Physical Chemistry

Electrochemistry
 What is electrochemistry?
electricity

◆ Electrochemistry is the study of interchange of chemical and electrical energy.

Electric Chemical
Power Reactions
 Lamp

Copper wires

Battery

Spontaneous reaction
H2O =H2 + O2 decompose
nonspontaneous reaction

DC power source

Electrode

Water
(containing some supported
electrolytes)
◆ Two types of devices used for interchange of chemical and electrical energy.

Electrical devices
Chemical
Energy Energy
1、 Electrochemical Cells

Electrolytic cell

Electrical Chemical
Energy Energy

Galvanic cell
1 .1 Galvanic or Voltaic cell

◆ Reactions are spontaneous

◆ The spontaneous reactions produce electrical energy.

Let’s look at an example:

Zn (s) + CuSO4 (aq) Cu (s) + ZnSO4 (aq)

Zinc sulphate
 Electrode
Cu Electrode
Zn
Salt Bridge
CuSO4
ZnSO4 aqueous
aqueous solution
solution

Electrolyte Electrode compartment

Daniell Cell
 Electrode semi-permeable membrane Cu Electrode
Zn

CuSO4
ZnSO4 aqueous
aqueous solution
solution
 Overall reaction: Zn + Cu2+ = Zn2+ + Cu
Electrode reactions or half-reactions

:
Anode : Zn – 2 e = Zn2+ (oxidation reaction)
Cathode : Cu2+ + 2 e = Cu (reduction reaction)
negative positive
potential
electrode electrode

e- I
1 .2 Electrolytic cell

◆ Reactions are nonspontaneous .

◆ Electrical
energy is needed to drive the
nonspontaneous reactions.
Let’s look at the following reaction:

2 NaCl = 2 Na + C12

Sodium Chloride Sodium Chlorine

Electrode reactions or half-reactions :
Anode : 2 Cl– – 2 e = Cl2 (oxidation)
Cathode : 2Na+ + 2 e = 2Na (reduction)
Overall reaction: 2NaCl = 2Na + C12
I

positive negative
electrode electrode
A summary of the difference between galvanic cell
and electrolytic cell

Electrolytic cell Galvanic cell

System consumes energy System releases energy

DG>0 ( nonspontaneous ) DG<0 ( spontaneous )

Anode Anode
Positive electrode Negative electrode

Cathode Cathode
Negative electrode Positive electrode
2、 Important knowledge about the current ( I or quantity of
electricity (Q）passing through an
electrochemical cell
series circuit

a closed circuit
 I

a closed circuit

Q= I  t
● The current ( I）passed through any part of the closed circuit must be the
same.

For a given time period ( t）, the quantity of electricity (Q） passed through
any part of the closed circuit is the same.
 I

a closed circuit

● TWO types of conductors in the closed circuit

◆ electronic conductors
The charge carriers are electrons.

Graphite Metal
 I

a closed circuit

◆ ionic conductors
The charge carriers are ions.
electrolyte solution
 I

a closed circuit

● Two important interfaces between electronic

conductor and ionic conductor in the closed circuit

Cathode/ electrolyte
Electrode / electrolyte
Anode / electrolyte
2.1 Electronic conductors and Faraday constant

The charge carriers are electrons.

● The quantity of electricity (Q）passing an electronic conductor can be
calculated by

Q = Ne  e = ne  F
Faraday constant

The The charge of The moles of

number of the electron electrons
electrons 1.602192 x 10-19 C
◆Faraday constant (F) : : the quantity of electricity
carried by one mole of electrons

F = 6.022  1023 mol-1  1.602192 x 10-19 C

= 96484 C mol-1  96500 C mol-1

Q = N e  e = ne  F

When the quantity of electricity passed through an

electrolytic cell is Q , (Q ⁄ F) moles of electrons are
supplied.
ne = Q ⁄ F
 I
Q

I I
I

Cathodic reaction consumes the electrons

Anodic reaction produces the electrons
The quantity of electricity carried by the electrons
consumed or produced by the electrode reaction must
be equal to the value of Q passed through the
electrode.
Suppose that at the cathode, only the metal ion M Z+ is
reduced to M and the quantity of electricity passed through the
electrolytic cell is Q [ (Q ⁄ F) moles of electrons are supplied ] :

M Z+ + Z e → M
So, the amount of M obtained at the cathode is:

n (in mole) = (Q ⁄ F) ⁄ z = Q ⁄ (Z F)
Or
m (in kg) = M Q ⁄ (Z F)

M is the molar mass of the metal.

 n (in mole) = (Q ⁄ F) ⁄ z = Q ⁄ (Z F)

The quantity of a substance produced by a cathode or anode reaction in electrolysis

is directly proportional to the quantity of electricity passed through the cell.

Faraday Laws of Electrolysis

 n =Q ⁄ (Z F) Q = nZ F

m = M Q ⁄ (Z F) Q=ZFm⁄ M

This is the principle of coulometer , a devise for

measurement of the quantity of electricity Q .

◆ Coulometer
Copper coulometer
Silver coulometer
Gas coulometer
2.3 Ionic conductors and
transport numbers
The charge carriers are ions.

I
Q

I I
I

cations and anions

The current that passes through an electrolyte solution is carried by all the
cations and anions in the solution.

