CHEM 43924

Electrochemistry 2018/2019

Boltzmann constant kB = 1.38 × 10-23 m2 kg s-2 K-1; Avogadro constant NA = 6.023 x 1023
mol-1; Charge of the electron = 1.60 x 10-19 C; p = 3.14

1.
a) Debye length k-1, which is a measure of the thickness of the ionic atmosphere is given
by,
𝜀# 𝜀$ 𝑘% 𝑇
𝜅 !" = #
𝑁& 𝑒 ' ∑ 𝑐( 𝑍('
Calculate the Debye length k-1 for a 0.001 M solution of NaCl in water at 25°C.
(Permittivity of the vacuum 𝜀) = 8.854 x 10-12 C2 J-1 m-1, relative permittivity for an
aqueous solution 𝜀$ = 78.5)
(15 marks)

b) An ion of charge ze0 and radius r is transferred from a solvent of dielectric constant
ei to a solvent of dielectric constant ef. Derive an expression to calculate the free
energy change associated with this transfer using the Born model.
According to the thermodynamic cycle for the Born model, work (free energy
change) in transferring a charged sphere from vacuum into the solvent (Born
equation) can be expressed as,
𝑍'𝑒' 1
∆𝐺*#+,-.(#/ = ( − 1)
8𝜋𝜀) 𝑟 𝜀$
(15 marks)

DGiàf = Gf - Gi = (Gf - Gvacuum ) - (Gi - Gvacuum )

= DG vacuumàf -DG vacuumài

Therefore, from Born equation

 𝑍'𝑒' 1 𝑍'𝑒' 1
∆𝐺(→1 =5 6 − 178 − 5 9 − 1:8
8𝜋𝜀) 𝑟 𝜀1 8𝜋𝜀) 𝜀(

𝑍'𝑒' 1 1
∆𝐺(→1 = 6 − 7
8𝜋𝜀) 𝑟 𝜀1 𝜀(

c) What is the Born free energy change involved in transferring a Na+ ion (radius = 95
pm) from a vacuum to water (aqueous media) 25°C?
(10 marks)

d) Correspondingly, calculate the energy of the ionic atmosphere for the same ion, in
10-3 M sodium chloride solution, which was considered in part (a).
According to ion-cloud theory, change in chemical potential due to ion/ion
interactions is derived as,
𝑁& (𝑍( 𝑒)'
∆𝜇(,3 =
8𝜋𝜀# 𝜀$ 𝜅 !"
(15 marks)

e) When a metal dissolution is coupled (M(s) à Mn+(aq) + ne) with a redox reaction
(O + ne à R), following thermodynamic and kinetic parameters were determined.
Anodic equilibrium potential (E0)a = -0.4 V
Cathodic equilibrium potential (E0)c = 0.2 V
Corrosion current (Icorr) = 0.2 A
Corrosion potential (Ecorr) = 0.0 V
 i. Sketch suitable Butler-Volmer graph (to show the current – potential
relationship) with appropriate labeling.
(15 marks)

0.2
V

= 0.0 V

M à Mn+ +
ne
-0.4
V

ii. Sketch suitable Evan’s diagram with appropriate labeling.

(15 marks)

ne
+
O ne
à n+ +
R M
0.2 à
M
V

0.0 V
O
+n
eà
-0.4 M n+ R
V +n
eà
M

e) The reference electrode, a specific type of electrode comprised of well-defined

materials, has a known stable potential to which all other electrode potentials are
referenced. Sketch suitable Butler-Volmer plots (to show the current – potential
relationship) for a good reference electrode and a working electrode on the same
graph.
(15 marks)