ELECTROCHEMICAL EQUILIBRIUM

Electrochemical reactions involves free electrons that are transferred from a metal
to a species in a solution.
Importance of EMF measurements
1. thermodynamics quantities for the reaction that occurs in the cell can be
obtained over a range of temperature.
2. activity coefficient of electrolyte can be calculated
3. electrochemical cells are of practical interest in that they offer the means to
convert the Gibbs energy change of a chemical reaction into work with out
the second-law losses of heat engine.

Coulombs Law
Electromagnetic interaction (attractive/repulsive interaction)

The electrostatic force F between two charges Q1 and Q2 separated by

distance r
In a vacuum
Q1Q2
F
4 o r 2
Q coulomb, C
r meter, m
F Newton, N = J mo permitivity of a vacuum and has the value 8.854x10 -12 C2/J-mol
In a medium having a relative permitivity,
F

Q1Q2
4 o r 2

Electric Field Strength, E at any point is the force exerted on a unit charge at that
point. The field strength at a distance r from a charge Q, in a medium of dielectric
constant is thus
E

F
Q

Electric Field is the negative gradient of the electric potential

E = -
In x direction

Electric potential at a point is the work required to bring a unit positive charge
from infinity to a point in question.

Q2 dr
=
4 r 2
o r

Q2
Equilibria Involving Potential Differences
4 or r
Work done on the charge when it is moved through an electric potential difference .

dw = dQ
Work required to bring two charge particles together from an infinite distance to a
desired distance.
Q1Q 2
w
4 o r
If ions with charge no. zi are transferred

dQ = ziFdni
F Faraday constant (96,485.309 c/mol)
zi charge no. of the ion in terms of the proton charge with the sign of the ion.
Solve problems 7.1 and 7.2
Faradays Law
1. The mass of an element produced at an electrode is proportional to the quantity
of electricity, Q passed through the liquid.
Q = It
I current (ampere, A)
T time (second, s)
2. The mass of an element liberated at an electrode is proportional to the equivalent
weight of the element.
Importance: Faradays work on electrolysis was of great importance in that it was the
first to suggest a relationship between matter and electricity

Classification of Substances
1. Non conductors do not conduct electricity
2. Conductors conducts electricity
a. Electronic conductors conduct electricity by flow of electrons
b. Electrolytes conduct electricity by migration of ions.
Electronic Conductor
Resistance of a conductor varies directly to its length and inversely to its cross
sectional area.
__
A
__
-------- l--------R

l
A

R resistance, ohms ,
l length, meter

l
R
A

A Area, m2
resistivity

The magnitude of the electric potential difference between the ends of the conductor
l

R
I

potential difference, volt

Ohms Law

Electrical Conductance, G the reciprocal of the resistance

G

1
R

1 A
A
k
l
l

G conductance, siemens
k - proportionality constant, the conductance of a
unit cell, conductivity, siemens/m

Problem:
Electrolytes
These are substances when dissolved in water or any other appropriate solvents can
conduct electricity, and also exhibits colligative properties.
For dilute solutions of non electrolytes:
1. P = Posolvent Xsolute
2. Tb = Kbm
3. Tf = Kfm
4. = CRT

The colligative properties of electrolytes are greater than the colligative properties of the nonelectrolytes
The Vant Hoff Factor, i
i

T f
Tb
P

P o Tb o T f o o

For dilute solutions of electrolytes:

1. P = iPosolvent Xsolute
2. Tb = iKbm
3. Tf = iKfm
4. = iCRT
Problem
Arrhenius Theory of Electrolytic Dissociation ( Weak Electrolytes)
1. Electrolytes in solution are ionized. + = 2. An equilibrium exists between ions and unionized molecule
3. At infinite dilution, electrolytes are 100% ionized.
Calculation of Degree of Dissociation, from Colligative Data
Consider a hypothetical reaction
AxBy
xA+ + yBStart
m
0
0
Reaction -m
xm ym
Equilibrium m m
xm ym
m total = m m + xm + ym
= m( 1 + x + y)
= m [1 + (x + y- 1)]
Let v = total number of ions
m total = m [1 + (v- 1)]
Tf = Kfm
= Kfm [1 + (v- 1)]
But:
Tf = i Kfm
i = Kfm [1 + (v- 1)]
Kfm
i = 1 + (v- 1)
=i1
v-1
Problem:
Conductance of an Electrolytes

