I 45 of the molecule of muriatic acid will be the I>27 The determination of 2 0.. the density of mercury gas. which 100 parts by weight of mercury according to Fourcroy and Thenard. /.36 for the would give numbers only slightly different. Gay-Lussac assumes that mercurous oxide.. which on our hypothesis is to say that one molecule of oxygen combines with two molecules of mercury.Relative Masses of Elementary Molecules. M. care- .

and if we admit the proportion for the black oxide to be the more exact. viz. If that is so. and in the second with three. and this is perhaps the white oxide. which It gives about 94 with regard to hydrogen as unity. The mass of a molecule of iron will therefore be to 48. 206 for the silver.9. We see that the second of these two quantities of oxygen is nearly half as great again as the first. that the two best known oxides of iron. one of which contains twice as much oxygen as the other. . here add a few words regarding the molecule of Davy. the red oxide having no analogue in the case of mercury. we may determine their elements by same manner the mass of their molecules.8 and 45 parts by weight of oxygen to 100 of iron. the black oxide and the red oxide. In the same way the other metals present for the most part two oxides in which the quantities of oxygen are as i to 2. has fixed the mass of the I shall potassium. 198 for that of * 123 for copper.46 fully discussed A vogadro. so that we are naturally led to suppose that in the first oxide one molecule of iron combines with two molecules of oxygen.. molecule of lead. etc. the mass of a molecule of oxygen as TOO to 15. by Hassenfratz. the proportion for the red oxide would be 47. assuming that potash is formed from potassium and oxygen united molecule to molecule. should apparently be analogous to this last oxide of iron and to the black oxide.* find example. so that from the proportions of in the for I weight. oxides of mercury of which we have spoken. which comes very near the proportion found directly by Proust.7 for 100 of iron.9 of oxygen to 100 of iron. are composed respectively of 31. although the experiments hitherto performed point to this substance Now the two containing a greater proportion of oxygen. would appear from this that there should be another oxide of iron which would contain 15.

viz. and that in sulphide of potassium the combination is molecule to molecule. this salt is composed the carbonate. oxygen. as we have done. that in potash one molecule of potassium takes two of which case we should again have to double the last It might also be (for the analogy drawn value and make it 162. if we adopt the other assumptions of Davy. since both from our hypothesis and from the density of the gas. Let us pause to consider gas On our hypothesis. in oxygen by weight oxygen to be 7. which will furnish us with the shall We now make opportunity of examining an important point in the M. about 81.5. If we suppose the molecule of potassium to have a different mass. accordance with the quantity of and has taken the molecule of this last Assuming. It is on the assumption of this last value for the molecule of it But may be in potassium that Davy finds 32.5. are of one molecule of carbonic acid with one molecule of ammonia i. and muriate of ammonia composed of equal volumes of ammonia and of the respective acids. calculating from the composition of muriate of potash. of one molecule of molecule of potassium at 40. and assuming that this salt is formed of one molecule of potassium with one of acid.9 of sulphur will be about 27 instead of 13^ as found by Davy on the latter assumption.5.9 for that of oxymuriatic acid.e. 47 a few applications of our principles to saline compounds. VII. that the neutral carbonate. On the supposition that the molecule of potassium is 81. (according to the values previously given and independently of any division). Gay-Lussac has shown theory of these compounds.Relative Masses of Elementary Molecules. the molecule of potassium will also be doubled. from other metals is not in this case a very safe guide) that two molecules of potassium combine with one of oxygen. which will bring about between this result and that derived from sulphurous acid according to our calculations the agreement which exists between Davy's OF THE UNIVERSITY . molecule to be nearly twice as great. in the substance. fluoborate. we must admit another relative number of molecules in the muriate. the molecule 32. is very nearly the molecule of oxymuriatic acid. which would bring back the molecule of potassium to 40..

substances form amongst themselves a series.75 for the mass of its molecule . carbon.). tome Ixix. Lastly. about which are placed the substances we term neutral. I express by the term oxygenicity the in virtue of which substances are ranked in this property scale. below it are those which are alkaline. to idea of acidity. on our hypothesis. alkali united molecule to mole- but certain considerations appear to be opposed to The the admission of this principle in all its generality.87. That is as much as to say. and this series is the same as that on which depends the positive or negative electricity they develop contact. one of nitrogen. and neutrality. two of oxygen. alkalinity. if there were another division on the union of the acid with the alkali. It would be brought down again to half this number. above it are those which are absolutely acid. M. is that I which have given in my Memoir on this subject According to it. may be general. and three of hydrogen. Gay-Lussac has suspected volume between a gaseous alkali that the and acid. which still seems me the most conformable to the phenomena. this molecule is reduced to 28. placing first those which play the part of an acid on mutual In this scale there is a point with respect to the others. all (Journal de Physique.48 A vogadro. that neutral salts are composed of acid and cule . composite substances occupy in this scale a place intermediate between those of which they are composed. so that a neutral substance results from the combination of two substances. when their state of aggregation permits them exhibit these qualities. having regard to to the degree of oxygenicity and to the proportion by weight of these constituent substances . in which they play the part of acid or alkali with respect to one another. equality of which by their union form a neutral salt. but admitting the division into two which had already taken place in the components. which would give 57. .