I   I    I    Ii Q   Q   Q   Qi
For the case of the molten NaCl ，

I  I Na   I Cl  Q  Q Na   QCl 

where isI Nathe current carried by Na+ and

 I Cl  carried by
is the current
Cl－ .
Current-carrying capacity of ions
 2.3.1 Transport (transference) numbers of
ions
◆ Definition
Transport number of the ion i（ti） is defined as the fraction of the total
current carried by the ion i .

I i Qi
ti  
I Q
I or Q is the current or the quantity of electricity passed through the electrolyte
solution.
Ii or Qi is the current or the quantity of electricity carried by the ion i.

I   I   I   Ii Q   Q    Q    Qi
The transport numbers of the anions and the cations adds up to unity.

 ti   t   t  1
For example, in molten NaCl, we have

I Na  Q Na  I Cl  QCl 
t Na    t Cl   
I Q I Q

t Na   t Cl   1
◆ Factors on transference number

(1) Temperature

Transference number of K+ in KCl solution at different concentrations and

temperatures.

0.005 M 0.01M 0.02 M

15 oC 0.4926 0.4925 0.4924
25 oC 0.4903 0.4902 0.4901
35 oC 0.4887 0.4886 0.4885
potassium
 (2) Co-existed ions

t t 1
Transference numbers of K+ or Cl – in different electrolytes at 0.01M and
25 oC.

electrolyte KCl KBr KI KNO3

t+ 0.4902 0.4833 0.4884 0.5084
electrolyte LiCl NaCl KCl HCl
t– 0.6711 0.6080 0.5098 0.1749
How to measure transport numbers ?

◆ Measurement of transport numbers by Hittorf method:

I i Qi
ti  
I Q
 Hittorf method
Example: electrolysis of HCl solution
(1) Before electrolysis

Cathode Anode

Cathodic region Bulk solution Anodic region

Anode: 2Cl- - 2e = Cl2 Cathode: 2H+ + 2e = H2

H+ H+
Anodic region
Cathodic Cl- Cl-
region H+ Cl- Cl-
Cl- H+
Cl-
H+
H+

HCl aqueous solution

Hittorf’s transference cell

(2) When the quantity of electricity (Q) passes through the electrolytic cell

In cathodic region ，for H+ :

nresidual = ninitial – nreact + n transfer

n transfer=nresidual+ nreact – ninitial

I i Qi
ti   tH+ = n transfer Fz/Q
I Q
In anodic region ，for Cl- :
nresidual = ninitial – nreact + n transfer

n transfer=nresidual+ nreact – ninitial

tCl- = n transfer Fz/Q

3. Conducting properties of electrolyte solutions

The ability to conduct an electric current

 Metal

A
Cross-sectional area
l

l
R
Resistance

A
Resistivity
 Metal

I
m n
U

Ohm’s law :

potential difference
U
R
I
Install a pair of electrodes into the liquid;

Introduce a potential difference between two parallelelectrodes.

I U
electrode electrode

electrolyte solution
3.1 Resistance and Conductance

◆ Resistance ( R )

Electrolyte solutions follow Ohm’s law

U
R
I
where R is the resistance, U is the potential difference, and I is the current .
◆ Conductance ( G )

Conductance G (S or  −1) is defined as reciprocal of the resistance:

1
G
R
 How to measure conductance?

1
G
R
measurement of conductance
= measuring resistance
◆ Measuring resistance

Resistance measuring device based on the principle of wheatstone bridge

Galvanometer Tunable capacitor

Resistor

Alternating current
韦斯顿电桥

Rx R1 R1 R4 1
  Rx   Gx 
R4 R3 R3 Rx
 Metallic conducting materials:

A
l

l 1 1 A
R 
A R  l
Resistance Resistivity

1 A
Let  G 
 l
Conductance Conductivity
 electrode electrode
l

Conductance (G) of a given electrolyte solution

decreases when the distance between the
electrodes ( l ) increases and increases when
the effective area of the electrodes (A ) increases.

1 A
G  κ
R l
3.2 Conductivity and molar conductivity

A
G κ
l
 is the conductivity (S m−1)
(formerly called the specific conductance)

A is the effective area available for conducting electrons through the electrolyte
solution (m2)

l is the distance between the electrodes (m).

 A
G κ κ G
l
l A

◆ Cell constant Kcell

For a given conductivity cell, l ⁄A is kept

unchanged .
Cell constant of a conductivity cell Kcell
is defined as:
l
K cell 
A
If the conductance of an electrolyte solution
(G) is measured in a cell whose Kcell is
known, the conductivity of this electrolyte
solution  can be obtained by:

l
κ  G   G  Kcell
A
 l
K cell 
A
A is the effective area available for conducting electrons through the electrolyte
solution (m2)

A is difficult to measure and usually lager than

the geometrical surface area of the electrode,
especially for the materials with high specific
surface area ，e.g. Pt black .
 
