THERMODYNAMIC TREATMENT OF ION-SOLVENT INTERACTIONS: THE BORN MODEL As we have discussed earlier, the ion-solvent interaction is one of solvent

dipoles interacting with the electric field of the ion. We will now calculate the free energy of the ion-solvent interaction, and in doing so will obtain the solvation energy part of the Henry's law standard state. There are two models to consider for the solvent: 1. a structure-less continuum of dielectric 2. discrete molecules with dipoles, polarizability, etc.

Discrete Model

Continuum Model

Although it seems farther from reality, the continuum model has proven to be a rather accurate representation of the interaction, and we will employ it in the present discussion. The continuum model of ion solvation is often referred to as the "Born model" in honor of its creator. We will calculate free energy of transfer of an ion from medium 1 of dielectric constant 1, to medium 2 of dielectric constant 2. This will be referred to as GBorn. If medium 1 is a vacuum, GBorn is just the free energy of solvation. The approach to the calculation is diagrammed below.

G1 G 2

1 G Born

G 3

Why is GoBorn labeled as a standard state free energy change? Because it is a free energy change in the Henrys law sense, ie, it only involves ion-solvent interaction, and includes no contributions from solute-solute (ion-ion) interactions, and no entropy of dilution. Now from the thermodynamic cycle,
o o G Born = G 1 + Go 2 + G3

(1)

This path corresponds to first discharging the ion in medium 1 (G1o), transferring the discharged ion from medium 1 to 2 (G2o), and finally recharging the ion in solvent 2 (G3o).The free energy of the second process is just the free energy difference of the discharged equivalent ion in the two solvents. There are no ion-solvent terms here, since there is no charge. The size of this term depends on the chemical rather than electrical properties of the ion. We will discuss this later, but for the moment we focus on the electrical terms. The energies of charging or discharging can be computed according to the following model in which we charge the ion by bringing infinitesimal pieces of charge from infinity and placing them on the surface of the ion. This process is continued until the final charge is reached.

ion of radius a

dq r= = 0

=
The Charging Process

potential at the ion surface

What is the energy of bringing in charge dq from infinity and placing it on the surface of a sphere with radius a? Recall

G(r) = q and dG = dq

(2)

What is ? To calculate this, it is necessary to recognize a property of any spherically symmetric charge distribution, namely that the electric field and potential are the same as those generated by an equivalent charge placed at the center of the sphere. This is just like gravity. The earth behaves as if all its mass were concentrated at the center of the earth. Thus, the field from the charge looks like

The potential of a point charge was calculated earlier as

(r) =

q 4 o r

(3)

Apparently, this is applicable to an ion of radius a, as long as we are outside the ion. In the charging process, a charge dq is brought from infinity to the surface of the ion at r = a. Thus, the appropriate potential is

(a) =

q 4 o a

(4)

Then,

dGcharging = dq =

q 4 o a

dq

(5)

This expression must be integrated from 0 charge to the final charge on the ion, Ze, where Z is the valence. That is,

G charging =
and

1 4 o a
2 2

Ze

qdq
0

(6)

G charging = Z e 8 o a

(7)

Gdischarging = - Gcharging

(8)

We are now in a position to compute the free energies of the charging and discharging steps.

G = o 1

8 o 1 a

Z e

(9)

G =+
o 3

8 o 2 a

Z e

(10)

Therefore

o Born

2 2 e ( 1 - 1 )+ o Z = G2 8 o a 2 1

(11)

Note that if 2 < 1, then Go >0 and it takes work to move ion from water to a less polar solvent, such as vacuum or a hydrocarbon. The term G2o will be important in certain cases when the discharged ion has unusual chemical properties, and we will discuss these later FREE ENERGY OF SOLVATION Consider transferring an ion from a vacuum to a medium of . Furthermore, consider a "pure" charge interaction, ie, the solvent does not have any specific chemical interactions with the discharged ion. Thus G2o = 0, and

G
Two points to note: a. G is < 0 if > 1

o solvation

e 1 = Z ( - 1) 8 o a
2 2

(12)

b. G decreases as the ionic radius increases. Why? The field and potential at the ion surface become less, because we are farther from the apparent center of charge concentration.

ENTHALPY AND ENTROPY OF SOLVATION The solvation free energy according to Born, for one mole, is
2 2 e NA 1 Z ( - 1) G solvation = 8 o a o

(13)

This represents the free energy change accompanying the creation of an ordered solvent structure around the central ion. Now

G o ( )P = - S o T
Therefore

(14)

Z e NA( ) - So solvation = 8 o a T
2 2

1 ( )

(15)

Now

1 1 d( ) = - ( 2 )d

(16)

and we have

S
Experimentally, it is found that

o solvation

2 2 e N A 1 d Z ) = ( 8 o a 2 dT

(17)

d <0 dT

(18)

Thus, Sosolvation <0. This can be interpreted as due to the increase in order of solvent molecules as they orient around the ion.

What about the enthalpy of solvation?

G o = H o TS o H o = G o + T S o H H
o solvation

N A Z 2e2 1 N A Z 2 e 2 1 d = ( 1) + T ( ) 8 o a 8 o a 2 dT N A Z 2e2 1 T 2 d = [( 1) + 2 ] 8 o a dT

(19)

solvation

Note: for calculations, the quantity e2NA/8o = 6.9 x 10-5 joules-meter For any >1, the term in brackets is negative, and the enthalpy of solvation is negative. This is as expected, because the ion-solvent interaction is attractive.