DILL CH_15 Solutions and Mixtures

• Entropy of solution
• Energy of solution
• Meanfield approximation
• Chemical potentials
• Interfacial tension
 Entropy of solution

The T ,V , N system allows simple use of lattice model We can think the number of
microstates in the following way:
The extremum for equilibrium is obtained for We first take a non-ordered subset
of NA molecule sites, the remaining
F  U - TS sites are then filled by B- type
Assume two types A, B of molecules in a lattice molecules.

total number given by N  N A  N B .

The number of microstates for particular
configurationis given by
N!
W 
NA ! NB !
 Calculating entropy
The entropy is calculated in the usual way from
S  k lnW .
Using Stirlings formula ln n !  n ln n  n
Ssol  k (N ln N  N A ln N A  N B ln N B )
 k (N A ln N  N B ln N  N A ln N A  N B ln N B )
N  N  N  N 
 Nk   A 
ln  A   B
ln  B 
 N  N  N  N 

 k (N A ln x A  N B ln x B )
where x A  N A / N  x is the mole fraction. Then
Ssol
 x ln x  (1  x ) ln(1  x )
Nk
 Understanding entropy maximum
Put N A of A-type molecules in a container already including
N B B -type molecules
If the molecules dont mix there is no increase of entropy.
If the molecules mix the entropy will increase from zero
to Ssol
 Energy of a solution
In Energy of nonideal solution depends on the order
of molecules as different bi-molecular interfaces
have different energies- we have AA, AB and BB
interface energies or bond energies.
U  mAAwAA  mBB wBB  mAB wAB
How to express number mxx in terms of N AN B ?

The total number of sides of a particles

is
zN A  2mAA  mAB since
 2 A-sides 
(Number of AA bonds)x  
 AA-bond 
 1 A-side 
(number of AB-bonds)x  
 AB-bond 
similarly
zN B  2mBB  mAB
 Mean field approximation
The total energy involves only one unknown mAB
 zw   zw   wAA  wBB 

U   AA 
 N   BB 
 N  w   m
   

A B AB AB
 2   2   2

The unknown mAB is calculated in the mean field

approximation starting from hypothesis that for any
N A and N B the particles are mixed as randomly as
possible.
Consider one particle site. The probability that it is occupied
by B - type molecule is pB  N / N B .
Since there are z-nearest neighbor for each A-molecule
the average number of AB interfaces is z (1  x ) for each A
molecule. In total
zN AN B
mAB   zNx (1  x )
N
 Total energy
zN AN B
Use mAB   zNx (1  x ) to calculate the total energy
N
 zw   zw   wAA  wBB  N AN B
U   AA  N    BB 
 N  z w  
   
 N
A B AB
 2   2   2
 zw   zw  N AN B

  AA  N   BB  N  kT 
 2  A  2  B AB
N
where we have defined exchange parameter
z  wAA  wBB 

AB  wAB 
kT  2 
This assumes that all interactions are equally favorable
Bragg-Williams mean-field approximation!

If AA interactions are strong clusters of A-atoms are

more common (if BB interactions are strong BB clusters
dominate. If AB interactions are strong AB clusters
dominate.
 Free energy
Calculate the free energy F  U - TS from
 zw   zw 

U   AA  N   BB  N  kT  N AN B
 
 2  A  2  B AB
N
and
N  N  N  N 
S  Nk   A 
ln  A   B
ln  B 
 N  N  N  N 
This gives
F N A, N B   zwAA   zw 
 N AN B
  
N  
BB 
 N  AB
kT  2kT  A  2kT  B N
  N   N 
 
 N A ln  A   N ln  B 
 N  B 
  N 
The mixing free energy is given as the difference between pure
states of NA and NB atom systems and the solution and is given by
FSolution  F (N A, N B )  F (N A, 0)  F (0, N B )
 Chemical potentials
The chemical potential of two component mixture is obtained from
 F   F 

A    
; B   
 N A   N B 
T ,N
B
T ,N
A

A    F 
  
 N 
 A 
NA NB zwAA NN B  N AN B 
    ln    1     AB
kT  N kT   N N N 2kT N2
 A  T ,N 
B

zwAA 2
 ln x A   AB 1  x A 
2kT
similarly for B atoms
B zwBB 2
 ln x B   AB 1  x B 
kT 2kT
 Approximations 1/2
The thermodynamical functions should be calculated
from partition function including sum over the number of AB contacts mAB
E (N A ,N B ,mAB )/kT
Q  W (N A, N B , mAB )e
mAB
where E is the energy for mAB contacts and W the number
of atom configurations for fixed mAB.

We approximated the exact partition function by mean field value

N!
Q eU /kT
NA !NB !
 Approksimations 2/2
The second approksimation was to left away rotations, vibrations
and electronic density of states. Including internal degrees we
would have
N N E (N A ,N B ,mAB )/kT N N N!
Q  qA A qB B  W (N A, N B , mAB )e  qA A qB B
NA ! NB !
e U /kT
mAB
N N
where qA A and qB B are internal partition functions of A and B molecules.
For free energy one obtains including internal degrees
F N A, N B   zwAA   zw  N AN B
   N   BB  N  
kT  2kT  A  2kT  B AB
N
  N   N 
 
 N A ln  A   N ln  B   N ln q  N ln q
 N  B  N  A A B B
    
and for the chemical potentials
A  x  zw
 ln  A   AA  AB 1  x A 
2

kT  qA  2kT
B  x  zw

 ln    B  BB
 AB 1  x B 
2

kT  q 
B 2kT