Molar Conductivity,

k
C

k electrolytic conductivity

C.- Molar concentration

The meaning of can be visualized as follows:
Consider the following cell with parallel plates a unit distance apart

Volume = 1mole/C
unit separation

unit cube, unit area

The molar conductivity is the conductance across the plates
Prob. The electrolytic conductivity of a 0.1M solution of acetic acid was found to be 5.3 x 10-4
siemens per cm. Calculate the molar conductivity
Variation of Conductance with Concentration
Molar conductivity increases with dilution for both strong and weak electrolytes, the
limiting value of the conductivity is known as the molar conductivity at infinite dilution,
o at zero concentration

1
C

as

C0
o

o -

limiting molar conductivity (when the ions are so far apart that they do not interact and
retard each other as they move toward the electrodes

Degree of dissociation from molar conductivity

From Ostwald Dilution Law

Initial amount
Reaction
Equilibrium

AB A+ + BC
0
0
-C
C
C
C- C
C
C

nT = C + C = C(1 )

C o
2
C C C
K
C 1
1

1 o

Strong Electrolytes
Debye Huckel Theory
I = (C1z12 + C2z22 + .)
I ionic strength
C concentration
Z valence
Example: KCl K+ + ClI = [ C(1)2 + C(-1)2
Molar conductivity decreases only slightly as its concentration is increase
Friedrich Kohlrausch showed that at low concentration the molar conductivities of strong
electrolytes vary as the square root of the concentration
= o (P + Q o) C

P and Q are constant

Law of Independent Migration of Ions at infinite dilution each ion migrates independently
of its co-ions and contributes to the total conductance of an electrolyte a definite
share which depends only on its nature and not at all on the ion with which it is
associated
o = +o + -o

+o & -o - ions conductivities at infinite dilution

Example: KCl
oKCl = oK+ + oCl= 1449.9 S-cm2/mol
Molar conductivities of ions at infinite dilution
1. Ionic Mobilities,
- speed of an ion as it moves under the influence of an electric field
Let
potential drop
C+ - concentration of a univalent cation
+ - mobility of the positive ion

Then

S+ = +
No of ions = + C+
k+ = current/potential drop
k

F C

k+ = F+C+
o

k
F C

C
C

+o = F +

-o = F -

Example: The mobility of a sodium ion in water at 25oC is 5.19 x 10-4 cm2/v-s. Calculate the
molar conductivity of the sodium ion.
2. Transport Number or transference number or migration number, t. is the fraction of
current carried by each ion present in solution
Consider
AaBb aA+ + bB
I+ - quantity of electricity carried by a mole of the ions A z whose charge
number is z+ crossing a given cross sectional area in unit time
I+ = aFz+ +
I- = aFz- az
aFz
t
t
aFz bFz
az bz
t

bz
az bz

For an electrically neutral solution

az+ = bzt

From ionic conductivities

0
t o

Hittorf Method

0
t o

Anode

Center

t+M+

t+M+

1mole Adischarge

1 mole M+

discharge

t-A-

net loss of
1 t-

Cathode

net no change
in concentration

t-A
net loss of
1 t+

At the cathode
A loss of 1 t+ = t- mol of M+, and a loss of t- mol of AAt the center
No change in concentration
At the anode
A loss of 1 t- = t+ mol of A-, and a loss of t+ mol of M+
The net loss is therefore t+ mol of MA
It follows that
amount lost from anode compartment =
amount lost from cathode compartment

t+
t-

Since
t+ + t- = 1
t+ = amount lost from anode compartment
amount deposited
t- = amount lost from cathode compartment
amount deposited
Problem: A solution of LiCl was electrolyzed in a Hittorf Cell. After a current of 0.79A had
been passed for 2 hours, the mass of LiCl in the anode compartment had decresed
by 0.793 gram.
a. Calculate the transport number of Li+ and Cl- ions
b. If o LiCl is 115.0 S-cm/mol, what are the molar ionic conductivities (o) and
ionic mobilities (}?
Equation for an Electrochemical Cell
1. Galvanic cells chemical reactions occur spontaneously

