DILL CH_16 Solvation

Transfer of molecules from vapor to liquid

Consider salt (A) in liguid water (B). B is said to be volatile - or
easily evaporated component. The solution
is in equilibrium with water vapor. In equilibrium B (gas)  B (liquid)

Remember from ch 15: 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

From Ch11: chemical potential of ideal gas: B  kT ln(pB / pB0 ,int )where
2mkT 3/2
pB0 ,int (gas)  kT ( ) qrotation qvibrationqelectronic
2
h
and for liquid state from lattice model (Eq. 15.17)
zwBB 2
B (liquid)  kT ln x B   kT AB 1  x B 
2
 Recall Ch 15: 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 B / N .
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
Recall from ch 15: 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   BB   
 N A    N B  z wAB 
 2   2   2  N
 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).
Vapor pressure as a function of salt content
From equality of chemical potentials
 zwBB 
0  2
pB / pB,int  x B exp  AB (1  x B ) 
 2kT 
This can be written pB  pB0 x B exp  AB (1  x B )2 
 
 zw 
where pB0  pB0 ,int exp  BB  The linear dependence corresponds to AB  0 (known as
 2kT  0
the ideal case) and leads to p  p x known as
B B B

Raoult's law. Salt reduces gas pressure!!

 Vapor pressure for ideal case

Starting from the right side where x B  1 we have pure

water without salt. Adding salt lowers the pressure.
This is not due to energetics as AB  0 along this line.
Sooner (right) its is due to increase of entropy enabled
by mixing. Entropy of condensed B is larger when it is
with A.
 Vapor pressure in the non-ideal case
Now consider non-ideal case. If atoms dislike we
have AB  0 and the molecules B will have higher gas pressure
than in the ideal case. They try to escape contacts with A's.

When B's like A's (AB  0 ) they try to increase the number of AB bonds
leading to lower pressure of B's than in the ideal case.

Next we consider the left side of Fig. 16.1 where

the salt component dominates the condensede phase
and the volatile component is a minority.

The volatile component can also be a gas - like

high pressure CO2 in carbonated beverages!
In this case water is the nonvolatile component.
 Henry’s law

To get the vapor pressure of B at low

concentratios let x B  0 in Eqs (16.3 -4) to obtain

pB  zwBB   z  wAA 


 x B exp AB  
  x exp  
wAB  
B
pB0 ,int  2kT   kT  2 


This shows that partial pressure becomes proportiona to x B

pB  kH x B

where
 z  w   h 
kH  pB0 ,int 
exp  
wAB  AA 
  p 0 
exp  Solution 
2  B ,int 
 kT   
 kT 
 Microscopic processes and Henry’s law

The enthalpy of the solution

  wAA 
 
hSolution  z wAB  
  2 

is presented by the processes in Fig. 13.3
The linear regime below x B  0.5 is known as the Henry's law region.
B's will concentrate in liquid A if either the affinity AB is strong or affinity
AA is weak.
A weak AA affinity means that medium A readily accomodates a molecule B
because it costs little to open a cavity in A.
Affinity of one molecule in pure compound

zwAA
Why the energy cost to remove one A molecule is  and not - zwAA ?
2
See Figure above.

Because we should always think of the pure A system as a homogeneous pure

compound where the share of molecules on the surface is negligibly small!

The total cohesion energy for a system with N molecules is then zNwAA / 2
since each bond energy wAA is shared between two molecules! For N-1
molecules we then have total energy z N  1 wAA / 2 and their difference
zwAA
is  !
2
 Recall from Ch 15 Chemical potentials
The chemical potential of two component mixture is obtained from (N  N A  N B )
 F   F 

A    ; B   
 N A   N B 
B
T ,N A
T ,N
A    F 
   
 N 
 A 
NA NB zwAA NN B  N AN B 
    ln    1     AB
kT  
 N A  kT T ,N  N  N N 2kT N2
B
zw 2
 ln x A  AA  AB 1  x A  similarly for B atoms
2kT
B zwBB 2
 ln x B   AB 1  x B     o  kT ln x
kT 2kT
B0 zw 2
  ln B  BB  AB 1  x B 
kT 2kT
 Activity coefficient
Express the gas-phase chemical potential of B
B (gas)  B0 (gas)  kT ln pB
and for the liquid phase
B (liquid)  B0 (liquid)  kT ln  B x B  x B  .
 
The function
B x B 
is called activity coefficient and B x B  x B activity and
the quantity
B0  B0 (liquid)  B0 (gas)
is called standard-state chemical potential.

Solvent convention B  1 as x B  1 and

Solute convention by B  1 as x B  0
  0  Can be used to fit B x B 
pB 
Setting B0 (liquid)  B0 (gas) gives  B x B  exp  B  to the experiment if
xB  kT 
  B0 is known
 Solvent and solute conventions
From lattice model the Solvent convention B  1 as x B  1 is
B0 zwBB

kT 2kT
and from Eq 16.13
 2
B  exp  AB 1  x B  
 
The nonideal concentration is due to AB interactions.