κ  G  Kcell  K cell   R
G

◆ Measurement of Cell constant Kcell ：

Fill the cell with an electrolyte solution of known

conductivity  (usually the standard electrolyte KCl ),
and then measures its resistance R to get G.
For a standard electrolyte KCl

 KCl
K cell    KCl RKCl
GKCl
◆ Factors on conductivity 
In an electrolyte solution
(1) The number of ions in the electrolyte
solution
(2) The migration rate of the ions in the
electrolyte solution

The interaction between the ions in the

electrolyte solution has an impact on the
migration rate
(1) Concentration
For strong electrolytes
,
(i) Acids and bases have higher
conductivity
(ii) C < 5 mol dm-3,  increases
with C
For a weak electrolyte , e.g.
CH3COOH, the conductivity only
changes slightly with concentration.

acetic acid
(2) Temperature

38 % H2SO4 was used in

acid-lead battery.
◆ Molar conductivity ( m )
Molar conductivity m ( S·m2 ·mol−1 ) is defined as:


m 
c
where c is the molar concentration of the added electrolyte in mol·m−3.

The typical values for molar conductivity of strong electrolyte solutions are:

1  102 ~ 4  102 Sm2  mol1

◆ Dependence of molar conductivity on concentration

m decreases with
concentration due to the
interaction between ions.
interionic attraction
If plotted m against C1/2

intercept For strong electrolytes,

linear relationship between m

and C1/2 can be observed when the
concentration is very low.

y = a x+ b
3.3 Kohlrausch empirical formula and limiting
molar conductivity

For strong electrolytes of very low concentration (c ≤ 0.001 mol /L) , linear
relationship between m and C1/2 can be observed.


m    A c m

Kohlrausch empirical formula

Kohlrausch empirical formula


m    A c m

A is an experimental constant.
m is the limiting value of m at infinite
dilution , namely limiting molar conductivity .
◆ Method for obtaining m of a strong electrolyte
To extrapolate the linear part of m ~ C1/2 at low
concentration to C = 0, m can be obtained.
This extrapolation method is not suitable for a
weak electrolyte.

limiting molar conductivity .

 3.4 Law of independent migration of ions and
limiting molar conductivity of ions

◆ Law of independent migration of ions

Kohlrausch’s law
For any electrolyte at infinite dilution ：
（1）The distance of ions in the solution is so large
that there is no interaction between them.
(2) Eeach ion is assumed to be migrating
independently.
(3) Each ion is assumed to independently make
its own contribution to molar conductivity.
 m ,  limiting molar conductivities of cations

m ,  limiting molar conductivities of anions

The value of m for an electrolyte M A   can

be obtained from the addition of individual
conductivities of ions:

M   A     M z   A z

  

m

 m,    
 m,
Kohlrausch’s law
Kohlrausch’s law is also valid for strong electrolyte in dilute solutions.

M   A     M z
  A z

 m     

m

m,   
 m,
◆ Calculation of limiting molar conductivity of weak electrolyte based on
Kohlrausch’s law

m ( HAc )  m ( H  )  m ( Ac  )

 m ( H  )  m (Cl  )  m ( Na  ) 

weak
electrolyte  ( Ac )   ( Na )   (Cl )

m
 
m
 
m


 m ( HCl )  m ( NaAc )  m ( NaCl)

Strong electrolytes
acetyl group
Extrapolation method
 3.5 Ionic mobility

◆ Definition

For the ion i in the solution, it migrates with a speed  i toward the electrode
when electric field E is applied.

i
ui  (m 2  V -1  s -1 )
E

The quantity u i is called ionic mobility.

3.5 Relation between transport number and
molar conductivity at infinite dilution t  t 
 

For an electrolyte M  A  M  A     M z   A z

At infinite dilution Kohlrausch’s law

  

m

 m,    
 m,

Contributed by anions
Total Contributed by cations
 Q  Q  Q
Contributed by anions
Total Contributed by cations
对电解质
Q M A M
Q A
    M z
  A z

t   
t 

  
Q Q

  

m

 m,    
 m,

  
  
 m,
So, 
t 

 m,
t 
 
 
m
 m
   
   
 m,

t 

 m,
t 
 
 
m
 m

t  m t  m
m ,   m ,  
 

  
 , t  , and t
m  can be measured experimentally.

So, we can obtain  

m, and  
m,
3.6 Factors affecting the values of 

m, and  
m,

◆ Charge ，radius
ions r / nm 102 m ions r / nm 102 m
H+ -- 3.4982 OH– -- 1.98
Li+ 0.68 0.387 F– 1.23 0.554
Na+ 0.98 0.501 Cl – 1.81 0.763
K+ 1.37 0.735 Br – 1.96 0.784
Mg2+ 0.74 1.061 CO32 – -- 1.66
Ca2+ 1.04 1.190 C2O42- -- 1.48
Sr2+ 1.04 1.189 Fe(CN)63 – -- 3.030
Al3+ 0.57 1.89 Fe(CN)64 – -- 4.420
Fe3+ 0.67 2.04
La3+ 1.04 2.09
 3.7 Application of conductivity measurement

◆ Determination of the purity of water

For pure water at 25 oC :
Kw = 10 −14, [H+] = [OH −] = 10 −7 mol dm− 3= 10−4 mol dm−3
m m = m (H+) + m (OH −)
=(3.4982+1.9800 ) 10−2 S m2 mol −1
= 5.4782  10−2 S m2 mol−1

 = Cm =5.4782 10−2 S m2 mol−1  10−4mol m −3

= 5.478  10−6 S m −1
 Conductivity of water
Tap water Distilled Deionized Pure water
water water
/S m-1 1 10-2 ~1 10-3 <1 10-4 5.478 10-6
◆ Determination of degree of ionization  and
ionization equilibrium constant
AB A+ + B–
c 0 0
c(1-) c c

m
  Why ?
m
c 2 2 c 2 cm
K   Ostwald’s dilution
(1   )c 1    m (m   m ) law
(c / c ) 2 2 c m c
K       
(1   )c / c
1 c 
 m ( m   m ) c
 4. The activity of electrolyte solution