Anode
(-)

e-

e-

Cathode
(+)

Mnemonic
Cathode electrode on the right, reduction reaction occurs (this is positive in
a galvanic cell because electrons are flowing into it)
Ox + ne- Red
Anode electrode on the left, oxidation reaction occurs
Red Ox+ ne2. Electrolytic cells chemical reactions are caused by an externally applied
potential difference.
Cathode
(-)

e-

e-

Anode
(+)

Electrochemical Cell
1. Cells with out liquid junction
Example
Pt

Pt

H2
Coating of Ag(s)
and AgCl(s)
HCl in H2O
Pt(s) I H2(g) I HCl(m) I AgCl(s) I Ag(s)
I represent phase boundaries

can be held at equilibrium indefinitely, and therefore they can be given exact
thermodynamic treatments.
EMF depends on the electrodes and the activity of the electrolyte solution

2. Cells with liquid junction

Example:

Zn(s) I Zn2+(m1) Cu2+(m2) I Cu(s)

Ag(s) I AgCl(s) I Cl-

Ag+(m) I Ag(s)

- junction between two liquids

- represents a salt bridge
Zn

Cu

ZnCl2(aq)

CuCl 2(aq)

Relationship between the electromotive force for a cell and the chemical potentials or
activities of the reactants and products:
Consider the ffg. Cell without a liquid junction
PtL I H2(g) I HCl(m) I AgCl(s) I Ag(s) I PtR
Electrode reaction
2AgCl(s)

2e- (PtR) 2Ag(s) + 2Cl-(m)

H2(g) 2H+(m) + 2e- (PtL)

Cell reaction:
H2(g) + 2AgCl(s) + 2e- (PtR) 2H+(m) + 2Ag(s) + 2Cl-(m) + 2e(PtL)
Or
H2(g) + 2AgCl(s) + 2e- (PtR) 2HCl(m) + 2Ag(s) + 2e(PtL)
Equilibrium relation:

i I = 0

Thus,
2(HCl,aq) + 2(Ag,s) 2FL - (H2,g) -2(AgCl,s) + 2FR
or
rG

= -2F(R - L)

rG

= -2FE

where
E = R - L
E electromotive force , Cell potential
- the difference in potential of the two electrodes, measured in volts, V.
Conventions Regarding Signs of EMF:
Net electrical work = IeI FE
-G = IeI nFE

G = - IeI FE
Relation Between Signs of G and EMF
G
+
0

Reactions
1. Spontaneous
2. Non-spontaneous
3. Equilibrium

EMF
+
0

Electromotive Force in terms of activities

Nernst Equation
-Ie-I FE = -Ie-I FEo + RT ln a product
a reactant
E = Eo RT
ln a product
Ie-IF
a reactant
At equilibrium
Eo = RT ln K
Ie-IF
where K is the equilibrium constant of the cell reaction

Activity of Electrolytes
i mi

or ai i mi
mo
where mo standard value of the molality (1mol/kg solvent)
ai

For strong electrolyte Av+Bv-,

m = (m++ m--)

m = m (++ --)

= (++ --)
+ + -

where
therefore

a Av+Bv- =

(m)

or

a Av+Bv- = m (++ --)

Solve problem 7.4

Debye- Huckel Theory
I = mi zi2
I = (m1 z12 + m2 z22 + ..)
where

zi charge of the ion

I ionic strength

For a single ion

log I = -A zi2 I1/2

1 2N A m solv
A

2.303
V

1
2

e2

4 o r kT

for aqueous solution at 25oC

A = 0.509
For electrolyte Av+Bv-

log = A z+ z- I1/2

Solve problem 7.8

Thermodynamics of Electrochemical Cells
1. Gibbs Energy Change in a Cell
Go = -zFEo
G = -zFE
2. Equilibrium Constant

3
2

Go = -RT lnKo
Eo = RTln Ko
zF
3. Entropy Change
So = zF Eo
T P
4. Enthalpy Change
Ho = - zFEo + zFT Eo
T
5. Heat Capacity Change
rCpo = zFT 2Eo
T2
Solve Problem: 7.11