BAE 820 Physical Principles of

Environmental Systems
Henry’s Law - Raoult's Law – Partition law

Dr. Zifei Liu

Biological and Agricultural

Engineering
 Henry's law
• At a constant temperature, the amount of a
given gas that dissolves in a given type
and volume of liquid is directly
proportional to the partial pressure of that
gas in equilibrium with that liquid.
Pi = KHCi
• Where Pi is the partial pressure of the
gaseous solute above the solution, Ci is the William Henry
concentration of the dissolved gas and KH (1774-1836)
is Henry’s constant with the dimensions of
pressure divided by concentration. KH is
different for each solute-solvent pair.

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 Henry's law
For a gas mixture, Henry's law helps to predict the
amount of each gas which will go into solution.
When a gas is in contact with the surface of a liquid,
the amount of the gas which will go into solution is
proportional to the partial pressure of that gas.
An equivalent way of stating the law is that the
solubility of a gas in a liquid is directly proportional
to the partial pressure of the gas above the liquid.
the solubility of gases generally decreases with
increasing temperature.
A simple rationale for Henry's law is that if the
partial pressure of a gas is twice as high, then on the
average twice as many molecules will hit the liquid
surface in a given time interval,

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 Air-water equilibrium

Dissolution
Pg or Cg
Air (atm, Pa, mol/L, ppm, …)
At equilibrium,
P
KH = g
Caq
Water Caq
(mol/L, mole ratio, ppm, …)
Volatilization

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 Various units of the Henry’s constant
(gases in water at 25ºC)

Form of
KH, pc=P/Caq KH, cp=Caq/P KH, px=P/x KH, cc=Caq/Cgas
equation
Units L∙atm/mol mol/(L∙atm) atm dimensionless
O2 769 1.3×10-3 4.26×104 3.18×10-2
N2 1639 6.1×10-4 9.08×104 1.49×10-2
CO2 29 3.4×10-2 1.63×103 0.832

Since all KH may be referred to as Henry's law constants, we must be quite

careful to check the units, and note which version of the equation is being used.

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 Unit conversions

1
KH, 𝑝𝑐 =
KH, 𝑐𝑝
KH, 𝑝𝑥 1000 K KH, 𝑝𝑐
= × H, 𝑝𝑐 = 55×
[𝑎𝑡𝑚] 18 [𝑎𝑡𝑚/𝑀] [𝑎𝑡𝑚/𝑀]

At 298K,
KH, 𝑝𝑐 𝑅𝑇 0.082×298 24.4
= = =
[𝑎𝑡𝑚/𝑀] KH, 𝑐𝑐 KH, 𝑐𝑐 KH, 𝑐𝑐

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 Henry’s constant
Except for high soluble gases such as NH3 where Henry’s law
constant varies slightly with concentration level in solution, the
solubility curves for most less soluble gases are straight lines and
obey Henry’s law.
KH (atm/M) in water at 25ºC
O2 769
N2 1639
CO2 29
NH3 0.013 to 0.019
H2 S 10
SO2 0.8
CH4 714

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 Solubility and Henry’s law constant

Solubility: the amount of a substance that will dissolve in a given

amount of solvent, g/L.
A saturated solution is one which is in equilibrium with undissolved
solute – it has reached limit of solubility. According to Henry’s law,
gases are more soluble at higher pressure.
The solubility
Sg=Pg/ KH

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 Raoult's law
• Partial vapor pressure of each component of an ideal
mixture of liquids is equal to the vapor pressure of the
pure component multiplied by its mole fraction in the
mixture.
Pi = Pi0Xi
• Where Pi is the partial pressure of the gaseous solute i
above the solution, Pi0 is the vapor pressure of the pure
component i, and Xi is the mole fraction of the
component i in the solution.
Francois-Marie Raoult
• When solution concentration is low (Xi →0) , Henry’s (1830-1901)
law is applicable. Henry's law is only applicable to gas
solute mole fractions less than 0.03.

