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Henry's law

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In chemistry, Henry's law is one of the gas laws formulated by the English chemist William Henry,
who studied the topic in the early 19th century. In his publication about the quantity of gases
absorbed by water,[1] he described the results of his experiments:
..."water takes up, of gas condensed by one, two, or more
additional atmospheres, a quantity which, ordinarily
compressed, would be equal to twice, thrice, &c. the volume
absorbed under the common pressure of the atmosphere."
In other words, the amount of dissolved gas is proportional to its
partial pressure in the gas phase. The proportionality factor is called
the Henry's law constant.
An everyday example of Henry's law is given by a carbonated soft
drink in a bottle. Before it is opened, the gas above the drink is
almost pure carbon dioxide at a pressure higher than atmospheric
pressure. The drink itself contains dissolved carbon dioxide. When
the bottle is opened, this gas escapes, giving the characteristic hiss.
Because the partial pressure of carbon dioxide above the liquid is
now much lower, some of the dissolved carbon dioxide comes out
of the solution as bubbles. If the drink is left in the open, the
concentration of carbon dioxide in solution will come into equilibrium
with the carbon dioxide in the air, and the drink will go "flat". Another
example is the depth-dependent dissolution of oxygen and nitrogen
in the blood of underwater
divers (decompression and decompression sickness).
Contents
[hide]

1Fundamental types and variants of Henry's law constants


o

1.1Henry's law solubility constants

1.2Henry's law volatility constants

2Values of Henry's law constants

3Temperature dependence

4Effective Henry's law constants

5Dependence on ionic strength (Sechenov equation)

6Miscellaneous
o

6.1In geochemistry

6.2Comparison to Raoult's law

6.3Standard chemical potential

7See also

8References

Fundamental types and variants of Henry's


law constants[edit]
There are many ways to define the proportionality constant of
Henry's law, which can be subdivided into two fundamental types:
One possibility is to put the aqueous phase into the numerator and
the gas phase into the denominator ("aq/gas").[2] This results in the
Henry's law solubility constant
. Its value increases with
increased solubility. Alternatively, numerator and denominator can
be switched ("gas/aq"), which results in the Henry's law volatility
constant
. The value of
decreases with increased solubility.
There are several variants of both fundamental types. This results
from the multiplicity of quantities that can be chosen to describe the
composition of the two phases. Typical choices for the aqueous
phase are molar concentration ( ), molality ( ), and molar mixing
ratio ( ). For the gas phase, molar concentration ( ) and partial
pressure ( ) are often used. It is not possible to use the gas-phase
mixing ratio ( ) because at a given gas-phase mixing ratio, the
aqueous-phase concentration
depends on the total pressure and
thus the ratio
is not a constant.[3][4] To specify the exact variant
of the Henry's law constant, two superscripts are used. They refer to
the numerator and the denominator of the definition. For
example,

refers to the Henry solubility defined as

Henry's law solubility constants

[edit]

Henry solubility defined via concentration (

)[edit]

Atmospheric chemists often define the Henry solubility as:


.
Here,
is the concentration of a species in the aqueous phase
and is the partial pressure of that species in the gas phase under
equilibrium conditions.
The SI unit for
is mol (m3 Pa)1. However, often the unit M
1
atm is used since
is usually expressed in M (1 M = 1 mol dm3)
and in atm (1 atm = 101325 Pa).
The dimensionless Henry solubility

[edit]

The Henry solubility can also be expressed as the dimensionless


ratio between the aqueous-phase concentration
of a species and
its gas-phase concentration :

For an ideal gas, the conversion is:

where

= gas constant and

= temperature.

Sometimes, this dimensionless constant is called the "water-air


partitioning coefficient"
. It is closely related to the various,
slightly different definitions of the "Ostwald coefficient" , as
discussed by Battino (1984).[5]
Henry solubility defined via aqueous-phase mixing ratio (

[edit]
Another Henry's law solubility constant is:

Here, is the molar mixing ratio in the aqueous phase. For a dilute,
aqueous solution the conversion between and
is:

where
Thus:

= density of water and

The SI unit for

= molar mass of water.

is Pa1. However, atm1 is still frequently used.

