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Solubility of Gases in Water






Solubility of Gases in Water is usually expressed in one of two ways, namely, as Bunsen's Absorption Coefficient, β, or as Ostwald's Solubility expression, Z. These terms have already been defined.

Gases may be divided broadly into two classes, namely, those that combine with water, such as ammonia, hydrogen chloride, sulphur dioxide, and the like; and those that are chemically inert. Amongst the latter class may be placed oxygen, nitrogen, etc. The former group usually possess high absorption coefficients, whilst the latter are frequently so slightly soluble, that for many chemical purposes they may be regarded as insoluble and may be collected and even stored over water. Xenon lies between the two groups, its solubility being greater than that of any other chemically neutral gas.

Gas10°15°20°25°30°
Hydrogen0.02140.02040.01950.01880.01820.01750.0170
Nitrogen0.02390.02150.01960.01790.01640.01500.0138
Oxygen0.04960.04390.03900.03500.03170.02900.0268
CO0.03540.03150.02820.02540.02320.02140.0200
CH40.05560.04810.04180.03690.03310.03010.0276
NO0.07380.06460.05710.05150.04710.04300.0400
N2O. . .1.14030.94790.78960.66540.5752. . .
CO21.7131.4241.1941.0190.8780.7590.665
Chlorine (β1)4.610(3.232)3.0952.6352.2601.9851.769
H2S4.6213.9353.3622.9132.5542.2572.014
SO279.7967.4856.6547.2839.3732.7927.16
HCl525.2496474456443432. . .
NH312991019910802710635. . .


Solubility of Gases in Water falls with rise of temperature, but in the case of the inert gases minimum values exist, the solubility falling in the cases of xenon and argon as the temperature rises from 0° to 40° C. Above this point the solubility rises again. For krypton the minimum lies between 30° and 40° C.; for helium at 10° C., and for neon probably in the neighbourhood of 0° C.

In the preceding table are given the solubilities of a few typical gases in water at various temperatures. Unless otherwise stated the solubility co-efficient is employed. β1 signifies measurement of the gaseous volume at N.T.P., but the pressure includes the vapour pressure of the liquid also, whereas β signifies the volume under the pressure of the gas itself of 760 mm.

Winkler directed attention to the fact that, in the case of many chemically inert and "permanent" gases, the percentage decrease in the solubility coefficient between 0° and 20° C. is approximately proportional to the cube root of the molecular weight of the gas. Thus:

Percentage decrease in β A.Cube Root of Molecular Weight. B.A/B
Hydrogen15.321.25912.2
Nitrogen34.333.03711.3
Oxygen36.553.17511.5
Carbon monoxide34.443.03711.3
Nitric oxide36.243.10711.7


The decrease in is attributed by Winkler to a fall in the viscosity of the solvent consequent upon rise of temperature. The two factors may be equated as follows:



where η0 and ηt represent the viscosities of water at 0° and t° C. respectively, and k is a constant, M being the molecular weight. If βt is calculated from this expression, the value agrees well with that found experimentally between 0° and 60° C. The following values for k have been deduced:

k
Argon4.4
Hydrogen, oxygen, and diatomic gases3.8
CO2 and triatomic gases3.2


Helium is exceptional, however. As a rule, for those gases that deviate markedly from Boyle's law, the value for k tends to rise with temperature.

The Inert Gases. - The study of the solubility of the gases of group 0 of the Periodic Table has proved very interesting. The data published by Antropoff are given in the following table:

Solubilities of the Inert Gases in Water

Temperature, ° CHeliumNeonArgonKryptonXenon
Sample ISample II
00.01340.01140.05610.12490.11660.2189
100.01000.01180.04380.09650.08770.1500
200.01380.01470.03790.07880.06700.1109
300.01610.01580.03480.07620.05970.0900
400.01910.02030.03380.7400.05610.0812
500.02260.03170.03430.08230.06100.0878


Solubilities of the inert gases
Solubilities of the inert gases in water (Antropoff, 1910).
These results are shown graphically in Fig. A remarkable feature of these determinations is the minimum of solubility shown by every gas. Estreicher had already in 1899 suggested that such a minimum ought to exist, and indeed found such to be the case with helium. The minimum for xenon and argon lies at 40° C.; for krypton between 30° and 40° C.; for helium, at 10° C., and for neon probably at 0° C. As a general rule, the solubility rises with the atomic weight, helium and neon being exceptional, possibly on account of erroneous determination. It is also worthy of note that the solubility of xenon is greater than that of any other gas which does not form a compound with the solvent.

The solubility of a gas increases with the pressure; for gases chemically neutral towards water,

β ∞ p

since under moderate pressures Boyle's Law is obeyed with fair accuracy, it follows that a volume of water at a given temperature will absorb the same volume of gas whatever the pressure. This is Henry's Law, enunciated in 1803. The same year Dalton observed that the amount of a gas absorbed from a gaseous mixture is directly proportional to its partial pressure. In both of these cases it is assumed that the gas does not combine with the water. If combination takes place these laws are not obeyed.

The methods employed for the determination of Solubility of Gases in Water and gases in water may be either chemical or physical. The former are useful in cases where chemically reactive gases such as oxygen, etc., are concerned. For neutral gases, like nitrogen, physical methods are essential.

The presence of dissolved salts tends to reduce the solubility of neutral gases in water. This is capable of explanation on the assumption that the electrolyte is hydrated, and that the water thus " fixed " is no longer able to absorb the gas. If this theory is accepted, it becomes possible to calculate the degree of hydration of the salt. A solution of alcohol in water is peculiar in its behaviour towards oxygen. Although oxygen is several times more soluble in alcohol than in water, addition of alcohol to water reduces the absorption of oxygen, a minimum being reached with about 30 per cent, of alcohol. Further addition of this liquid raises the absorption coefficient.


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