Chapter 5

EQUILIBRIUM
ELECTROCHEMISTRY

1
I. Structure and Electrical Properties of Interfacial Regions

145

phase phase ex

CCL

i!

reg ion o
bulk bulk

terl ace

face regi
1 '
sur

interphase
Fig. 3.1 Structure of the interphase
Two phases in contact are separated by a surface called a
phase boundary
properties of aorcapacitor
interface
without leakage. For the first type of interface, the
electrical potential difference between the two phases is a result of charge
2
transfer across the interface; these interfaces are termed non-polarizable. In
this case, charge transfer involves the transfer of electrons from a metal
 Classification of electrical potentials at interfaces
Chemical potential: The distribution equilibrium for uncharged species distributed
between two phases is determined by the equality of the chemical potentials of the
components in the two phases. The chemical potential of the ith component in
phase α is defined by the relationship µι
" !G % " !U %
µi = $ ' =$ '
# !N i &P,T,N j(i # !N i &V,S,N j(i

Electrochemical potential: Charged particles is to be transferred from the given

reference state, further specified by the absence of an electric field, into the bulk of
an electrically charged phase. Work must be expended not only to overcome
chemical bonding forces but also to overcome electric forces. The work expended is
!
given by µ termed the electrochemical potential
i

µ ! = µi! + Zi F" ! ! " Is Inner electrical potential

3
 inner electrical potential
The inner electrical potential may consist of two components:
- The phase may possess some excess electrical charge supplied from outside.
This charge produces an outer electrical potential Ψ
- A particle transferred from this point further on in the direction of the other phase
must overcome the effect of electric forces in the interphase. This component is
called the surface electrical potential χ

!" = # + $

4
 Electrochemical potentials

!
Charge particle: µ i = µ + zi F"
!
i
!

!
o ,α o,!
α
µi = µ i + RT ln ai µi = µ i
+ RT ln ai + zi F" !

α α
Uncharged species (Zi = 0): µ i = µi
kl kl kl
Electron of metal: µ e = µ + (!1)F!
e

5
 The Galvani potential difference
The condition for equilibrium of charged specie in α and β phase
α β
µi = µi µi! + zi F" ! = µi! + zi F" !
! !
# " " µ ! µ
Galvani potential: !!" = ! ! ! = i i
zF
For Metal/Metal interface
M1 M2 M2 M1
µe = µe µ
! MM12 ! = ! M 2 " ! M1 = e
" µ e
F
µeM1 ! F! 1 = µeM 2 ! F! 2
The difference of the inner electrical potentials of the phases is
called the Galvani potential difference (galvani potential) 6
 The Volta potential difference

Volta potential difference: The difference of the outer electrical

potentials
!!"# = ! # " ! "
7
 Energy Levels

Vacuum
E=0 Level
Empty LUMO
States
Fermi
Energy

Level
Filled HOMO
States

An Atom A Small A Large Bulk

Molecule Molecule Material
Chemistry is controlled by the states around the filled/empty transition.
 Band Structure Large
spacing
Infinitesimal Small but between
spacing non-zero filled and
between spacing empty states
filled and between
empty states filled and
empty states
Valence
Band
Band Gap

Core
Bands

Metal Semiconductor Insulator

Our focus in this course is on metals.

 Fermi Level
• focus on the electrons near the filled/empty boundary.
• each material s energy state distribution is unique; different EF.
Minimum
energy to
remove
electron E=0 (vacuum level)
from
sample
EF (Fermi level)
EF (Fermi level)

Metal 1 Metal 2
• the closer an electron is to the vacuum level, the weaker it is bound to the solid
• or, the more energetic is the electron

Two Conductors in Contact

–+
electron flow
–+
–+
leads to charge separation
–+
–+ Contact potential difference

Fermi level the same throughout sample

 An Ion in Solution
• ion s electronic structure: HOMO, LUMO, HOMO-LUMO gap.

Lowest Unoccupied Molecular Orbital

HOMO-LUMO Gap Fermi level

Highest Occupied Molecular Orbital

 Metal in an Electrolyte Solution

Fermi levels + –

are aligned + –

+ –

Charge is transferred to
equilibrate Fermi levels,
producing a charge
separation and a contact
potential difference.
 Two Electrolyte Solutions

Fermi level

A charge separation
arises to align the
Fermi level and + –

produces a potential + –

at the interface. + –

 Junction Potentials
• In any circuit there are junction potentials
whenever two dissimilar materials come into
contact.

• We focus on the metal-solution interface in

electrochemistry
II. Galvanic cell (Electrochemical cell)
Fig 18-14 Pg 877

The copper/zinc electrochemical cell. The voltmeter measures the

difference in electrical potentials between the two electrodes.