Henry solubility defined via molality (

)[edit]

It can be advantageous to describe the aqueous phase in terms of


molality instead of concentration. The molality of a solution does not
change with
since it refers to the mass of the solvent. In contrast,
the concentration does change with , since the density of a
solution and thus its volume are temperature-dependent. Defining
the aqueous-phase composition via molality has the advantage that
any temperature dependence of the Henry's law constant is a true
solubility phenomenon and not introduced indirectly via a density
change of the solution. Using molality, the Henry solubility can be
defined as:

Here,

is used as the symbol for molality (instead of

) to avoid

confusion with the symbol


for mass. The SI unit for
is mol
1
(kg Pa) . There is no simple way to calculate
from
since
the conversion between concentration
and molality
involves all solutes of a solution. For a solution with a total of
solutes with indices
, the conversion is:

where = density of the solution, and


= molar mass. Here,
identical to one of the in the denominator. If there is only one
solute, the equation simplifies to:

is

Henry's law is only valid for dilute solutions where


and
. In this case the conversion reduces further to:

and thus:

The Bunsen coefficient

[edit]

According to Sazonov and Shaw (2006),[4] the dimensionless


Bunsen coefficient is defined as: "The volume of saturating gas,
reduced to 273.15 K and 1 bar, which is absorbed by unit volume of
pure solvent at the temperature of measurement and partial
pressure of 1 bar". If the gas is ideal, the pressure cancels out, and
the conversion to
simply is:

with
= 273.15 K. Note, that according to this definition, the
conversion factor is not temperature-dependent! Independent of the
temperature that the Bunsen coefficient refers to, 273.15 K is
always used for the conversion. The Bunsen coefficient, which is
named after Robert Bunsen, has been used mainly in the older
literature.
The Kuenen coefficient

[edit]

According to Sazonov and Shaw (2006),[4] the Kuenen coefficient


is defined as: "The volume of saturating gas, reduced to 273.15 K
and 1 bar, which is dissolved by unit mass of pure solvent at the
temperature of measurement and partial pressure 1 bar". If the gas
is ideal, the relation to
is:

where is the density of the solvent and


= 273.15 K. The SI
unit for is m3 kg1. The Kuenen coefficient, which is named
after Johannes Kuenen, has been used mainly in the older
literature. IUPAC considers it to be obsolete.[6]

Henry's law volatility constants

[edit]

)[edit]

The Henry volatility defined via concentration (

A common way to define a Henry volatility is dividing the partial


pressure by the aqueous-phase concentration:

The SI unit for

is Pa m3 mol1.

The Henry volatility defined via aqueous-phase mixing ratio (


)[edit]
Another Henry volatility is:

The SI unit for

is Pa. However, atm is still frequently used.

The dimensionless Henry volatility

[edit]

The Henry volatility can also be expressed as the dimensionless


ratio between the gas-phase concentration
of a species and its
aqueous-phase concentration :

In chemical engineering and environmental chemistry, this


dimensionless constant is often called the airwater partitioning
coefficient

Values of Henry's law constants[edit]


A large compilation of Henry's law constants has been published by
Sander (2015).[2] A few selected values are shown in the table
below:
Henry's law constants (gases in water at 298.15 K)

equation:

unit:

(dimensionless)

O2

770

1.3103

4.3104

3.2102

H2

1300

7.8104

7.1104

1.9102

CO2

29

3.4102

1.6103

8.3101

N2

1600

6.1104

9.1104

1.5102

He

2700

3.7104

1.5105

9.1103

Ne

2200

4.5104

1.2105

1.1102

Ar

710

1.4103

4.0104

3.4102

CO

1100

9.5104

5.8104

2.3102

Temperature dependence[edit]
When the temperature of a system changes, the Henry constant will
also change. The temperature dependence of equilibrium constants
can generally be described with the van 't Hoff equation which also
applies to Henry's law constants:

where
= enthalpy of dissolution. Note that the letter
in
the symbol
refers to enthalpy and is not related to the
letter
for Henry's law constants. Integrating the above equation
and creating an expression based on
at the reference
temperature
= 298.15 K yields:

