Thermodynamics of Solutions

• Phases: Part of a system that is chemically and

physically homogeneous, bounded by a distinct
interface with other phases and physically separable
from other phases.
• Components: Smallest number of chemical entities
necessary to describe the composition of every
phase in the system.
• Solutions: Homogeneous mixture of two or more
chemical components in which their concentrations
may be freely varied within certain limits.
 Thermodynamics of Ions in
Solutions
    RT ln m
• Electrolyte solutions – deviations from
ideal behaviour occur at molalities as low
as 0.01 mole/kg.
• How do we obtain thermodynamic
properties of ionic species in solution?
 Thermodynamics (II)
• For the H+(aq) ion, we define
– fH = 0 kJ/mole at all temperatures
– S = 0 J/(K mole) at all temperatures
– fG = 0 kJ/mole at all temperatures
 Activities in Electrolyte
Solutions
• For the following discussion
– Solvent “s”
– Cation “+”
– Anion “-“
• Consider 1 mole of an electrolyte dissociating into
+ cations and - anions
G = ns s + n 
= ns s + n+ + + n- -
• Note – since  = + + -   = + + + - -
 The Mean Ionic Chemical
Potential
• We define
 =  / 
• We now proceed to define the activities
 =  + RT ln a
+ = + + RT ln a+
- = - + RT ln a-
 =  + RT ln a
The Relationship Between a and
a
• Since   =  / 
 =  + RT ln a =  ( + RT ln a)
Since  =  / 
• This gives us the relationship between the
electrolyte activity and the mean activity
(a)= a
The Relationship Between a , a- and
a+
• We note that  = + + + - -
and   =  / 
• This gives us the following relationship
v( + RT ln a) = + (+ + RT ln a+) +
- ( - + RT ln a-)
• Since   = + + + - -
(a) = (a+)+ (a-)-
 Activities in Electrolyte
Solutions
• The activities of various components in an
electrolyte solution are defined as follows
a+ = + m+
a- = - m-
a+ = + m+
• As with the activities
() = (+)+ (-)-
(m) = (m+)+ (m-)-
 The Chemical Potential
Expression
     RT ln a      RT lnm    
    RT lnm        RT lnm    RT ln  


   RT lnm   RT ln    
 
  RT ln  
• This can be factored into two parts
    RT lnm   RT ln   

  
  RT ln  
Deviations from
The ideal part ideal behaviour
 Activity Coefficients As a Function of
Data obtained from Molality
Glasstone et al., Introduction to Electrochemistry, Van Nostrand (1942).
CRC Handbook of Chemistry and Physics, 63rd ed.; R.C. Weast Ed.; CRC Press,
Boca Raton, Fl (1982).

1.60
CaCl2
1.40
1.20
1.00 HCl
+ 0.80
LaCl3
0.60
KCl
0.40
0.20
H2SO
0.00
0.00 0.50 1.00 4
1.50
m(1/2) / (mol(1/2)/kg(1/2))
 Mole Fractions
nA nA
XA   ,
 n (nA  n B  nC  )

where XA is called the “mole fraction” of

component A in some phase.

If the same component is used in more than one phase,

Then we can define the mole fraction of component
A in phase i as X Ai

For a simple binary system, XA + XB = 1

Partial Molar Volumes & Mixing
Temperature Dependence
of Partial Molar Volumes
 Partial Molar Quantities

• Defined because most solutions DO NOT mix

ideally, but rather deviate from simple linear
mixing as a result of atomic interactions of
dissimilar ions or molecules within a phase.
• Partial molar quantities are defined by the “true”
mixing relations of a particular thermodynamic
variable and can be calculated graphically by
extrapolating the tangent at the mole fraction of
interest back to the end-member composition.
 Partial Molar Gibbs Free Energy
As noted earlier, the change in Gibbs free energy function determines the
direction in which a reaction will proceed toward equilibrium. Because of
its importance and frequent use, we designate a special label called the
chemical potential, µ, for the partial molar Gibbs free energy.

