CHEN623: Fundamentals and Applications of

Thermodynamics to Chemical Engineers

Course Instructors: Professor Ioannis G. Economou

Mr. Arvin Arugay
Chemical Engineering Program
Texas A&M University at Qatar
PO Box 23874, Doha, Qatar
e-mail: ioannis.economou@qatar.tamu.edu
Solubilities of Gases in Liquids
Prausnitz et al. Chapter 10
L18 – Solubilities of Gases in Liquids CHEN 623: Fundaments and Applications Fall 2022
of Thermodynamics to Chemical Engineers 1
 INTRODUCTION

• The solubility of gases in liquids is a naturally occurring process

with important implications:
– Blood dissolves oxygen in all mammalian species, including
humans,
– Sea water dissolves oxygen to sustain marine life.
• Solubility of gases in liquids is important in a number of industrial
processes:
– Liquid absorption is used to separate gas mixtures,
– Water solubility of gases from industrial processes should be
accurately known for environmental control.
• Fundamental equation that describes the gas solubility in liquid, at
equilibrium:

f i gas = f i liquid

L18 – Solubilities of Gases in Liquids CHEN 623: Fundaments and Applications Fall 2022
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 THE IDEAL SOLUBILITY OF A GAS

• Ideal solubility:
– Neglect gas phase nonidealities,
– Neglect pressure effect on the liquid phase (Poynting correction),
– Neglect nonidealities due to solute – solvent interactions:
pi = xi Pi sat
pt
soubility
• How do we treat gases at the supercritical state? my

• What is the effect of solute – solvent interactions?

Solubilities (mole fraction x 104) of gases in liquids
at 25 oC and 1.013 bar partial pressure

L18 – Solubilities of Gases in Liquids CHEN 623: Fundaments and Applications Fall 2022
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 HENRY’S LAW AND ITS THERMODYNAMIC
SIGNIFICANCE
• Henry’s law can be conveniently used to describe gas solubility in
liquids, for relatively low solubility values:
pi = yi P = H i ,solventxi =  i fi 0 xi
• In this expression, it is implicitly assumed that:  2  f (x2 ) independent
• This is a good approximation for low x2 values, given that: ofcomposition

RT ln  2 = A(1 − x2 ) + B(1 − x2 ) + ...

2 3

• In general, one has to account also for gas phase non-idealities based
on the fugacity coefficient:
f i = i yi P = H i ,solventxi
Henry’s constants (bar) in ethylene oxide

L18 – Solubilities of Gases in Liquids CHEN 623: Fundaments and Applications Fall 2022
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 EFFECT OF PRESSURE ON GAS SOLUBILITY –
THERMODYNAMIC ANALYSIS
• The effect of pressure on Henry’s constant is significant at high
pressures. We have seen that:
  ln f i L  vi fi L
  = and since : H i , solvent  lim one gets :
  P T , x RT xi → 0 xi
  ln H i , solvent  vi
  =
 P  RT
 T
• Integration of the latter results in:
P É

ss
) + v (P − Psolvent )
r v dP
i 
 ln H (P
fi ( Pr ) s
ln = ln H i , solvent + P solvent
i , solvent
i
xi RT RT

I
Krichevsky-Kasarnovsky equation

L18 – Solubilities of Gases in Liquids CHEN 623: Fundaments and Applications Fall 2022
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 EFFECT OF PRESSURE ON GAS SOLUBILITY –
EXPERIMENTAL EVIDENCE
Solubility of H2 in H2O
Solubility of N2 in NH3

y IIa
of W of
Solubility of N2 in H2O

Deviations due to activity

coefficient effects (γ depends on
8
composition) and due to changes
in N2 partial molar volume

L18 – Solubilities of Gases in Liquids CHEN 623: Fundaments and Applications Fall 2022
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 EFFECT OF PRESSURE ON GAS SOLUBILITY –
THERMODYNAMIC ANALYSIS ACCOUNTING FOR NON-IDEALITIES
• Using a simple two-suffix Margules equation for γ of solvent and the
unsymmetric convention for the solute, one gets:

enter I fi ( ) A 2 vi ( P − Psolvent

s
)
( xsolvent − 1) +
s
Psolvent
ln = ln H i , solvent +
xi RT RT
for
account Krichevsky-Ilinskaya equation
intergtislaues
CO2 in phenol
• This equation has a wide applicability for solutions
(SRK used in calcs)
of light gases in solvents where the solubility is
appreciable.
H ( s
Psolvent ) , A and v 
• The three parameters i , solvent i are
calculated from a combination of experimental
data and an equation of state correlation.