* The recognition of the simple observed on combination. that from the union of certain definite numbers of these molecules there should result a certain definite degree of oxygenicity which would be that of neutrality. It appears. they simply show that this substance is very I had already remarked in my Memoir that the oxygenic. being analogous to those of oxygen. that we must admit that the degree of oxygenicity which corresponds to neutrality is not quite fixed. as Davy conceives them. and in particular in cases where neutral substances are the result. on the proalready portion by weight and the degree of oxygenicity of the components.Relative Masses of Elementary Molecules. 49 one the acid. then. if between the number of the different simple combining molecules. that. although the compound aggregation permitting it were endowed with these qualities. The oxygenicity in two bodies which com- bine. although approximating more or less to a fixed limit. leads us now to a more exact manner of conceiving the state of Memoir neutrality. supposed to be oxides. properties of the alkalies. namely. ratios in Thus amongst which molecules can combine. and that this state depends on the excess of mass of one of the components (from which the acid or alkaline quality might result) being prevented from exercising these qualities by the simple combination with the contrary principle which retains it by its attraction. the other alkaline. as we have assumed for oxygenicity in general. which gives the The properties of oxymuriatic acid. in a certain proportion (see ratios referred to). * D . are not at all extraordinary from this point of view . there is one which gives neutrality . cannot be supposed to have such a relation to the masses of their molecules. and would only depend. The excess of mass thus held back is that which is necessary to complete a certain simple relation it otherwise might have a state of to act as an acid or an alkali. are easily explained according to these ideas.

According to this theory it is evident that if the oxygenicity of two acids and two alkalies which combine respectively in pairs. the oxygenicities it of the various neutral compounds and is this point which would give the neutral state in the combination of two substances which could combine in all proportions. what are the simple . the compound would diverge further from this precise point. the components. or of combination molecule to molecule which we see between carbonic and a few other acids on the one hand and ammonia on the be other simple ratios other. and expounded by M. de evident that this way of regarding the compound substances Memoir quoted with his Traite* Laplace on this point. is not extremely different.50 Avogadro. equality of volumes. neutrality of reconciles the theory given in the the ideas put forward by M. closely to the definite if in the compound approximating most compound formed according principles let point of oxygenicity mentioned above. the ratio may be the same in both compounds but in the contrary may vary in such a way that instead of the . so that to this ratio. and if at the same time the mass of the molecule of one of the acids is not in a different ratio to its alkali from that of the other acid with regard to its own alkali. . as it were. Nevertheless. one of the one molecule of the other escape. there may which give the neutral state. or at least conjecture. or in ratios expressible It is by any number of molecules whatever.. &c. the simplicity which will always exist amongst these ratios. about which there component oscillate. the ratio between the numbers of molecules which gives neutrality case. Haiiy in de Physique. will sometimes put us in a position to determine. in conjunction with the information we may obtain from other sources as to the mass of the molecules and the degree of oxygenicity of such as i to 2. or took up one in addition.

BRISTO PLACE. are Dalton's system supposes that compounds this is made in general in fixed proportions. but it is the task these theoretical estimates. in spite of the division of the molecules. UNIVERSITY . on account of the enormous size of the molecules which would result from ratios expressed by larger numbers. and this distinction may serve to reconcile M. stable compounds and shows with regard to It would appear those most interesting to the chemist. that it is only combinations of this sort that can take place and the more what experiment amongst gases. This agreement is an in favour of our hypothesis. compounds with the theory of fixed propor- THE DAR1EN PRESS. is in all probability confined within narrow limits. although we set out from a general principle. EDINBURGH. which only leaves between the integral which We molecules distances of the same order as those between the elementary molecules. Berthollet's ideas as to tions. can give rise to more compli: cated ratios. and Dalton has only been guided by considerations of detail.Relative Masses of Elementary Molecules. and even to combinations in all proportions but these compounds will be so to speak of a different type from those with which we have been concerned. which is at bottom Dalton's system furnished with a new means of merely precision from the connection we have found between it argument and the general fact established by M. VIII. Gay-Lussac. It will have been in general Memoir that there are remarked on reading this many points of agreement between our special results and those of Dalton. 5 1 which may occur in a given case of experiment to confirm or correct ratios . perceive that the close packing of the molecules in solids and liquids.

52 pp. Quick=Lime. No. 48 pp. By the Papers published in the Philosophical Transactions.D. 3. M. FOUNDATIONS OF THE ATOMIC THEORY: Comprising Papers and Extracts by JOHN DALTON. Uniform. TETIOT PLACE. Crown Octavo. No. 1802-1808. 6d. Price is. 6d. WILLIAM 18 F.ALEMBIC CLUB REPRINTS OF IMPORTANT & SCARCE HISTORICAL WORKS RELATING TO CHEMISTRY. 2d. By JOSEPH BLACK. F. No. and THOMAS THOMSON. net. 1755. M. DISH. CLAY. Hon. Postage of any of the above to any part of the World. Publisher. EDINBURGH. AIR. i.. EXPERIMENTS ON 1784-1785. each extra. . and other Alcaline Substances. EXPERIMENTS UPON MAGNESIA ALBA.D. M.R. Volumes already Published. 47 pp. WILLIAM HYDE WOLLASTON. 2. net. net. Price is.S.D. Price HENRY CAVENis. Cloth. 6d.

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