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New Course Electrochemistry PPTX, Slides of Electrochemistry

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2018/2019

Uploaded on 11/09/2019

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Energetics of ionic solvation : Non-structural Treatment.
Born Model (1920)
Born Model (1920)
We consider the following situation.
Initial state: no ion/solvent interactions.
This corresponds to ion in vacuum
Vacuum
Ion
This corresponds to ion in vacuum
.
Final State: ion/solvent interactions operative.
This corresponds to ion in solution.
Thermodynamics states that for reversible
Process taking place at const T & P
Vacuum
Free energy change
GS
Process taking place at const
.
T & P
,
Free Energy change G equals net work
(other than PV work) done on system.
We need to calculate the work done in
Transferring an ion from vacuum into a solvent
Solvent
Charged
Transferring an ion from vacuum into a solvent
.
A solvent such as water has a complex structure.
To simplify our analysis we dispense with structure
Charged
sphere
nucleus
Electron
cloud
ii
qze
i
r
i
r
Net charge
and regard the solvent as a structurless dielectric
continuum. This medium has a dielectric constant
given by SThe ion also has structure (ion +
associated hydration sheath). We represent the ion
d d
nucleus
as
a
c
arge
sp
ere
o
net
c
arge
qi=
ziean
d
ra
d
ius
ri.
l
Dielectric constant S
Gibbs energy of solvation computed via
Structured solvent Structur
l
ess
Dielectric
continuum
a thermodynamic cycle.

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Energetics of ionic solvation : Non-structural Treatment.Born Model (1920)Born Model (1920)

We consider the following situation.Initial state: no ion/solvent interactions.This corresponds to ion in vacuum

Vacuum

Ion

This corresponds to ion in vacuum

Final State: ion/solvent interactions operative.This corresponds to ion in solution.Thermodynamics states that for reversibleProcess taking place at const T & P

Vacuum

Free energy change 

G

S

Process taking place at const. T & P,Free Energy change

G equals net work

(other than PV work) done on system.We need to calculate the work done inTransferring an ion from vacuum into a solvent

Solvent

Charged

Transferring an ion from vacuum into a solvent. A solvent such as water has a complex structure.To simplify our analysis we dispense with structure

Chargedsphere

nucleus

Electroncloud

i^

i

q

z e

i r

i

r

Net charge

and regard the solvent as a structurless dielectriccontinuum. This medium has a dielectric constantgiven by

S

The ion also has structure (ion +

associated hydration sheath). We represent the ion

h

d

h

f

h

d

d

nucleus

as a charged sphere of net charge q

i

= z

e and radiusi

r

i

l

Dielectric constant

S

Gibbs energy of solvation computed via

Structured solvent

StructurlessDielectriccontinuum

a thermodynamic cycle.