The van't Hoff equation in this form is only valid for a limited
temperature range in which
temperature.

does not change much with

The following table lists some temperature dependencies:

Values of

(in K)

O2

H2

CO2

N2

He

Ne

Ar

CO

1700

500

2400

1300

230

490

1300

1300

Solubility of permanent gases usually decreases with increasing


temperature at around room temperature. However, for aqueous
solutions, the Henry's law solubility constant for many species goes
through a minimum. For most permanent gases, the minimum is
below 120 C. Often, the smaller the gas molecule (and the lower
the gas solubility in water), the lower the temperature of the
maximum of the Henry's law constant. Thus, the maximum is about

30 C for helium, 92 to 93 C for argon, nitrogen and oxygen, and


114 C for xenon.[7]

Effective Henry's law constants

[edit]

The Henry's law constants mentioned so far do not consider any


chemical equilibria in the aqueous phase. This type is called the
"intrinsic" (or "physical") Henry's law constant. For example, the
intrinsic Henry's law solubility constant of methanal can be defined
as:

In aqueous solution, methanal is almost completely hydrated:

The total concentration of dissolved methanal is:

Taking this equilibrium into account, an effective Henry's law


constant

can be defined:

For acids and bases, the effective Henry's law constant is not a
useful quantity because it depends on the pH of the solution. [3] In
order to obtain a pH-independent constant, the product of the
intrinsic Henry's law constant
and the acidity constant
is
often used for strong acids like hydrochloric acid (
):

Although
is usually also called a Henry's law constant, it should
be noted that it is a different quantity and it has different units
than
.

Dependence on ionic strength (Sechenov


equation)[edit]
Values of Henry's law constants for aqueous solutions depend on
the composition of the solution, i.e., on its ionic strength and on
dissolved organics. In general, the solubility of a gas decreases with
increasing salinity ("salting out"). However, a "salting in" effect has
also been observed, for example for the effective Henry's law
constant of glyoxal. The effect can be described with the Sechenov
equation, named after the Russian physiologist Ivan
Sechenov (sometimes the German transliteration "Setschenow" of
the Cyrillic name is used). There are many alternative

ways to define the Sechenov equation, depending on how the


aqueous-phase composition is described (based on concentration,
molality, or molar fraction) and which variant of the Henry's law
constant is used. Describing the solution in terms of molality is
preferred because molality is invariant to temperature and to the
addition of dry salt to the solution. Thus, the Sechenov equation can
be written as:

where
= Henry's law constant in pure water,
= Henry's
law constant in the salt solution,
= molality-based Sechenov
constant, and

= molality of the salt.

Miscellaneous[edit]
In geochemistry[edit]
In geochemistry, a version of Henry's law applies to the solubility of
a noble gas in contact with silicate melt. One equation used is

where:
C = the number concentrations of the solute gas in the melt and
gas phases
= 1/kBT, an inverse temperature scale: kB = the Boltzmann
constant
E = the excess chemical potentials of the solute gas in the two
phases.

Comparison to Raoult's law[edit]


Henry's law is a limiting law that only applies for
'sufficiently 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.
For a dilute solution, the concentration of the solute
is approximately proportional to its mole fraction x,
and Henry's law can be written as:
This can be compared with Raoult's law:

where p* is the vapor pressure of the pure


component.

At first sight, Raoult's law appears to be a


special case of Henry's law where KH = p*.
This is true for pairs of closely related
substances, such as benzene andtoluene,
which obey Raoult's law over the entire
composition range: such mixtures are
called "ideal mixtures".
The general case is that both laws are limit
laws, and they apply at opposite ends of
the composition range. The vapor pressure
of the component in large excess, such as
the solvent for a dilute solution, is
proportional to its mole fraction, and the
constant of proportionality is the vapor
pressure of the pure substance (Raoult's
law). The vapor pressure of the solute is
also proportional to the solute's mole
fraction, but the constant of proportionality
is different and must be determined
experimentally (Henry's law). In
mathematical terms:

Raoult's law:
Henry's law:
Raoult's law can also be related to
non-gas solutes.

