Henry ’s law

Henry s law The mass of gas which is dissolved by a given volume of a liquid at constant temperature is directly proportional to the pressure of the gas. The law is only obeyed provided there is no chemical reaction between the gas and the liquid. 

For dilute solutions, solute-solute interactions are unimportant (i.e., Henry s law will hold), and the variation of surface tension with concentration will be linear (at least for nonelectrolytes). Thus... 

The ideal gas law equation of state thus leads to a linear or Henry s law isotherm. A natural modification adds a co-area term ... 

The constants in Eqs. XVII-88-XVI1-90 may be calculated fiom theory to give the Henry s law constant K from Eq. XVII-87, the experimental n /P dien gives the surface area. Alternatively, the constants may be arrived at from an experimental K (assuming that A is known) and either the isosteric heat of adsorption... 

We conclude with the matter of adsorbate-adsorbate interactions these give rise to deviations from Henry s law behavior. These may be expressed in the form of a virial equation, much as is done for imperfect gases. Following Steele [8], one can write... 

Make a plot of Eq. XVII-69 as 6 versus P, and, for comparison, one of a Langmuir adsorption isotherm of same limiting or Henry s law slope. Comment on the comparison. 

The Freundlich equation is defective as a model because of the physically unrealistic/((2) consequences of this are that Henry s law is not approached at low P, nor is a limiting adsorption reached at high P. These difficulties can be patched by supposing that... 

It should be noted that, whatever the fonu of Henry s law (i.e. in whatever composition units), Raoult s law must necessarily be expressed in mole fraction. This says nothing about the appropriateness of mole fractions in condensed systems, e.g. in equilibrium expressions it arises simply from the fact that it is a statement about... 

The standard state of an electrolyte is the hypothetical ideally dilute solution (Henry s law) at a molarity of 1 mol kg (Actually, as will be seen, electrolyte data are conventionally reported as for the fonnation of mdividual ions.) Standard states for non-electrolytes in dilute solution are rarely invoked. 

Substances at high dilution, e.g. a gas at low pressure or a solute in dilute solution, show simple behaviour. The ideal-gas law and Henry s law for dilute solutions antedate the development of the fonualism of classical themiodynamics. Earlier sections in this article have shown how these experimental laws lead to simple dieniiodynamic equations, but these results are added to therniodynaniics they are not part of the fonualism. Simple molecular theories, even if they are not always recognized as statistical mechanics, e.g. the kinetic theory of gases , make the experimental results seem trivially obvious. 

If tire diffusion coefficient is independent of tire concentration, equation (C2.1.22) reduces to tire usual fonn of Pick s second law. Analytical solutions to diffusion equations for several types of boundary conditions have been derived [M]- In tlie particular situation of a steady state, tire flux is constant. Using Henry s law (c = kp) to relate tire concentration on both sides of tire membrane to tire partial pressure, tire constant flux can be written as... 

In glassy polymers tire interactions of tire penetrant molecules witli tire polymer matrix differ from one sorjDtion site to anotlier. A limiting description of tire interaction distribution is known under tire name of tire dual-soriDtion model [, 60]. In tliis model, tire concentration of tire penetrant molecules consists of two parts. One obeys Henry s law and tire otlier a Langmuir isotlienn ... 

The hydrogencarbonate ion, produced in nature by this reaction, is one of the main causes of temporary hardness in water. Carbon dioxide is fairly soluble in water, 1 cm dissolving 1.7 cm of the gas at stp. The variation of solubility with pressure does not obey Henry s law, since the reaction... 

A number of properties can be computed from various chemical descriptors. These include physical properties, such as surface area, volume, molecular weight, ovality, and moments of inertia. Chemical properties available include boiling point, melting point, critical variables, Henry s law constant, heat capacity, log P, refractivity, and solubility. 

Activity coefficient (referenced to Henry s law) Concentration basis 7c c,B ... 

Henry s Law. The solubility of a gas is directly proportional to the partial pressure exerted by the gas ... 

The results of a comparison between values of n estimated by the DRK and BET methods present a con. used picture. In a number of investigations linear DRK plots have been obtained over restricted ranges of the isotherm, and in some cases reasonable agreement has been reported between the DRK and BET values. Kiselev and his co-workers have pointed out, however, that since the DR and the DRK equations do not reduce to Henry s Law n = const x p) as n - 0, they are not readily susceptible of statistical-thermodynamic treatment. Moreover, it is not easy to see how exactly the same form of equation can apply to two quite diverse processes involving entirely diiferent mechanisms. We are obliged to conclude that the significance of the DRK plot is obscure, and its validity for surface area estimation very doubtful. 

This experiment provides an alternative approach to measuring the partition coefficient (Henry s law constant) for volatile organic compounds in water. A OV-101 packed column and flame ionization detector are used. 

Henry s law corresponds physically to the situation in which the adsorbed phase is so dilute that there is neither competition for surface sites nor any significant interaction between adsorbed molecules. At higher concentrations both of these effects become important and the form of the isotherm becomes more complex. The isotherms have been classified into five different types (9) (Eig. 4). Isotherms for a microporous adsorbent are generally of type I the more complex forms are associated with multilayer adsorption and capillary condensation. 

Equation 6 shows that the adsorption of component 1 at a partial pressureis reduced in the presence of component 2 as a result of competition for the available surface sites. There ate only a few systems for which this expression (with 5 1 = q 2 = 5 ) provides an accurate quantitative representation, but it provides useful quaUtative or semiquantitative guidance for many systems. In particular, it has the correct asymptotic behavior and provides expHcit recognition of the effect of competitive adsorption. For example, if component 2 is either strongly adsorbed or present at much higher concentration than component 1, the isotherm for component 1 is reduced to a simple linear form in which the apparent Henry s law constant depends onp. ... 

This has the advantage that the expressions for the adsotbed-phase concentration ate simple and expHcit, and, as in the Langmuir expression, the effect of competition between sorbates is accounted for. However, the expression does not reduce to Henry s law in the low concentration limit and therefore violates the requirements of thermodynamic consistency. Whereas it may be useful as a basis for the correlation of experimental data, it should be treated with caution and should not be used as a basis for extrapolation beyond the experimental range. 

The solubihty of a gas in water is affected by temperature, total pressure, the presence of other dissolved materials, and the molecular nature of the gas. Oxygen solubihty is inversely proportional to the water temperature and, at a given temperature, directly proportional to the partial pressure of the oxygen in contact with the water. Under equihbrium conditions, Henry s law apphes... 

Hydrogen Chloride—Water System. Hydrogen chloride is highly soluble in water and this aqueous solution does not obey Henry s law at ah concentrations. Solubhity data are summarized in Table 5. The relationship between the pressure and vapor composition of unsaturated aqueous hydrochloric acid solutions is given in Reference 12. The vapor—Hquid equiHbria for the water—hydrogen chloride system at pressures up to 1632 kPa and at temperatures ranging from —10 to +70° C are documented in Reference 13. 

Chlorine. The solubiUty of chlorine [7782-50-5] in hydrochloric acid is an important factor in the purification of by-product hydrochloric acid. The concentration of chlorine in solution, S, is proportional to the partial pressure of chlorine, p, in the gas phase and follows Henry s law, S = i/p, in the... 

Hydrogen Chloride-Organic Compound Systems. The solubihty of hydrogen chloride in many solvents follows Henry s law. Notable exceptions are HCl in polyhydroxy compounds such as ethylene glycol (see Glycols), which have characteristics similar to those of water. Solubility data of hydrogen chloride in various organic solvents are Hsted in Table 10. 

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