Henry's law/Citable Version

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Henry's law is one of the gas laws, formulated by the British chemist, William Henry, in 1803. It states that:

At a constant temperature, the amount of a given gas dissolved in a given type and volume of liquid is directly proportional to the partial pressure of that gas in equilibrium with that liquid.

Formula and Henry constant

A formula for Henry's Law is:

where:

is approximately 2.7182818, the base of the natural logarithm (also called Euler's number)
is the partial pressure of the solute above the solution
is the concentration of the solute in the solution (in one of its many units)
is the Henry's Law constant, which has units such as L·atm/mol, atm/(mol fraction) or Pa·m3/mol.

Taking the natural logarithm of the formula, gives us the more commonly used formula:[1] [2][3][4]

Some values for k include:

oxygen (O2) : 769.2 L·atm/mol      
carbon dioxide (CO2) : 29.4 L·atm/mol      
hydrogen (H2) : 1282.1 L·atm/mol    

when these gases are dissolved in water at 298 kelvins.

As shown in Table 1 below, there are other forms of Henry's Law each of which defines the constant k differently and requires different dimensional units.[5] The form of the equation presented above is consistent with the example numerical values presented for oxygen, carbon dioxide and hydrogen and with their corresponding dimensional units.

Note that the unit of concentration was chosen to be molarity. Hence the dimensional units: L is liters of solution, atm is the partial pressure of the gaseous solute above the solution (in atmospheres of absolute pressure), and mol is the moles of the gaseous solute in the solution. Also note that the Henry's Law constant, k, varies with the solvent and the temperature.

Other forms of Henry's law

There are various other forms Henry's Law which are discussed in the technical literature.[5][6][7]

Table 1: Some forms of Henry's law and constants (gases in water at 298 K), derived from [7]
equation:
dimension:
O2 769.23 1.3 E-3 4.259 E4 3.180 E-2
H2 1282.05 7.8 E-4 7.099 E4 1.907 E-2
CO2 29.41 3.4 E-2 0.163 E4 0.8317
N2 1639.34 6.1 E-4 9.077 E4 1.492 E-2
He 2702.7 3.7 E-4 14.97 E4 9.051 E-3
Ne 2222.22 4.5 E-4 12.30 E4 1.101 E-2
Ar 714.28 1.4 E-3 3.955 E4 3.425 E-2
CO 1052.63 9.5 E-4 5.828 E4 2.324 E-2

where:

= moles of gas per liter of solution
= liters of solution
= partial pressure of gas above the solution, in atmospheres of absolute pressure
= mole fraction of gas in solution = moles of gas per total moles ≈ moles of gas per mole of water
= atmospheres of absolute pressure

As can be seen by comparing the equations in the above table, the Henry's Law constant is simply the inverse of the constant . Since all may be referred to as the Henry's Law constant, readers of the technical literature must be quite careful to note which version of the Henry's Law equation is being used.[5]

It should also be noted the Henry's Law is a limiting law that only applies for dilute solutions. The range of concentrations in which it applies becomes narrower the more the system diverges from ideal behavior. Roughly speaking, that is the more chemically different the solute is from the solvent.

It also only applies for solutions where the solvent does not react chemically with the gas being dissolved. A common example of a gas that does react with the solvent is carbon dioxide, which rapidly forms hydrated carbon dioxide and then carbonic acid (H2CO3) with water.

Temperature dependence of the Henry constant

When the temperature of a system changes, the Henry constant will also change.[5][8] This is why some people prefer to name it Henry coefficient. There are multiple equations assessing the effect of temperature on the constant. This form of the van 't Hoff equation is one example:[7]

where

k for a given temperature is the Henry's Law constant (as defined in the first section of this article), identical with kH,pc defined in Table 1,
T is in kelvins,
(theta) refers to the temperature of 298 K.

The above equation is an approximation only and should be used only when no better experimentally derived formula for a given gas exists.

The following table lists some values for constant C (dimension of kelvins) in the equation above:

Table 2: Values of C (in K)
Gas O2 H2 CO2 N2 He Ne Ar CO
C 1700 500 2400 1300 230 490 1300 1300

Because solubility of gases decreases with increasing temperature, the partial pressure a given gas concentration has in liquid must increase. While heating water (saturated with nitrogen) from 25 °C to 95 °C the solubility will decrease to about 43% of its initial value. Partial pressure of CO2 in seawater doubles with every 16 K increase in temperature.[9]

The constant C may be regarded as:

where

is the enthalpy of solution
is the universal gas constant.

Henry's law in geophysics

In geophysics a version of Henry's law applies to the solubility of a noble gas in contact with silicate melt. One equation used is

where:

subscript m = melt
subscript g = gas phase
= the densities of the solute gas in the melt and gas phase
an inverse temperature scale
= the Boltzmann constant
and = the excess chemical potential of the solute in the two phases.

Raoult's law compared to Henry's Law

As can be seen in the mathematical expressions of the two laws, both laws state that the partial pressure of a liquid mixture component is proportional to the concentration of that component in the liquid mixture:

Henry's law:  
Raoult's law:
where:
= partial pressure of a solute gas above a solution
= concentration of the solute gas in the solution
= Henry's law constant
= partial pressure of component in a liquid mixture
= vapor pressure of the pure component in the liquid mixture
= mol fraction of component in the liquid mixture

In a dilute solution, the solute gas approximately obey's Henry's law and the solvent approximately obeys Raoult's law.[2]

References

  1. University of Delaware physical chemistry lecture
  2. 2.0 2.1 Robert G. Mortimer (2000). Physical Chemistry, Second Edition. Academic Press. ISBN 0-12-508345-9. 
  3. Green, Don W. and Perry, Robert H. (deceased) (1997). Perry's Chemical Engineers' Handbook, 6th Edition. McGraw-Hill. ISBN 0-07-049479-7.  (See page 14-9)
  4. Online Introductory Chemistry: Solubiltiy of gases in liquids
  5. 5.0 5.1 5.2 5.3 Francis L. Smith and Allan H. Harvey (September 2007). "Avoid Common Pitfalls When Using Henry's Law". CEP (Chemical Engineering Progress). ISSN 0360-7275.
  6. University of Arizona chemistry class notes
  7. 7.0 7.1 7.2 An extensive list of Henry's law constants, and a conversion tool
  8. Green, Don W. and Perry, Robert H. (deceased) (1984). Perry's Chemical Engineers' Handbook, 6th Edition. McGraw-Hill. ISBN 0-07-049479-7.  (See pages 3-101 to 3.103 for tabulated Henry's constant values versus temperature for various gases)
  9. Takahashi, T. et al (2002). Global sea-air CO2 flux based on climatological surface ocean CO2 and seasonal biological and temperature effects, Deep-Sea Research (Part II, Topical Studies in Oceanography) 49, 9-10, pp. 1601-1622.