Circuit: 1⏐2⏐3⏐…⏐N⏐M

The electromotive force: E  =  ΔΦ12  +  ΔΦ23  +  ...  +  ΔΦNM

→ E  =  ΦM  –  Φ1  
16
 Flow of Charge
How does charge flow in a cell?
If concentrations are
1M, then the cell is
– V+
e– e– at standard
conditions and the
measured potential
is +1.10 V.

Zn Cu
Zn2+

Cl– K+ Cu2+

NO3–
NO3–
 Electrolytic Cell
What about running the cell in reverse?
• apply an external voltage of
– DC V + opposite polarity.
e– e–
• magnitude must exceed the
+1.10 V that the cell
produces on its own.
• Cu electrode now dissolves
and Zn now plates out on its
Zn Cu
electrode.
Zn2+

Cl– K+ Cu2+

NO3–
NO3–
 Gibbs Function and Work
• Start with the First Law of Thermodynamics and some standard thermodynamic
relations. We find

dU = dq + dw
dq = T dS
dw = !P dV + dwelectrical
dU = T dS ! P dV + dwelectrical
dH P = dU P + P dV
dGT = dHT ! T dS
= dUT, P + P dV ! T dS
= T dS ! P dV + dwelectrical + P dV ! T dS

dGT, P = dwelectrical
And therefore, the Gibbs function is at the heart of electrochemistry, for it
identifies the amount of work we can extract electrically from a system.
 Gibbs and the Cell Potential
• Here we can easily see how this Gibbs function relates to a
potential.
welectrical = V Q
since Q = n F
= nF E

!GT, P = "welectrical = "n F E

•
 Thermodynamic of galvanic cell
ΔG
ΔG = – nFE → E=−
nF
⎛ ∂ΔG ⎞
ΔG = ΔH + T⎜ ⎟
⎝ ∂T ⎠ P

ΔH ⎡ dE ⎤
E =− + T ⎢ ⎥
nF ⎣ dT ⎦
(E1 and E2 – EMF of
dE ΔE E1 − E2
Thermal coefficient of EMF: ≈ = galvani cell at T1
dT ΔT T1 − T2 andT2)

⎛ ΔG ⎞ dE dE
ΔS = −⎜ ⎟ = nF ΔH = −nFE + nFT
⎝ ∂T ⎠ dT dT 21
 Nernst equation
νa A + νb B ⇄ νc C + νd D
ΔGT,P = Σ νi.µi
µi = µio + RT ln ai
o aνC C .aνD d
ΔG = ∑ν i µ + RT ln i
aνA a .aνB b
aCνC .aDν d
Π ai = =1 ΔGo = Σ νi µoi
a Aν a .aBν b
0 aνC c .aνD d ΔGTo, P RT aνC C .aνD d
ΔG = ΔG + RT ln E=− − ln
νa νb
a A .aB nF nF aν a .aν b
A B

RT aνA a .aνB b
o
E=E + ln
nF aνC c .aνD d
ν
o RT ∏ ai i (tc)
E=E + ln νj
nF ∏ a j (sp)
22
 Example: Daniell Cell
Cu is cathode (it is reduced). Zn is anode (it is oxidized).

Cu2 +(aq ) + 2 e – ! Cu( s) Zn (s ) ! Zn 2+ (aq ) + 2 e –

Cu 2+(aq ) + Zn( s ) ! Zn 2+(aq ) + Cu (s )

Note that n=2 for this reaction. =1

o RT aCu aZn 2+
E=E ! ln
n F a 2+ aZn
Cu =1

Activity for solid materials is 1; replace activities with concentrations.

o
E=E !
RT
ln
[ Zn 2+ ]
= 1.10 ! 0.01285 ln
[ Zn 2+ ]
2F Cu 2+
[ ] Cu 2+ [ ]
 Equilibrium: ΔG = 0

⎛ a νC .a ν d ⎞
ΔG T ,P = ΔG o
T ,P + RT ln⎜ C D ⎟ = ΔG 0 + RT ln K = 0
T ,P
⎜ a ν a .a ν b ⎟
⎝ A B ⎠ cb

ΔGo = – nFEo = – RT ln K

o RT
E =+ ln K cb
nF

⎛ aν C .aν d ⎞
K = ⎜ C D ⎟
⎜ aν a .aν b ⎟
⎝ A B ⎠ cb

24
 Standard Reference States
In order to quantify thermodynamics, we choose by convention a reference
state. Most common choice is called Standard Ambient Temperature
and Pressure (SATP) .
Temperature = 298 K (25 ˚C)
Pressure = 1 bar (105 Pa)
Concentration = 1 molal (mol of solute/kg of solvent)

BUT…

atmosphere is a widely used unit of pressure.

