Hydrogen bonding. Part 34. The factors that influence the solubility of gases and vapours in water at 298 K, and a new method for its determination

Abstract
The solubility of 408 gaseous compounds in water at 298 K has been correlated through eqn. (i), where the solubility is expressed as the Ostwald solubility coefficient, Lw, and the solute explanatory variables are R2 an excess molar refraction, π2 H the dipolarity/polarizability, Σα2 H and Σβ2 H the effective hydrogen-bond acidity and basicity, and Vx the McGowan characteristic volume. A similar equation using the log L16 parameter instead of Vx can also be used; L16 is the Ostwald solubility coefficient on hexadecane at 298 K. log Lw=–0.994 + 0.577R2+ 2.549 π2 H+ 3.813Σα2 H+ 4.841Σβ2 H– 0.869 Vx(i), n= 408 ρ= 0.9976 sd = 0.151 F= 16810 The main factors leading to increased solubility are solute π2 H, Σα2 H and Σβ2 H values; conversely, the corresponding properties of water are dipolarity/polarizability, hydrogen-bond basicity and hydrogen-bond acidity. Solute size plays a minor role, and slightly decreases solubility, contrary to observations on all non-aqueous solvents. It is shown that this peculiar behaviour of water is due to (a) a greater increase in the unfavourable cavity effect with increase in solute size, for solvent water, and (b) a smaller increase in the favourable general dispersion interaction with size, for solvent water. A new method for the determination of log Lw values is put forward, using the relationship Lw=L16/P where L16 is as above, and P is either the water–hexadecane partition coefficient or the water–alkane partition coefficient. For 14 solutes using the former P-value, agreement with values calculated through eqn. (i) is 0.08 log units on average and for 45 solutes using the latter P-value, the corresponding agreement is 0.15 log units, with log Lw values ranging up to 8 log units.