Activity of a molecule or ion in a solution is

referred to as effective concentration.
◆ Molecular activity and activity coefficient

For nonideal solution of non-electrolytes，the chemical

potential of solute B is given by

 B   B (T )  RT ln a B ,m

a B,m is the activity of solute B.

mB
aB , m   B , m 
m
mB: the molality of B
B,m: the activity coefficient of B
 Electrolyte solution

The chemical potential of the electrolyte B can also be

expressed by

B = B (T ) + RT ln a B

Difference: dissociation
M+ A  + M Z+ +  A Z
 4.1 Ionic activity and activity coefficient

For M+A dissociates into ions in solution：

M+ A  + M Z+ +  A Z

We define ionic activity by ,

m m
a     a    
m m
a+ and a : ionic activity
m+ and m  : the molality of cations and anions
 + and   : ionic activity coefficient.
For an electrolyte M+A - with its molality being m
M+ A  + M Z+ +  A Z

So m    m, m    m
 The chemical potential of ions is given by

   (T )  RT ln a
  


   (T )  RT ln a
  

The chemical potential of the electrolyte (M+A ) B is given by

 B         

M+ A  + M Z+ +  A Z
 B= + + +  
= + [ + ( T ) + RT ln a+ ]
+ [( T ) + RT ln a ]
= (+ + +  ) + RT ln (a++a )

Since the chemical potential of the electrolyte B can also be

expressed by
B = B (T ) + RT ln a B

So, we have： B (T) ＝+ + (T) +   (T)

aB＝ a+ + a 

 aB＝ a+ + a  Geometrical average

Because the solution only containing single ion does not

exist, the activity of individual ion is unmeasurable.
4.2 Mean ionic activity and mean ionic activity
coefficient

For an electrolyte M+A - , we define

   1/  = + + 
mean ionic activity a  (a  a )

mean ionic activity    (     )1/

 

coefficient

   1/
mean ionic molality m  (m  m )
Geometrical average
 a = a++a 
= [(m+/m)+]+[(m/m)]
= [m++ m/(m) ](++  )
= [(m/m) ] 

m
a     
m
If  is measurable, a  can be then calculated.
◆ Factors affecting mean ionic activity coefficient
1) Concentration

1) m 0, ± 1
2) m , ± has minimal value

1
2) Temperature

Dependence of ± on temperature for 1:1 type electrolytes

T/oC 0 10 20 25

KCl 0.768 0.769 0.770 0.769

KOH 0.795 0.798 0.798 0.798

NaOH 0.767 0.768 0.766 0.766

3) Valence types

type electrolyte 0.1 m 0.2 m 1.0 m

1:1 RbNO3 0.734 0.658 0.430
NH4ClO4 0.730 0.660 0.482
1:2 BaCl2 0.508 0.450 0.401
CaCl2 0.510 0.457 0.419
1:3 LaCl3 0.314 0.274 0.342
FeCl3 0.325 0.280 0.270
Conclusion:

1) Electrolytes of same valence type have similar

activity coefficient at same concentration. The
coefficient does not depend on the nature of
electrolyte.

2) Activity coefficient strongly depends on both

concentration and valence types.
 4.3 Ionic strength

◆ Definition
The ionic strength, I, of a solution is a function of the
concentration of all ions present in that solution
1
I   mi Z i2 Lewis (1921)
2 i
kg 1).
mi : the molality of ion i (mol·
zi : the charge number of ion i
the sum is taken over all ions in the solution
In a dilute solution

ni ni ni ci ci
mi     
WA Ws ln s ln  V s ln  A

When the solvent is water,  A =1 kg/L

mi  ci
1 1 1
I   mi Z i 
2
 ci Z i   ci Z i
2 2

2 2  s ln i 2
 ◆ Relation with ±
Lewis Empirical equation for a dilute solution:

ln     I or ln    C I

0.0 0.5 1.0 1.5 2.0

0.0

natural
-0.2 a constant
logarithm
-0.4

-0.6

ln± vs. I1/2 for KCl

4.6 Debye–Hü
ckel limiting law for strong electrolyte

The Debye–Hü ckel equation or Debye–Hü ckel

limiting law, named for its developers Peter Debye
and Erich Hü ckel, provides one way to obtain
activity coefficients
◆ Ionic atmosphere model in Debye–Hü
ckel theory

The cloud of ions of one charge type that tend to accumulate

by interionic attraction around an ion of the other charge
type (counter ion) in an electrolyte solution.

cations

anions

Radius: 10-7 ~ 10-9 m

◆ Debye–Hü
ckel equation
The activity coefficient of an ion in a dilute solution:

ln  i   AZ i
2
I Valid when I < 0.01 m

A is a constant that depends on the solvent.

A is 1.172 kg1/2mol−1/2 ( an experimental value) for an aqueous

solution at 25oC.
Using a base-10 logarithm,

lg  i   AZ i2 I Valid when I < 0.01 m

A is 0.509 kg1 / 2 mol−1/ 2 for an aqueous solution at 25oC.

