Thermodynamics of solutions
Thermodynamics 4
Overview of Lecture
l
l
l
l
l
Definition of a solution.
Partial properties and mixing properties.
Principle exact differentials for solutions and chemical potential.
Fugacity & fugacity coefficient for pure substance and solutions.
Derivation of solution properties from residual Gibbs free
energy.
l Ideal solution and excess properties.
l Activity coefficient.
l Derivation of solution properties from excess Gibbs free energy.
7.1
Mark J. Biggs, 2003
Thermodynamics of solutions
Thermodynamics 4
Solutions
l A solution is a mixture where species-species interactions are
important.
l Differences between interactions of species pairs i-j in a solution
means equation 6.1 is NOT valid in general for solutions; i.e.
N
msolution xi mi
i =1
l The equality holds in this relationship strictly only for ideal gas
mixtures where interactions between molecules are negligible.
l The equality also generally holds in this relationship well when
interactions i-j are similar for all i-j (e.g. homologous series).
7.2
Mark J. Biggs, 2003
Thermodynamics of solutions
Thermodynamics 4
Molar, partial molar and solution properties
l The effect of a species on a solution property is in general
characterised in terms of the partial molar property
mi =
M
ni
Equation 7.1
p ,T ,n j
l The solution property is now generalized to
N
m = xi mi
Equation 7.2
i =1
l We now have three groups of properties:
Properties of pure species-i: mi
Partial properties of species-i in a solution: mi
Property of a solution (mixture): m
7.3
Mark J. Biggs, 2003
Thermodynamics of solutions
Thermodynamics 4
Gibbs-Duhem equation
l Previous developments can be used to obtain the Gibbs-Duhem
equation
m
m
dp +
p T , x
T
p,x
dT xi dmi = 0
Equation 7.3
i =1
l For constant temperature and pressure, this becomes
N
x dm
i =1
=0
Equation 7.3a
7.4
Mark J. Biggs, 2003
Thermodynamics of solutions
Thermodynamics 4
Partial molar properties for binary systems
l Example 7.1
Derive expressions for the partial properties of each species in a
binary solution in terms of the corresponding solution property
and mole fractions, and consider their graphical interpretation.
l Graphical interpretation
m2
m2 ( x2 )
m1
m1 ( x2 )
Pure 1
x2 = 1 x1
Pure 2
7.5
Mark J. Biggs, 2003
Thermodynamics of solutions
Change of property on mixing
Thermodynamics 4
l Consider graphically equations 6.1 (ideal) and 7.2 (real)
mid = xi mi
m1
m2
mmixing
m = xi mi
Pure 1
Pure 2
l The difference between the curves is the property change on
mixing
N
mmixing = xi ( mi mi )
Equation 7.4
i =1
7.6
Mark J. Biggs, 2003
Thermodynamics of solutions
Partial molar properties for an ideal gas
Thermodynamics 4
l Gibbs Theorem: except for the molar volume
miig (T , p ) = mi (T , pi )
l Example 7.2
Determine the partial molar volume of an ideal gas and discuss
how it differs from the above theorem.
l For molar volume, internal energy and enthalpy of an ideal gas
ig
mmixing
=0
7.7
Mark J. Biggs, 2003
Thermodynamics of solutions
Exact differentials and chemical potential
Thermodynamics 4
l The equations 3.3-3.6 can be generalised to multiple species
the Gibbs free energy is of particular practical interest
N
dG = Vdp SdT +
i =1
G
ni
dni
p ,T ,n j
l The partial molar Gibbs free energy is termed the chemical
potential
G
i = g i =
Equation 7.5
ni T , p ,n
j
l Equation 7.5 may be re-written in molar terms
N
dg = vdp sdT + i dxi
i =1
Equation 7.6
7.8
Mark J. Biggs, 2003
Thermodynamics of solutions
Chemical potential of an ideal gas mixture
Thermodynamics 4
l It can be shown that
iig = g iig = g iig + RT ln yi
Equation 7.7
l The alternative form can also be obtained
iig = g iig = i (T ) + RT ln pi
Equation 7.8
l Using equation 7.2 gives the Gibbs free energy as
N
i =1
i =1
g ig = yi i (T ) + RT yi ln pi
l We can see chemical potential has some annoying habits:
absolute values do not exist.
i as p 0 or yi 0.
