Born Model : Thermodynamic cycle to calculate the work done

in transferring a charged sphere from vacuum into the solvent.

Main assumption: Charged sphere

Only charge on ion is in vacuum
Vacuum
Responsible for ion/solvent
i t
interaction.
ti
Hence ion/solvent
Remove charge Work of discharging WD
interactions are solely
electrostatic in nature.

Uncharged
h d sphere
h
in vacuum
The following thermodynamic cycle is
developed. The ion i , represented as a GS Zero electrostatic work of transfer
charged sphere of radius R,is
considered
id d in
i to
t be
b initially
i iti ll located
l t d in
i a WT = 0
vacuum, and the work Wd required to Solvent
strip the ion of its charge q = zie is Uncharged sphere
determined . Then this uncharged in solvent
sphere
p is transferred into the solvent
dielectric medium . We assume that
this transfer process involves no work .
Then the charge on the sphere inside Charging process Work of charging WC
the solvent is restored to its full value
q = zie and the work done in charging
Wc is determined . Finally, the ion is
Charged sphere
transferred from the solvent back into
in solvent
vacuum . The work done in this
transfer process is - Gs .
 In a thermodynamic cycle the algebraic From fundamental electrostatics we recall
Sum of all the work terms is zero. that the electrostatic potential at a certain
point in space is defined as the work done
Wd  Wtr  Wc  G s  0 to transport a unit positive charge from
G s  Wc  Wd infinity to that specific point . Now the
electrostatic potential at a point located a
We now evaluate the work done in charging a distance r from a charged
h sphere
h  (r)
( ) is
sphere of radius R from q = 0 to q = zie , given by the product of the electric field
where zi denotes the valence of ion i and e is strength E(r) (which defines the electric
the fundamental electronic charge . To do force per unit charge) acting on the moving
this
h we start off with h an uncharged
h sphere
h test charge
h andd the
h distance
d r through
h h
and add infinitesimal amounts dq to the sphere which the charge is carried .
until the final charge level is attained .The R R
product of electrostatic potential  and the
 r     E r dr  
1 q q
4 0  r 2
dr 
charge
h increment dq
d gives theh work k increment 4 0 R

dw.
Direction of
dw   dq Increasing
potential
p

The total work done in charging the sphere

is obtained by summing over all the little Direction of
Direction of
Positively Electric field
increments dw. Charged sphere
transport
of
f charge
g Unit positive
zi e zi e Test charge

Wc   dw  dq Total charging zi e zi e

Wc   r  R dq 
1 q
4 0 0 R
0 0
work Wc dq
0

1   zi e  
2

0 = permittivity of vacuum = 8.854 x 10-12 C2N-1m-2   

4 0  2 R 
 Work done in discharging sphere Note that in the expression for Gs there is a
iss negative
negat ve of charging
charg ng work, Wd = - Wc negative sign heading the rhs . Now since the
dielectric constant r > 1 always and so 1/r < 1 then
Gs will always be negative . The solvation proceeds
1  zi e  
2
Wd     spontaneously : ions prefer to be solvated than to be
4 0  2 R  in vacuum . Hence solvation is thermodynamically
f
favourable.
l Theh Born equation also
l predicts
d that
h the h
The recharging work done when the smaller the ion (smaller R) and the larger the
sphere is present in the solvent dielectric constant , the greater will be the solvation
dielectric
d electr c iss mod
modified
f ed by the free energy .
macroscopic dielectric constant of
the medium r . The Entropy and enthalpy of solvation are readily
evaluated. Note that HS is a quantity readily
compared with experiment.
1  zi e  
2
Wc    H s  Gs  TS s
4 0  2 r R 

Born expression for Gibbs energy of  Gs  N A zi2 e 2 1  r

Solvation. S s    
 T  P 4 0 2 R  r T
2

1  zi e   1
2
Gs  Wd
vac
 Wc
diel
    N A zi2 e 2  1 T  r 
1  H s   1   2 
4 0  2 R   r  4 0 2 R   r  r T 

Molar Gibbs
Energy of   zi e 2   1  A clear prediction is that the
solvation Gs  
N N A  q2   1  solvation free energy should
  1       1  
A
4 0  2 R   r  4 0  2 R   r  vary inversely with ion size R