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 Vapor pressure
• When a liquid comes in contact with the air, a fraction of it will go into vapor
phase and mix with the air. If the liquid is a pure substance, the partial pressure
at equilibrium is called vapor pressure.
• Higher vapor pressure means higher potential of volatilization (vaporization).
Vapor pressure increases with increasing temperature, and for organic
molecules, it may be estimated from molecular structure. Generally, vapor
pressure increases with decreasing molecular weight.

Vapor pressure at 25ºC (kPa)

Water 3.17
NH3 1003
H2S 2026
CO2 6401

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Engineering 10
 Raoult's law

When a substance is dissolved in a solution,

the vapor pressure of the solution will
generally decrease. The vapor pressure of a
solution is lower than that of the pure
solvent.
The partial pressure of a solvent vapor in
equilibrium with a solution is proportional
to the ratio of the number of solvent
molecules to non-volatile solute molecules.

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 Two opposite ends of the composition
range
Raoult's law and Henry’s law apply at
opposite ends of the composition range.
Both laws are limit laws.
𝑃𝑖
• Raoult's law: lim = 𝑃𝑖0
𝑥→1 𝑋𝑖
𝑃𝑖
• Henry’s law: lim = 𝐾𝐻
𝑥→0 𝐶𝑖

Henry's law can be used to describe a

minority component and Raoult's law can
be used to describe a majority component.

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Engineering 12
 The van 't Hoff equation
When the temperature of a system changes, the Henry
constant will also change. This is why some people prefer to
name it Henry coefficient.
𝑑𝑙𝑛𝐾𝑒𝑞 Δ𝐻
1 =
𝑑 𝑅
𝑇

In which, 𝐾𝑒𝑞 is the equilibrium constant; Δ𝐻 is the reaction

enthalpy; R is the gas constant.
KH, pc (T) = KH0, pc exp[-C(1/T-1/298)]
Where KH0, pc is KH, pc at the standard temperature (298K), C J.H. van’t Hoff
is a constant in Kelvins. For O2, C=1700K. (1852-1911)
For NH3/water solution, C=3670K. A simplified equation is The first winner of Noble
Prize in Chemistry (1901)
KH, pc (T) = 1000 exp (3.133-4200/T)

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 Solubility and temperature
Solids solubility usually Gas solubility almost always decreases
increases as T increases. as T increases (KH, pc increases)

That is why sometimes in the summer there are some fish kills
due to the warmer water and less oxygen available for the fish.

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 Influence of pH on NH3
NH4+  NH3+H+ For NH3, at 25ºC,
Ka = [NH3][H+]/ [NH4+] pKa=9.3
[NH3]/ [NH4+]= Ka/ [H+]

100%
NH4+ NH3
75%
Percent species

50%

25%

0%
4 6 8 10 12
pH
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Engineering
 Influence of pH H2S
H2S  H++HS-
For H2S, at 25ºC,
Ka = [H+][HS-]/[H2S]
pKa=7.1
[H2S]/[HS-]=[H+]/Ka

100%
H2S HS-
75%
Percent species

50%

25%

0%
4 6 8 10 12
pH

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Engineering
 Partitioning equilibrium between two
immiscible solvents
The word “partition” means a substance is distributed between two phases (or two
immiscible solvents) in a dynamic equilibrium. The ratio of the concentrations of a
solute in two immiscible solvents (solvent 1 and solvent 2) is constant when
equilibrium has been reached. This constant is known as the partition coefficient,
Kpartition.
𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑖𝑛 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 1
Kpartition =
𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑖𝑛 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 2

The partition law holds true for dilute solutions. For concentrated solutions,
interactions between solvent and solute have to be considered and the
concentration terms should be expressed by “activity”.

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 Absorption vs. Adsorption
Absorption is the process in which a Adsorption is the adhesion of atoms,
fluid permeates or is dissolved by a ions, or molecules to a surface. This
liquid or a solid (absorbent). process creates a film of the adsorbate
on the surface of the adsorbent.
Absorption is a bulk process which
involves the whole volume of the Adsorption is a surface-based process.
material.