Solute convention B  1 as x B  0
B0 zwBB z  wAA 

  AB  wAB 
kT 2kT kT  2 
describes the process in Fig. 16.3. When the solute is
the exchangeable component B0 represents the free energy cost
of inserting a B molecule at infinite dilution into otherwise pure A
solvent. Then
B  exp  AB x B x B  2 .
 
Adding solute and boiling temperature
Pure water boils at pB  1atm at T  Tb 0  100 0C:
 zw 
0 
pB  1atm  pB ,int exp  BB  Eq. 16.18
 2RTb 0 
 2 
for salty water (x B slightly less than 1) from Eq. 16.2  since 1  x B   0 
 
 zw 
pB  1atm  pB ,intx B exp  BB  Eq. 16.19
0
 2RTb1 

zwBB  1 1 
setting Eq. 16.18 = Eq. 16.19 and taking logarithm ln x B    
2R Tb 0 Tb1 
For small salt concentration and T  Tb1  Tb 0 one obtains
o
using Taylor approximations, hvap  zwBB / 2 and x A  1  x B
RTb20x A
T 
o
hvap
All information needed are the boiling point salt concentration and
the enthalpy of vaporization of pure water.
Adding salt and the freezing of water

Adding salt lowers the freezing point by reducing the escape of

water molecules from liquid to solid state.
 Depressing of freezing point

The lowering of the freezing point by solute can be treated

in the same way as the elevation of the boiling point
kTf2x A
Tf  Tf  T 
o
hfus
where Tf  T and Tf is the freezing point of pure water (B).
o o o
The melting enthalpy is given by hfus  hliquid  hsolid
 Adding solute and osmotic pressure
The Suppose that we have pure liquid B on right and a
mixture of A and B on left. Between there is a
semipermeable membrane that prevents B to go trough
while A's can move trough.

A pressure difference developes to make the

flow of B's equal from left to right and right to left.

Chemical potential of B must be equal on both sides:

B pure, p   B mixture, p  , x B 
 Understanding osmotic pressure

To find the relation between osmotic pressure and x A we

use the thermodynamic cycle above.
(1) Increase the pressure to p  . (2) Add solute at constant pressure. For step (1)
p 
B B V
B pure, p     B pure, p    dp use Maxwell equation   vB
p p N B
p
where vB is the molar volume of B to obtain
p 
B pure, p     B pure, p    vB dp  B pure, p   vB
p
as vB is typically pressure independent.
 Understanding osmotic pressure
Step (2)
Add solute so solvent at any pressure p0 gives
B mixture, p0   B pure, p0   RT ln B x B 
So add solute at point pure, p    to obtain
B mixture, p +    B pure, p   vB  RT ln B x B  Eq. 16.34

Substitute Eq. 16.30 to Eq. 16.34

vB  RT ln B x B 

To get the osmotic pressure in terms of dilute solution B  1 use

x B  1  x A and expand the logarithm to get for ideal solution
RTx A nART nART
    cART .
vB nB vB V
Transfer of solute to another medium1/2
In the previus example solute was kept on one side of the membrane.
Here we discuss two different solvents A and B and transfer of
solute s between them trough a membrane - say.
The concentrations on the A and B sides are xsA and xsB .

The partitioning coefficient is defined KAB  xsB / xsA .

The total number of solute molecules is fixed. The

chemical potentials of the solute are sA and sB . In equilibrium
sA  sB
Use lattice model for s in each liquid
s (A) zwss 2
 ln xsA   sA 1  xsA 
kT 2kT
s (B ) zw 2
 ln xsB  ss  sB 1  xsB 
kT 2kT
Transfer of solute to another medium 2/2
Setting the chemical potentials equal
gives
 x 
 2 2
  sA 1  xsA  - sB 1  xsB 
B sB 
ln KA  ln 
 xsA 
This can be expressed also in form
 x   0
(B )   0
(A)   
B
ln KA  ln  sB    s s
 ln  sB 
 xsA  kT  sA 

The quantity  0  s0 (A)  s0 (B ) is called free energy of transfer.

For very dilute solute on both sides xsA, xsB  1.Then in solute
convention sA  1 as xsA  0 and sB  1 as xsB  0 one obtains

s0 (A)  s0 (B )

ln KAB   sA  sB
kT
Applications
Lattice model and solute partitioning
 Partitioning and lattice model
From Eq. 16.44 we obtain using definition of 
 z   w  w  
 w  w 

sA  sB    wsB  ss BB   w  ss AA 
 kT    sA
 2   2 
 z  wAA wBB 

  wsB  wsA   
 kT  2 2 
In Figure 16.11 the partitioning process is driven by energetic cost of:
Opening a cavity in B (Step 1, - wBB / 2 )
Transferring a solute molecule from medium A
into the cavity B (Step 2 , wsB  wSA )
Closing the cavity in A (Step 3, wAA / 2)

Writing the chemical potential using solute convention as

s (A)  s0 (A)  kT ln csA   s0 (A)  kT ln csA 
points out how the convention simplifies the chemical potential in
very dilute case.