7.9
Mark J. Biggs, 2003
Thermodynamics of solutions
Fugacity
Thermodynamics 4
l In analogy to equation 7.8
i = g i = i (T ) + RT ln fi
where fi is the fugacity, which equals pi in the ideal gas limit.
l Taking the difference between this and the ideal gas limit gives
f
iR = g iR = RT ln i = RT ln i
p
i
where i is termed the fugacity coefficient.
l In the case of a pure substance, gi is identical to gi and the same
relationships hold except the fugacity and fugacity coefficient
are given slightly different symbols of fi and i respectively. 7.10
Mark J. Biggs, 2003
Thermodynamics of solutions
Thermodynamics 4
Fugacity of a fluid described by the Virial EOS
l Example 7.3
Derive the following for a pure fluid at constant-temperature
P
ln i = ( Z 1)
0
dp
p
Simplify this for Z(p, T) = 1 + B(T)p/RT.
7.11
Mark J. Biggs, 2003
Thermodynamics of solutions
Derivation of solution properties from gR
Thermodynamics 4
l It may be shown that
GR
d
RT
N
VR
HR
=
dp
dT
+
ln i dni
2
RT
i =1
RT
Equation 7.9
l From this we may write
R
v R ( g RT )
=
RT
p
( g RT )
hR
and
=
2
RT
T
R
T ,x
and
ln i =
p,x
( G R RT )
ni
T , p ,n j
7.12
Mark J. Biggs, 2003
Thermodynamics of solutions
Thermodynamics 4
Fugacity of a fluid described by the Virial EOS
l Example 7.4
Obtain the following for a species-i in a solution
P
dp
ln i = ( Z i 1)
p
0
Simplify this for Z = 1 + B(T)P/RT, where B is now defined for
a solution.
7.13
Mark J. Biggs, 2003
Thermodynamics of solutions
Ideal solutions definition and properties
Thermodynamics 4
l Ideal solution (is) mixtures assume
intermolecular interactions between species are identical
molecules of each species occupy the same volume
l In analogy with equation 7.7
iis = g iis = g i + RT ln xi
l From this definition, it can be shown that for u, h and v
N
mis = xi mi
i =1
and
N
i =1
i =1
s is = xi si R xi ln xi
7.14
Mark J. Biggs, 2003
Thermodynamics of solutions
Ideal solutions fugacity
Thermodynamics 4
l It may be shown that
fi is = xi f i
where the fugacities of the pure species are evaluated at the
pressure and temperature of the solution this is termed the
Lewis-Randall rule.
l From this, it may be shown that
is =
i
7.15
Mark J. Biggs, 2003
Thermodynamics of solutions
Thermodynamics 4
Excess properties
l We may define solution excess properties
m E = m mis
and analogous partial excess properties
miE = mi miis
l Note: there is NO such thing as an excess property of species-i.
l Excess and residual properties are related
N
m = m xi miR
E
i =1
7.16
Mark J. Biggs, 2003
Thermodynamics of solutions
Derivation of excess properties
Thermodynamics 4
l From equation 7.9
E
v E ( g RT )
=
RT
p
T ,x
( g RT )
hE
=
RT 2
T
E
p ,x
( G E RT )
fi
ln
= ln i =
x f
ni
i i
T , p ,n j
where i is the activity coefficient.
7.17
Mark J. Biggs, 2003
Thermodynamics of solutions
Thermodynamics 4
Wrap-up
l Solutions are systems where interactions between species are
important they may be gas, liquid or solid or multiphase.
l This means a shift from use of properties of pure species to
partial molar properties.
l A particular partial molar property is the chemical potential.
l The effectively equivalent fugacity is often used instead, and it
is particularly useful when working with residual properties.
l All solution properties may be generated from gR.
l The effectively equivalent activity is also often used instead, and
it is particularly useful when working with excess properties.
l All solution properties may be generated from gE.
7.18
Mark J. Biggs, 2003