Absorption Adsorption

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 Partitioning between liquid and solid phases
• Freundlich isotherm
𝑥
= Kc1/n
𝑚
• Langmuir isotherm
𝑥 𝑄0𝑏𝑐
=
𝑚 1+𝑏𝑐
Where,
x is the quantity adsorbed.
m is the mass of adsorbent (solid).
K is the Freundlich partition coefficient.
c is the equilibrium concentration of adsorbate in solution..
1/n is the Freundlich exponent. For solutions with low concentrations, 1/n≈1(linear
isotherm).
Q0 is the maximum adsorption at fixed temperature.
b is the Langmuir adsorption constant constant related to net enthalpy of adsorption.
Freundlich isotherm is widely used for NH4+ partition between liquid and solid phase.

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 Problem solving #5-1

• The lowest level of oxygen gas dissolved in water that will

support life is ~ 1.3 × 10 - 4 mol/L. Calculate the solubility of
oxygen in water at 25ºC. At the normal atmospheric pressure
of oxygen, is there adequate oxygen in water to support life?
• Given: The Henry’s law constant for oxygen in water is 769
atm/M, or 1.3× 10−3 mol/L/atm.

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 Problem solving #5-2
• How many grams of carbon dioxide gas is dissolved in a 1 L bottle of
carbonated water if the manufacturer uses a pressure of 2.4 atm in the
bottling process at 25 °C?
• Given: KH of CO2 in water = 29 atm/(mol/L) at 25 °C

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 Problem #3-3
• In a preliminary study, you added 10 mL of the
compound to 1 L of waste which resulted in the pH of the
waste being reduced from 8.5 to 5.5. The untreated waste
has total ammoniacal-N [NH3+NH4+] concentration of
250 mgN/L and [H2S+HS-] of 5 mg/L.
• What are the changes in NH3 and H2S concentrations
(based on theory) in the waste before and after
application of the amendment?
• Given pKa=7.1 for H2S, pKa=9.3 for NH3

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Engineering
 Problem solution #5-1
• Partial pressure of oxygen gas in the atmosphere is 21%,
or 0.21 atm.

Soxygen = Pg/ KH = 0.21/769 = 2.7× 10−4 mol/L

Adequate to sustain life in water!

 Problem solution #5-2

C = Pg/ KH = 2.4 atm/29 atm/(mol/L) = 0.08 mol/L

g of CO2 = 0.08 mol × 44 g/mol = 3.52 g
 Problem #3-3
For NH3, pKa=9.3
[NH4+]= [NH3][H+]/10^(-9.3)
[NH3]*14/17+[NH4+]*14/18=250
So,
[NH3]*14/17+ [NH3][H+]/10^(-9.3)*14/18=250
[NH3]=250/{14/17+[H+]/10^(-9.3)*14/18}

For H2S, pKa=7.1

[HS-]=[H2S]*10^(-7.1)/[H+]
[H2S]+[HS-]=5
So,
[H2S]+[H2S]*10^(-7.1)/[H+]=5
[H2S]=5/{1+10^(-7.1)/[H+]}
 Problem #3-3
Before application of the amendment, pH=8.5,
[NH3]=250/{14/17+10^(-8.5)/10^(-9.3)*14/18}=43.62 mg/L
[H2S]=5/{1+10^(-7.1)/10^(-8.5)}=0.19 mg/L

After application of the amendment, pH=5.5,

[NH3]=250/{14/17+10^(-5.5)/10^(-9.3)*14/18}=0.51 mg/L
[H2S]=5/{1+10^(-7.1)/10^(-5.5)}=4.88 mg/L

So, after application of the amendment, NH3 concentration is reduced from

43.62 mg/L to 0.51 mg/L. However, H2S concentration increased from 0.19
mg/L to 4.88 mg/L.