GA 
A   
X A P,T ,X
B ,X C ,

We must define a reference state from which to calculate differences in

chemical potential. The reference state is referred to as the standard state
and can be arbitrarily selected to be the most convenient for calculation.

The standard state is often assumed to be pure phases at standard atmospheric

temperature and pressure (25°C and 1 bar). Thermodynamic data are tabulated
for most phases of petrological interest and are designated with the superscript °,
for example, G°, to avoid confusion.
 Chemical Thermodynamics
MASTER EQUATION

dG  VdP  SdT   i dX i
i

  dX
i i   A dX A  B dX B  C dX C   n dX n
i

This equation demonstrates that changes in Gibbs free energy are

dependent on:
• changes in the chemical potential, µ, through the
concentration of the components expressed as mole
fractions of the various phases in the system
• changes in molar volume of the system through dP
• chnages in molar entropy of the system through dT
 Equilibrium and the Chemical Potential
• Chemical potential is analogous to gravitational or electrical
potentials: the most stable state is the one where the overall
potential is lowest.
• At equilibrium the chemical potentials for any specific
component in ALL phases must be equal. This means that the
system will change spontaneously to adjust by the Law of
Mass Action to cause this state to be obtained.
 mel t
H 2O  gas
H2 O  biotit e
H 2O   n
H 2O

 mel t
CaO  gas
CaO  biotit e
CaO   n
CaO

If  melt
H 2O  gas
H2 O then system will have to adjust the massmelt
(concentration) to make them equal:  H 2O   gas
H2 O
Gibbs Free Energy of Mixing
 Activity - Composition Relations
The activity of any component is always less than the
corresponding Gibbs free energy of the pure phase, where the
activity is equal to unity by definition (remember the choice
of standard state).

  Ai  GA  RT ln aAi

A  G ;  B  G
A B
a i
A  X
i
A
i
A

For ideal solutions (remember dG of mixing is linear),  1

i
A
such that the activity is equal to the mole fraction.


  G  RT ln X
i
A A
i
A
 Fugacity Defined
For gaseous phases at fixed temperature: dGT = VdP
- Assume Ideal Gas Law PV  nRT;n  1
RT
V
P
RT 
dGT  VdP   dP  RT ln dP
P

PA = XAPtotal and the fugacity coefficient is defined as fA/PA, which

Is analogous to the activity coefficient. As the gas component
Becomes more ideal, fA goes to unity.

A  G  RT ln f A
A
 Equilibrium Constants
Mg2SiO4 + SiO2 = 2MgSiO3
olivine melt opx

G = 2  
opx ol mel t
MgSiO3 Mg 2 SiO4 SiO2 0

SiO
mel t
 GSiO
2
 glass
 RT ln a mel
2 SiO
t
2

 ol
Mg 2 SiO4 G  ol
Mg 2 SiO4  RT ln a ol
Mg 2 SiO4

 opx
MgSiO3 G  opx
MgSiO3  RT ln a opx
MgSiO3
 Equilibrium Constants, con’t.

 opx  ol  glass
RT ln( a opx
MgSiO3 ) 2

2G G G 
MgSiO3 Mg 2 SiO4 SiO2
(aol
a
Mg 2 SiO4
mel t
SiO2 )

G  RT ln K eq
F

where dG°F is referred to as the change in standard state

Gibbs free energy of formation, which may be obtained
from tabulated information
(aMgSiO
opx
)2

K eq  3

(aMg
ol
2 SiO4
 a mel t
SiO 2
)
Arrhenius Equation and Activation Energy

Kinetic Rate = A exp -Ea/RT

log D = log A - Ea/2.303RT

y = b + m•x

Slope = dy/dx = -Ea/2.303R

Intercept = b = log A

All processes that are

thermally activated have
similar form!