Standard chemical
potential[edit]
Henry's law has been shown to
apply to a wide range of solutes in
the limit of "infinite dilution" (x0),
including non-volatile substances
such as sucrose. In these cases, it
is necessary to state the law in
terms of chemical potentials. For a
solute in an ideal dilute solution,
the chemical potential depends on
the concentration:

, where

for a

volatile solute; co = 1 mol/L.


For non-ideal solutions,
the activity
coefficient c depends on the
concentration and must be
determined at the

concentration of interest. The


activity coefficient can also be
obtained for non-volatile
solutes, where the vapor
pressure of the pure
substance is negligible, by
using the Gibbs-Duhem
relation:

By measuring the change


in vapor pressure (and
hence chemical potential)
of the solvent, the
chemical potential of the
solute can be deduced.
The standard state for a
dilute solution is also
defined in terms of infinitedilution behavior. Although
the standard
concentration co is taken to
be 1 mol/l by convention,
the standard state is a
hypothetical solution of
1 mol/l in which the solute
has its limiting infinitedilution properties. This
has the effect that all nonideal behavior is described
by the activity coefficient:
the activity coefficient at
1 mol/l is not necessarily
unity (and is frequently
quite different from unity).
All the relations above can
also be expressed in
terms of molalities b rather
than concentrations, e.g.:

, where

for a

volatile solute; bo = 1 mol/kg.


The standard
chemical potential mo,
the activity
coefficient m and the
Henry's law
constant KH,b all have

different numerical
values when molalities
are used in place of
concentrations.

See also[edit]

Pervaporation

Partition
coefficient

Sieverts' law

Henry adsorption
constant

References[edit]
1.

Jump
up^ Henry, W.
(1803).
"Experiments
on the quantity
of gases
absorbed by
water, at
different
temperatures,
and under
different
pressures". Phil
. Trans. R. Soc.
Lond. 93: 29
274.doi:10.109
8/rstl.1803.000
4.

2.

^ Jump up
to:a b Sander, R.
(2015), "Compil
ation of Henry's
law constants
(version 4.0)
for water as
solvent", Atmos
. Chem.
Phys. 15:
43994981, do
i:10.5194/acp15-4399-2015

3.

^ Jump up
to:a b Sander, R.
(1999).
"Modeling
atmospheric
chemistry:
Interactions
between gasphase species
and liquid
cloud/aerosol
particles". Surv.
Geophys. 20:
131.

4.

^ Jump up
to:a b c Sazonov,
V. P.; Shaw, D.
G.
(2006). "Introdu
ction to the
solubility data
series".

5.

Jump
up^ Battino,
R.; Rettich, T.
R.; Tominaga,
T. (1984). "The
solubility of
nitrogen and air
in liquids". J.
Phys. Chem.
Ref. Data 13:
563600.

6.

Jump
up^ Gamsjger
, H.; Lorimer, J.
W.; Salomon,
M.; Shaw, D.
G.; Tomkins, R.
P. T. (2010).
"The IUPACNIST Solubility
Data Series: A
guide to
preparation
and use of
compilations
and
evaluations
(IUPAC
Technical
Report)". Pure
Appl.
Chem. 82:
11371159. do

i:10.1351/pacrep-09-10-33.
7.

Concepts

Jump
up^ Cohen, P.,
ed. (1989). The
ASME
Handbook on
Water
Technology for
Thermal Power
Systems. The
American
Society of
Mechanical
Engineers.
p. 442. ISBN 9
78-0-79180634-0.

Acid dissociation constant


Binding constant
Binding selectivity
Buffer solution
Chemical equilibrium
Chemical stability
Chelation
Determination of equilibrium constants
Dissociation constant
Distribution coefficient
Dynamic equilibrium
Equilibrium chemistry
Equilibrium constant
Equilibrium unfolding
Equilibrium stage
Hammett acidity function
Henry's law

Liquidliquid extraction
Macrocycle effect
Phase diagram
Predominance diagram
Phase rule
Reaction quotient
Self-ionization of water
Solubility equilibrium
Stability constants of complexes
Thermodynamic equilibrium
Thermodynamic activity
Vaporliquid equilibrium

Categories:
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Equilibrium chemistry

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