L18 – Solubilities of Gases in Liquids CHEN 623: Fundaments and Applications Fall 2022
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 EFFECT OF TEMPERATURE ON GAS SOLUBILITY

• Rule of thumb (often wrong): As the temperature rises, gas solubility

falls.
• For non-volatile solvents and low solute solubility:
  ln x2  h2   ln x2  s2 Henrys’ constants (bar)
  = − and   = of gases in liquids
 1/ T P R   ln T  P R

where:

2
G
2 (
h2  h − h = h − h + h2L − h2L and
L L
2
G
2
ÉÉ
) ( )
Fatigues
s2  s2L − s2G = (s2L − s2G )+ (s2L − s2L )

entropy of entropy of mixing

condensation = - Rlnx2

L18 – Solubilities of Gases in Liquids Fall 2022

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 ENTROPY OF SOLUTION OF GASES IN LIQUIDS

Entropy of solution of gases in liquids as a

function of gas solubility at 25 oC and 1 atm

(J mol-1 K-1)

L18 – Solubilities of Gases in Liquids CHEN 623: Fundaments and Applications Fall 2022
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 NON-LINEAR TEMPERATURE EFFECT
ON GAS SOLUBILITY
Henry’s constants for gases in water Hydrocarbon solubility in water
1.E-02

HYDROCARBON MOLE FRACTION

1-Butene
1.E-03

1.E-04
1-Hexene 1-Decene

1.E-05

1-Octene

1.E-06

1.E-07
250 350 450 550 650
TEMPERATURE (K)
Negatively infinite slope as
approaching solvent Tc
L18 – Solubilities of Gases in Liquids CHEN 623: Fundaments and Applications Fall 2022
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 THERMODYNAMIC ANALYSIS OF HENRY’S
CONSTANT OF GASES IN LIQUIDS
Methane in H2O
• Henry’s constant of a solute in a solvent can be
analyzed in terms of pure solvent properties
and solvent – solute interactions:

To Chand
B It
excess
potential
Ainteraction
messinthe

between
Southand
solvent

Icity Eminem
m
dent
solvent
deper
The maximum in Henry’s
constant is driven by the
maximum of non-idealities of Boulougouris et al.,
solvent – solute mixing. J.Phys.Chem. B,
105, 7792 (2001).
L18 – Solubilities of Gases in Liquids Fall 2022
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 ESTIMATION OF GAS SOLUBILITY

• Experimental data on gas solubility in liquids are limited

and mostly at 25 oC.
• Reliable correlations / theories are needed.
Solubility at 25 oC and 1 atm partial pressure
as a function of solvent as a function of solute
solubility parameter Lennard-Jones ε/k parameter

Regular solution
theory (no excess
entropy of mixing):
1/ 2
  vapu 
   
 v 
molar
volume
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 CORRELATION BASED ON
REGULAR SOLUTION THEORY
• Dissolution process:
(a) The solute “condenses” isothermally to a hypothetical liquid with a
volume close to the partial molar volume,
(b) The solute and the solvent mix at no volume change.
L
f pure
+ RT ln  2 x2
,2
g = g I + g II = RT ln G
f 2
RT ln  2 = v (1 −  2 ) 12
L 2
• In regular solution theory, it is:
2
• Since Δg = 0, then:
d 1
=
L
f pure,2  v2L (1 −  2 )2 12 
exp 
fed

equilibrium x2 f 2G  RT 
In regular solution theory: v2L (1 −  2 ) 12  f (T )
2
•

• Φ1 is composition-dependent so an iterative scheme is needed.

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 CORRELATION BASED ON
REGULAR SOLUTION THEORY (more)
• Thermodynamic parameters are usually fitted to experimental data.
“Liquid” volumes and solubility Fugacity of a hypothetical liquid
parameters at 25 oC at 1 atm

At considerably higher pressures, a Poynting correction is needed for

the fugacity: L
 v2 (P − 1.01325 )
f L
pure, 2 (at P) = f L
pure, 2 (at 1.01325 bar ) exp  
 RT 
L18 – Solubilities of Gases in Liquids CHEN 623: Fundaments and Applications Fall 2022
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 GAS SOLUBILITY IN MIXED SOLVENTS

• Solubility data for gases in mixed solvents are scarce.

• Relatively simple thermodynamic models allow a fair estimate of the
solubility in a mixed solvent based on the solubility in corresponding
pure solvents.
• Starting from a simple two-suffix Margules expansion for the excess
Gibbs energy of a ternary mixture (2 is solute):
gE
= a12 x1 x2 + a13 x1 x3 + a23 x2 x3
RT
interaction
one obtains: cross
M team
ln H 2,mixture = x1 ln H 2,1 + x3 ln H 2,3 − a13 x1 x3

• Constant a13 must be estimated from VLE data for the solvent mixture.
e
• The equation can be generalized to multicomponent mixtures.

L18 – Solubilities of Gases in Liquids CHEN 623: Fundaments and Applications Fall 2022
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 HENRY’S CONSTANTS IN SOLVENT MIXTURES

Calculated Henry’s constants in

solvent mixtures at 25 oC

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