Lewis empirical equation for a dilute solution:

ln    C I
    1/
   (    )

1
ln    (  ln      ln   )


ln     AZ 2
 I
ln     A Z  Z  I
Debye–Hückel
ln     AZ 2 I equation
Valid when I < 0.01 m

 Z  Z
5. Reversible cell
5.1 Cell notation
Instead of drawing a cell picture, chemists have
devised a shorthand way of completely describing a
galvanic cell called line notation

Zn(s)ZnSO4(c1)CuSO4(c2) Cu(s)
1. Write the anode on the left: Zn(s)

2. Draw a single vertical line to represent the phase boundary: Zn(s)

3. Write the reactive part of the anode compartment with its initial concentration (if known):
Zn(s)ZnSO4(c1)

4. Indicate salt bridge using double vertical line : Zn(s)ZnSO4(c1)

semi-permeable membrane using vertical dotted line

5. Write the reactive part of the cathode compartment with its initial concentration (if known):
Zn(s)ZnSO4(c1)CuSO4(c2)

6. Draw a single vertical line to represent the phase boundary, and finally write the cathode on the
right.

Zn(s)ZnSO4(c1)CuSO4(c2) Cu(s)
 5.2 Definition of reversible cell
A cell in which conversion of chemical energy to
electrical energy in a thermodynamically reversible
manner.
(1) Reversible reaction: The electrode reaction reverts when shift from charge to discharge.

(2) Reversible process:

proceed at infinitely slow speed

I0
 ◆ Weston standard cell: a highly reversible cell

Invented by Edward Weston

in 1893

mercury anode cadmium amalgam

cathode

Cd(Hg)xCdSO4·
8/3 H2O CdSO4 (saturated)  CdSO4 ·
8/3 H2O
Hg2 SO4 (s) Hg(l)
Anode reaction： Cd  2e ⇌ Cd2+
Cathode reaction：Hg2SO4(s) + 2e ⇌ 2 Hg (l ) + SO42
Overall reaction： Cd + Hg2SO4(s) ⇌2Hg (l ) + CdSO4

Electromotive force of Weston standard cell

E (V) = 1.01845 – 4.05 10-5(T –293.15)

– 9.5 10-7(T –293.15)2 + 1 10-8 (T –293.15)3

Can be used between –8 and 51 oC.

 Why used as a standard cell?

Cd(Hg)x is a two-phase system. When the

content of Cd(s) in Hg(l) varies between 7 % and
13 %, no significant change of the electrode
potential of Cd(Hg)x|Cd2+, can be detected.
 i = 0: satisfy the
thermodynamic
reversibility

Poggendorff’s counteraction method

 EW: working cell
Es: standard cell
Ex: unknown cell
i=0

E X  k  AC1
i=0

ES  k  AC 2

AC 1
 EX   ES
AC 2
5.8 Thermodynamics of reversible cell
5.8.1 Relation between the cell electromotive force E and
the Gibbs energy of the overall cell reaction rGm

Under constant temperature and pressure:

– (dG) T,P  W ′ W ′---- non-expansion work

For a reversible process,

– (dG) T,P = W ′
 – (dG) T,P = W ′
In a reversible cell, the non-expansion work is electrical
work
W ′= EdQ dQ=zFd
W ′= z FE d = – (dG) T,P

– z FE = (G ⁄   ) T,P = rGm

rGm =– z FE
z: The number of electrons transferred in chemical reaction
F: Faraday constant
E: Cell electromotive force
 For a general reaction:

cC+dD=gG+hH
If this reaction occurs in a reversible cell:
 r Gm   zFE

When all the reactants and products are in their

standard states:
 r Gm   zFE

E : standard electromotive force

5.8.2 Relation between E and rSm of the overall
cell reaction
derivative

 r Gm
( ) P   r S m  r S m  zF (E T ) P
T

rGm =– z FE

Can be obtained by
measuring E at different
(E/T)p ：
temperatures
temperature coefficient of electromotive force
5.8.3 Relation between E and rHm of the overall
cell reaction
 E 
 r H m   r Gm  T r S m   zFE  zFT  
 T  P
  E  
 r H m  zF T    E
  T  P 

By measuring E and (E/T)P,

thermodynamic quantities of the cell
reaction rGm, rSm, and rHm can be
determined.
5.8.4 Calculation of the heat released by a reaction
conducted in a reversible cell ( Qr )
Qr  TS  E 
S  zF  
 E   T  P
 zFT  
 T  P

 E 
  0 Qr=0
 T  P
 E 
  0
 T  P
Qr>0 the cell absorbs heat
 E 
  0
 T  P
Qr<0 the cell releases heat
 Under constant temperature and pressure:
◆ A chemical reaction occur without additional non-
expansion work, the heat released Q is equal to the
change in enthalpy
 E 
Q   r H m   r Gm  T r S m   zFE  zFT  
 T  P
◆ IF this chemical reaction occur in a reversible cell,
the heat released Q is NOT equal to the change in
enthalpy
 E 
Qr  TS  nFT  
 T  P
Relation between thermodynamic quantities
for cell reaction and electromotive force E:
 r Gm   zFE  r Gm   zFE

 r S m  zF (E T ) P

 E 
 r H m   r Gm  T r S m   zFE  zFT  
 T  P

 E 
Qr  TS  nFT  
 T  P
5.8.4 Nernst equation and electrochemical
measurement of mean activity coefficient 
For a general reaction:
cC+dD=gG+hH
Van’t Horff equation
g h
 aG aH
 r Gm   r Gm  RT ln c d
aC aD

 r Gm   zFE  r Gm   zFE

r h
 RT aG aH
EE  ln c d
zF aC aD
Nernst equation for cell reaction
 r h
RT a a

EE  ln G
c
H
d
zF a a C D

E is equal to E when the

activity of any chemical
species is unit.