• 1 atm = 1.0134 bar
Reference State for Pressure is usually 1 atm
The most commonly used reference state is that of 1 M (mol/liter).
 Solids, Solvents, Liquids

• SOLID: reference is itself

• PURE LIQUID: reference is itself

• SOLVENT: reference is itself

a = 1 for all of these materials

Increase amount of these: reaction goes longer, but not faster.

III. The I.U.P.A.C convention for
Electrochemistry

27
 An Electrochemical Cell
The Weston Cell

Saturated CdSO4
solution

CdSO4 (s)
Hg2SO4 (s)

Cd(Hg) (l)
Hg (l)

—
+

 1. Cell Notation

Cd(12.5% Hg amalgam) | CdSO4(aq, sat) | Hg2SO4 (s) | Hg

(l)
Zn ⏐ Zn2+ (a1) ¦ Cu2+ (a2) ⏐ Cu or
Zn ⏐ Zn2+ (a1) ║ Cu2+ (a2) ⏐ Cu

A shorthand cell notation has been developed for convenience.

  write components in sequence
  separate phases with a single vertical line |
  a salt bridge or membrane is represented by a double vertical line ||
  included a specification of the species concentration
Salt bridges: Eliminate liquid potentials between two compartments.

Ecell

bridge
∆ aq φ
Cancel each other out
∆ aq
bridgeφ

Representation of boundaries in cells:

Phase boundary
Liquid junction
Boundary excluding liquid potentials

30
2.4 The cell2. The
reaction cell reaction
!Chemical reaction operating in electrochemical cell.
!Cathode is located at the right hand side of the electrochemical cell,

Zn ( s ) ZnSO4 ( aq ) CuSO4 ( aq ) Cu ( s )
anode cathode

!Reactions written in their reduction form:

Cu2+ ( aq ) + 2e − → Cu ( s ) eqn. 3.8

Half cell reactions
2+
Zn ( aq ) + 2e −
→ Zn ( s ) eqn. 3.9

!The cell reaction: cathode – anode (right hand – left hand),

Cu2+ ( aq ) + Zn ( s ) → Cu ( s ) + Zn2+ ( aq ) eqn. 3.10 31

11
 3. Cell Potential
Because we tabulate reduction potentials, the cell potential is calculated
(from those tabulated numbers) as

Ecell = Ecathode - Eanode

The minus sign is present only because we are using reduction potential
tables and, by definition, an anode is where oxidation occurs.
 4. Standard Electrode Potentials

Standard reduction potential (E0) is the voltage associated with

a reduction reaction at an electrode when all solutes are 1 M
and all gases are at 1 atm.

Reduction Reaction

2e- + 2H+ (1 M) H2 (1 atm)

E0 = 0 V

Standard hydrogen electrode (SHE) 19.3

 Standard as a Reference
  Once chosen, this reference cell is employed as one half-cell with all other
cells. Since its potential is assigned the value of 0.000 V, all of the potential
difference measured experimentally is attributed to the other, test electrode.
  Since we are cataloguing reduction potentials, the cells are formed by
connecting the Standard Hydrogen Electrode (SHE) as the anode and the
other half-cell as the cathode.
  Consider:
Pt | H2 (1.00 atm) | H+ (1.00 M) || Cu2+ (1.00 M) | Cu
Measured potential = +0.340 V
  Since the activity of all components in the Cu cell are standard, +0.340 V is
the STANDARD REDUCTION POTENTIAL of the Cu2+/Cu couple.
 Measure standard Electrode Potentials

Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

Anode (oxidation): Zn (s) Zn2+ (1 M) + 2e-
Cathode (reduction): 2e- + 2H+ (1 M) H2 (1 atm)
Zn (s) + 2H+ (1 M) Zn2+ + H2 (1 atm)
19.3
 Standard Electrode Potentials
E0cell = 0.76 V

Standard emf (E0 cell

)
0 0
E0cell = Ecathode - Eanode

Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

E0cell = E0H+/H2 - E0Zn2+ /Zn
0.76 V = 0 - E0Zn2+/Zn
0 2+
EZn /Zn = - 0.76 V

Zn2+ (1 M) + 2e- Zn E0 = -0.76 V

19.3
•  E0 is for the reaction as written
•  The more positive E0 the
greater the tendency for the
substance to be reduced
•  The half-cell reactions are
reversible
•  The sign of E0 changes when
the reaction is reversed
•  Changing the stoichiometric
coefficients of a half-cell
reaction does not change the
value of E0

19.3
IV. Type of electrodes
Types of electrodes:

Redox Electrodes Metal/Metal Ion

Fe3+ ( aq )

e − Cu2+ ( aq )

Pt Fe2+ ( aq ) Cu

RT ! aFe2+ " RT ! 1 "

