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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]
3Temperature dependence
6Miscellaneous
o
6.1In geochemistry
7See also
8References
[edit]
)[edit]
[edit]
where
= temperature.
[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:
)[edit]
Here,
) to avoid
is
and thus:
[edit]
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]
[edit]
)[edit]
is Pa m3 mol1.
[edit]
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.
Values of
(in K)
O2
H2
CO2
N2
He
Ne
Ar
CO
1700
500
2400
1300
230
490
1300
1300
[edit]
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
.
where
= Henry's law constant in pure water,
= Henry's
law constant in the salt solution,
= molality-based Sechenov
constant, and
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.
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
, where
for a
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.
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:
Physical chemistry
Equilibrium chemistry
Engineering
thermodynamics
Gas laws
Underwater diving
physics
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