Walther H. Nernst (Germany)

1920 Noble Prize in Chemistry
6. Electrode potential
 Daniell cell

How does the electromotive force establish

in a cell?
The value of liquid junction potential j

The value of j can reach ca. 30 mV, which is too large

for the measurement of E.
◆ Factors affecting the value of j

Pt, H2(P)  HCl(m)  HCl (m')  H2(P), Pt

For uni-univalence electrolytes

RT m RT m
E j  (t   t  ) ln  (2t   1) ln
F m' F m'

The larger the difference between t+ and t and the

greater the difference between m and m’, the larger
the value of  j
◆ Effects of salt bridge
The salt bridge is often used to connect the two
electrode compartments to reduce the junction
potential.
Salt bridge electrolyte：
1) does not react with the solution
2) transference number of cation is close to that of
anion
3) high concentration.
ions K+ NH4+ Cl- NO3-
102m 0.7352 0.734 0.7634 0.7144
/Sm2mol-1
t+ of some common salt bridge electrolytes
C/mol dm-3 0.01 0.05 0.10 0.20
KCl 0.490 0.490 0.490 0.489
NH4Cl 0.491 0.491 0.491 0.491
KNO3 0.508 0.509 0.510 0.512

Concentration-dependence of Ej on the salt bridge

electrolyte KCl
C/ mol dm-3 0 0.2 1.0 2.5 3.5

j 28.2 19.95 8.4 3.4 1.1

 6.2 Relation between interfacial potential differences
and electromotive force E
Cu(s)Zn(s)ZnSO4(m1)CuSO4(m2)Cu (s)
1) discussion
E   Cu/Zn   Zn/Zn 2   j   Cu 2 /Cu

 e ,Cu - e ,Zn   Zn 2 /Zn   j   Cu 2 /Cu

Cu(s)Zn(s)ZnSO4(m1) CuSO4(m2)Cu (s)

When a salt bridge is used, j  0
E  e ,Cu - e ,Zn   Zn 2 /Zn   Cu 2 /Cu

 (e ,Cu   Cu 2 /Cu ) - (e ,Zn   Zn 2 /Zn )   ' -  '

 
6.3 Absolute electrode potentials , relative electrode
potential and standard electrode potentials

◆ Absolute electrode potentials

E   ' -  '
+′and  ′ are the absolute potentials of positive and
negative electrodes.

Absolute potential of an individual electrode is

unmeasurable.
◆ Electrode potential and standard electrode potential

Setting a reference:
E=+
=(+reference)(reference)
+ 
=reference measurable
 is relative electrode potential (usually called
electrode potential)
◆ Normal hydrogen electrode

In 1953, International Union of Pure and Applied

Chemistry (IUPAC) defined normal hydrogen
electrode as the reference for measurement of
electrode potential.
platinized platinum foil
electrode
pure hydrogen gas at standard
pressure
activity of H+ being 1.
aH   1
Setting NHE as a reference:

=NHE

So,
 NHE   '
NHE  '
NHE 0

 
H / H2
  NHE  0
Set a cell with NHE serving as negative electrode
and the unknown electrode as positive electrode.

(–) NHEunknown electrode (+)

E of this cell: measured

E  '
unknown  '
NHE  unknown   NHE  unknown
When all the chemical species in the unknown electrode
are in their standard states, the electrode potential
measured is standard electrode potential .
 E  unknown

(-) NHE  Cu2+ (a=0.1)Cu (+) E = 0.342V

The electrode potential of the Cu  Cu2+ (a=0.1)
electrode is thus Cu2+/Cu = +0.342V .

Note: Since the unkonw electrode is positive

electrode where a reduction reaction occurs. The
measured electrode potential is also called
reduction electrode potential .
So, the electrode reaction is always written in the
reduction form.

Ox + z e- = Red

Cu2+ + 2e- = Cu
 6.4 Nernst equation for electrode reaction
For general electrode reaction (written in the reduction
form) :
c C + d D + z e- = g G + h H
 RT i
   ln  ai
zF i

g h
RT a a
   ln G
c
H
d
zF a a C D

Nernst equation for electrode reaction or half-cell

reaction
 Cell reaction: Zn + Cu2+  Zn2++ Cu
Electrode reaction (written in the reduction form) :
(+): Cu2+ + 2e  Cu (1)

Zn2+ + 2e  Zn (2)
( - ):

(1)  (2) = Cell reaction

E    
RT aCu RT aZn
 (  
 ln )  (  

ln )
2 F aCu 2 2 F a Zn 2

  RT aCu  aZn 2
 (   ) 
  ln
2F aZn  aCu 2
RT aZn 2
E  
ln Nernst equation for cell reaction
2F aCu 2
 6.5 Reference electrode
◆ Problems with NHE (primary standard)
1) The platinized Pt electrode is easily poisoned by the adsorption of impurities from the
solution and the gas.

2) An elaborate purification is required to purify the hydrogen.