M
∆ φ=∆ φ − M
ln # o
$$ ∆ Maqφ = ∆ Maqφ o − ln # $$
aq
F
aq
# a 3+
% Fe & 2F #% aCu2+ &

Metal/Insoluble-Salt Gas Electrodes

H+ ( aq )
AgCl

Cl- ( aq ) H2 ( g )
Ag Pt

RT RT ! 1 "
∆ Maqφ = ∆ aq
M o
φ −
F
( )
ln aCl- ∆ Maqφ = ∆ aq
M o
φ −
F
ln #
# a + $$
% H &
6
38
 Reference electrode, Ag/AgCl
- -
mistry
AgCl
89 (r)
+ e ! Ag(r) + Cl (aq)
0
1
E = 222 mV (S.H.E)
0
2
E (KCl bh) = 197 mV (S.H.E)

3
RT 0 0
E=E " ln aCl- ; E = E " 0.059 log aCl-
nF
4
RT o
5
.2,303 = 0.05916 (25 C)
nF
Ag/AgCl electrode: (1) Ag(s) wire, (2) filling hole, (3) KCl(aq)
(4) Ag(s) wire coated with AgCl(s), (5) ceramic, quartz, or glass
39
ion of KCl(aq) equal (1) 0.1 mol L−1, (2) 1.0 mol L−1, (3) sat-
KCl(s) can be calculated and compared with values given
Calomel electrode
.13]. The calomel and silver/silver chloride electrodes have
bility. A disadvantage of the calomel reference electrode is
particularly hazardous chemical.
Hg2Cl2 reference electrode is shown in Figure 5.1.
- -
Hg 2Cl(2r) + 2 e ! 2 Hg(l) + 2 Cl (aq)
1

2
E o = 268 mV (S.H.E)
3
RT 0 0
E=E " ln aCl- ; E = E " 0.059 log aCl-
4 nF
5

6
RT 0 - 2
7 E=E " ln [Cl ]
2F
of calomel reference electrode: (1) platinum wire, (2) filling
(usually saturated), (4) liquid mercury, (5) mercury–calomel
ss frit, and (7) ceramic, or quartz, or glass porous plug.
40
 Concentration Cell
Nernst equation demonstrates that potential depends upon concentration.

A cell made of the same materials, but with different concentrations, will also
produce a potential difference.
Cu | Cu2+ (0.001 M) || Cu2+ (1.00 M) | Cu
What is standard cell potential E˚ for this cell?
What is the cell potential E? What is n , the number of electrons transferred?
Which electrode, anode or cathode, will be in numerator?

o 0.0257
E=E !
"
ln $
Cu 2+
[
anode '
% ]
n $ Cu 2+
# [ '
cathode & ]
0.0257 " 0.001%
= 0! ln = +0.089 V
2 # 1.00 &
42
43
5.1 Potentiometric titrations
!Concentration of Fe2+(aq) determined by titration with Ce4+(aq)
!Titration monitor by electrode potential.

Ecell
Ce4+
Pt Pt
H2 (g)

Salt Bridge
Ce4+ ( aq ) + e − → Ce3+ ( aq )
o
ECe 4+
/ Ce3+
= 1.44 V
Fe3+ Ce4+

Fe3+ ( aq ) + e − → Fe2+ ( aq )
o
HCl (aq) Fe2+ Ce3+ EFe3+
/Fe2+
= 0.771V

44
3
!Electrode potential vs concentration ratio

o RT ! x "
Nernst Ecell = E Fe3+ /Fe2+
− ln # $ eqn. 5.1
F % 1− x &

1.0
Fe3+ ( aq ) + e − → Fe2+ ( aq )
0.9 o
EFe3+
/Fe2+
= 0.771V
Ecell / V

0.8
0.7
0.6
0.5
0.0 0.2 0.4 0.6 0.8 1.0
x
45
Fig 5.1 Potential as a function of the relative Fe2+/Fe3+. 4
 #% RT cell ( Ce4+ / Ce3+ $ c
&
) V ! F
Va =
! F titration curve
Typical potentiometric
Fe2+

of "a Fe
exp #
% RTwith
cCe4+ solution
2+
( o
Ecell − EFe 3+

1 + exp E
a standard Ce4+. %# RT cell
(
− E o
Fe3+ / Fe2+ $
&
)

1.4
1.2 Fig 5.2 Typical potentiome
Ecell / V

curve of a Fe2+ solution wit

1.0 Ce4+.
V = 10 cm-3
0.8
cFe2+ = cCe4+
0.6
4 8 12 16
Va / cm-3
46
 Some extra work

  Luther’s rule

  Latimer’s diagram

 Frost’s diagram

 E-pH (Pourbaix’s diagram)

47