3) The changes in pressure or in the depth of immersion of the electrode in the solution may
produce an variation in the potential of the electrode.

4) The preparation and the maintenance of the unit activity solution are complicated.
◆ Some electrodes with stable potential usually used as the secondary standard, named as
reference electrode .

mercury-mercurous salt electrodes because of their good reproducibility and ease of construction
and maintenance.

Saturated calomel electrode (SCE)

Hg(l)Hg2Cl2(s)KCl (m)
0/ V＝ 0.2412  6.61 10-4 (T  25)  1.7 
10-6 (T  25)2  9 10-10 (T-25)3
The mercury-mercurous sulfate electrode:
Hg(l)  Hg2SO4(s)  SO42 (m)
⊖ ＝ +0.640 V

The mercury-mercuric oxide electrode:

Hg(l)  HgO(s)  OH (m)
⊖ ＝ +0.098 V

The silver-silver chloride electrode:

Ag(s)  AgCl(s)  Cl-(m)
⊖ ＝ 0.197 V
7. Design of reversible cell
7.1 Types of reversible electrodes

The electrodes constituting a reversible cell are

reversible electrodes, and three types of such
electrodes are known. The combination any two
reversible electrodes gives a reversible cell.

I 0
(1) The first type of electrode
◆ metal – metal ion electrode

Consisting of a metal plate immersed in a solution containing the corresponding metal ions.

Electrode Electrode reaction

Cu2+  Cu (s) : Cu2+ + 2e– Cu

Na+Na(Hg)x:

Na+ +e– + xHg  Na(Hg)x

Ag(CN)2 – Ag(s) :

Ag(CN)2– + e–  Ag + 2 CN–
◆ Gas electrode
A gas passing through an inert electrode (e.g. Pt) immersed in a solution containing the
corresponding ions of the gas.

Electrode Electrode reaction

H+(a+)|H2(p),Pt 2H++2e →H2

OH-(a-)|H2(p),Pt 2H2O+2e →H2+2OH-

H+(a+)|O2(p),Pt O2+4H++4e-→2H2O

OH-(a-)|O2(p),Pt O2+2H2O+4e- →4OH-

Cl- (a-)|Cl2(p),Pt Cl2+2e- →2Cl-

(2) The second type of electrode

◆ metal–insoluble salt–anion electrode

a metal plate coated with insoluble salt containing the metal, and immersed in a solution
containing the anions of the salt.

Ag(s)AgCl(s)Cl- AgCl + e-  Ag + Cl-

Hg(l)Hg2Cl2(s)Cl-(c):

Hg2Cl2 + 2e-  2Hg + 2Cl-

Pb(s)PbSO4(s)  SO42-(c):

PbSO4 + 2e-  Pb + SO42-

◆ metal – insoluble oxide – H+( or OH-) electrode
consisting of a metal plate coated with insoluble oxide containing the metal, and immersed
in a acid or base solution.

AgAg2OOH Ag2O  H 2O  2e  2 Ag  2OH

AgAg2O H+
Ag2O  2H   2e  2 Ag  H 2O

HgHgOOH
HgO  H 2O  2e  Hg  2OH 

HgHgO H+ HgO  2H   2e  Hg  H 2O
(3) The third type of electrode:
oxidation-reduction electrodes

immersion of an inert metal collector (usually Pt) in a solution which contains two ions of
the same element or molecules in different states of oxidation.

Pt(s)Sn4+, Sn2+
Sn4+ + 2e-  Sn2+

Pt(s)Fe(CN)63-(c1), Fe(CN)64-(c2) :

Fe(CN)63- + e-  Fe(CN)64-

Pt(s) quinone (醌), quinhydrone

 7.2 Types of reversible cell
◆ Chemical cells
In a chemical cell, the cell reaction is a chemical reaction.

Chemical cell with single electrolyte

Ag(s)AgCl(s) HCl (c)H2(P) Pt(s)

2Ag + 2HCl  2AgCl + H2

Chemical cell with double electrolytes

Zn(s)ZnSO4(c1)CuSO4(c2) Cu (s)

Zn + Cu2+  Zn2++ Cu
◆ Concentration cells
A galvanic cell in which the chemical energy
converted into electrical energy is arising from the
concentration difference of a species at the two
electrodes of the cell.
In a concentration chemical cell, the cell reaction is
NOT a chemical reaction.
Concentration cell with single electrolyte
K ( Hg ) (a1)KCl (m) K (Hg) (a2)
）K (a1)  e  K+ (m)
+）K+ (m) + e  K (a2)

cell reaction K ( a 1 )  K (a 2 )

RT a 2 
EE  ln
ZF a 1
0
RT a 2 RT a1
 ln  ln
F a1 F a2
 Concentration cell with double electrolytes

AgAgNO3 (m1)  AgNO3 (m2) Ag

）Ag  e  Ag+ (m1)
+）Ag+ (m2) + e  Ag

cell reaction Ag+ (m2)  Ag+ (m1)

RT m1 1
 RT m2  2
EE  ln  ln
F m2  2 F m1 1
0
7.3 Design of the reversible cell

How to construct a reversible cell based

on a given cell reaction ?
(1) Write the two half-reactions based on a given cell reaction

Very important !

(2) Determine electrodes and electrolyte

(3) Write cell donation

(4) Make checking

◆ Examples for oxidation-reduction reaction

Zn + CuSO4 = ZnSO4 +Cu

Half-reactions:

Zn – 2e- = Zn2+ Anode

Cu2+ + 2e- = Cu
Cathode

Anode: ZnZn2+;
Cathode: CuCu2+;
Electrolyte: ZnSO4; CuSO4
Salt bridge

Zn(s) ZnSO4(c1) CuSO4(c2) Cu(s)

◆ Examples

AgCl = Ag+ + Cl-

Half-reactions:
Anode
Ag – e- = Ag+
AgCl + e- = Ag + Cl- Cathode

Anode: AgAg+
Cathode: AgAgClCl-;
Electrolyte: AgNO3; KCl;
Salt bridge

Ag(s) AgNO3(c1) KCl(c2) AgCl(s)Ag(s)

◆ Examples for neutralization reaction

H2O = H+ + OH-

Half-reactions:
H2 – 2e- = 2H+ Anode
2H2O + 2e = H2 + 2OH-
Cathode

Anode: Pt(s)H2(P)H+;
Cathode: Pt(s)H2(P)OH-;
Electrolyte: HCl, NaOH;
Salt bridge

Pt(s)H2(P)HCl(c1) NaOH (c2)H2(P) Pt(s)

◆ Examples

H2 (P1)  H2 (P2) ( P1 P2)

Half-reactions:
Anode
H2 (P1)  2e  2 H+ (m)

2 H+ (m) + 2e  H2 (P2) Cathode

Anode: Pt, H2 (P1)H+

Cathode: Pt, H2 (P2)H+
Electrolyte: HCl

Pt, H2 (P1)HCl (m)H2 (P2), Pt

7.11 Decomposition voltage and overpotential
Reversible cell correlates electrochemistry and thermodynamics and
has great theoretical importance, but it has no practical use.

Either electrolytic cell or galvanic cell always works in irreversible way.

Why ?
7.11.1 Decomposition voltage

Electrolysis of water

Measurement of the value of the

current ( I ) as the voltage
applied (V ) increases.

H2SO4
 current

Decomposition voltage: the minimum potential difference which must

be applied between electrodes before decomposition occurs and a
current flows.
 7.11.2 Electrode polarization and overpotential

When the current passes through a galvanic or electrolytic cell (namely under
irreversible conditions), the electrode potential will differ from the reversible value,
this phenomenon is defined as polarization.

The discrepancy between reversible potential re and irreversible potential is ir
called overpotential ().

=| re - ir|

The value of  is positive.

 c = cathode c = cathode

a = anode a = anode

In a galvanic cell
Polarization causes decrease in electromotive force of galvanic cell.

c, ir < c, re

c =c, re- c, ir
a, ir > a, re
a =a, ir- a, re
 In an electrolytic cell

Polarization causes increase in decomposition voltage of electrolytic cell.

c, ir < c, re

c =c, re- c, ir
a, ir > a, re
a =a, ir- a, re
7.11.2 Origins of electrode polarization

(1) Concentration polarization

(2) Activation polarization or electrochemical polarization

(1) Concentration polarization

caused by concentration changes in the environment adjacent to the surface.

i0 =0

Cu Cu2+ RT 
   ln aCu2
nF

C Cu2+ (near the surface ) = C Cu2+ (bulk)

RT

re    ln aCu2 (bulk )
nF
i >0 as an anode

Cu - 2e-= Cu2+

C Cu2+ (near the surface ) > C Cu2+ (bulk)

RT
ir    ln aCu2 (near the surface)  re
nF
i >0 as a cathode

Cu2+ + 2e- = Cu

C Cu2+ (near the surface ) < C Cu2+ (bulk)

RT
ir    ln aCu2 (near the surface)  re
nF
Elimination of concentration polarization :

(1) Stir the solution in electroplating

(2) Discharge the battery with intervals

 (2) Activation polarization and hydrogen overpotential
The term activation polarization makes reference to retarding factors that are an inherent part of th
kinetics of all electrochemical reactions.

Five steps:

(1) H+ migrates toward the surface of the cathode

(2) Adsorption of H+

(3) H+ ions gain electrons to form absorbed H2

(4) Desorption of H2

(5) H2 diffuses to bulk solution

The evolution of hydrogen gas at the electrode surface :

The rate at which hydrogen ions are transformed into hydrogen gas is a
function of several factors, including the rate of electron transfer from a metal
to hydrogen ions. In fact, there is a wide variability in this transfer rate of
electrons by various metals and, as a result, the rate of hydrogen evolution
from different metal surfaces can vary greatly.
 In 1905, Tafel reported the I ~ V curves of hydrogen evolution on
different metal surfaces and obtained an empirical equation :

 = a + b log j

j is the current density.

"a" and "b" are characteristic constants of the electrode system.

 Categories a Metals

Metal with high 1.0-1.5 Hg(1.41), Pb(1.56),

hydrogen Zn(1.24), Sn(1.20)
overpotential
Metal with middle 0.5-0.7 Fe(0.7), Ni(0.63),
hydrogen Cu(0.87)
overpotential
Metal with low 0.1-0.3 Pt(0.05), Pd(0.24)
hydrogen
overpotential
How to lower hydrogen overpotential ？

 = a + b log j

1) Use material with low overpotential (less value of a) as electrode.

2) Decrease the current density j by increasing the effective area of the

electrode using porous electrode techniques.