Chapter 3

Kinetics of electrochemical processes

 Electrolysis

Electric energy Chemical energy

Galvanic cell
 Contents
1. Electrolysis
2. Overpotential
3. Applications of electrolysis
4. Electrochemical corrosion
 Electrolysis

ion (+)
(Conductor q cation q (Conductor
type 1) type 1)
ANODE ion(-) CATHODE
Oxidation reaction anion Reduction reaction
2Cl-  Cl2 + 2e Cu2+ + 2e  Cu

Fe2+  Fe3+ + e (Conductor 2H2O + 2e  H2 + 2OH-

type 2)
 Faraday electrolysis laws
1st Law: The mass of a substance altered at an electrode during
electrolysis is directly proportional to the quantity of electricity transferred
at that electrode.
m= k0It = k0.q
k0: constant
q: quantity of electricity (C- culong= 1 A.s)

2nd law: For a given quantity of electricity, the mass of a substance altered
at an electrode is directly proportional to the substance's equivalent
weight
𝒒 𝑴
m= k0.q= .
𝑭 𝒛

F= 96485 C (96500 C): Faraday number

M: molar mass of the substance
z: valency number of ions of the substance (electrons transferred per ion).
M/z: equivalent weight of the substance.

Current efficiency:  = mactual/mtheory (<1).

 Notation
(Textbook)

For batteries
(-) electrode: (oxidation reaction)
ex: Zn – 2e = Zn2+

(+) electrode: (Reduction reaction)

ex: Cu2+ + 2e = Cu

(-) (+)
 Notation
(Textbook)
For electrolysis
anode: (oxidation reaction)
ex: Cu – 2e = Cu2+

cathode: (Reduction reaction)

ex: Zn2+ + 2e = Zn
4H+ + 4e = 2H2 
Cathode Anode

Loss Electron is Oxidation Reduction at Cathode

 Electrolysis of H2SO4 using inert Pt electrode

Anode Strong
reductant

B C A 2 H2O - 4 e− = O2(g) + 4 H+
0 = 1,23 V
mA

V K
2 SO42- - 2 e− = S2O82-
0 = 2,01 V
(-)Pt (+)Pt

Cathode Strong
oxidant

H2SO4 2 H2O + 2 e− = H2(g) + 2 OH−

0 = -0,83 V

2H+ + 2 e− = H2(g)
Cathode Anode 0 = 0 V
 0 (Ox/Red)=
Electrode potential/ Redox potential

high 0 (Ox/Red)  strong “Ox”

high 0 (Ox/Red)  weak “Red”
 Electrolysis of H2SO4 using inert Pt electrode

Anode:
B C A 2H2O - 4e = 4H+ +O2
mA
(oxidation reaction)
V K
Cathode:
(-)Pt (+)Pt 4H+ + 4e = 2H2 
(Reduction reaction)
Total:
H2SO4 2H2O = O2 + 2H2

Cathode Anode Electrolysis of H2O

 Thermodynamically
2H2O = O2 + 2H2
unfavorable reaction can
G0298 = +56,7 Kcal/mol occur by the electricity

I B
In the electrolysis process: (mA)

Products (O2 and H2) are only

observed at a certain voltage
applied to the circuit – named
decomposition potential/voltage A
(Ef).
O Ef E (V)
Decomposition voltage (Ef)
(Electrolysis of H2SO4)
+ Minimum voltage needed for a electrolysis
process to produce products on the
electrodes
+ Without overpotential, Ef is equal to the emf of
the cell with similar electrodes.
Electrode polarization
• The deviation of voltage from the value at
equilibrium upon the passage of current is called
polarization.
• For an electrode, the deviation of electrode
potential from its equilibrium state is called the
electrode polarization.
• overpotential, denoted as η and expressed in volts.

 (cathode)  E (cathode, equilibrium)  E (cathode)

 (anode)  E (anode)  E (anode, equilibrium)
 B
Electrochemical polarization
E
- +
B C A E  Ep
A I
O Ef E (V)
mA R
V K
Ep: polarization
(-)Pt (+)Pt
potential
H2SO4
(-) H2 H2O O 2 (+)
Pt, H2 H+ Pt, O2 H2O

0 H+/H2=0V Ep =+ - -
0 O2,H+/H2O=1,23V

(-) Pt, H2 H2O (H2SO4)O2, Pt (+)

 Electrochemical polarization
(-) Pt, H2 H2O (H2SO4)O2, Pt (+)
(-): 2H+ + 2e = H2
R.T PH 2 R.T aH2 
( )   0
H  / H2
 . ln 2   H  / H 
0
. ln
n.F aH  2
n.F PH 2

(+): 0,5O2 + 2H+ + 2e = H2O

R.T aH 2 O R.T aH2  .PO02.5
(  )   0
H 2O / O2  . ln 2 0.5   H 2O / O2 
0
. ln
n.F aH  .PO2 n.F aH 2 O
 Electrochemical polarization
(-) Pt, H2 H2O (H2SO4)O2, Pt (+)

-
Ep = + - -
+
 Electrochemical polarization

Ep = (+) - (-)
- When E increases: O2, H2 increase  (+)
increases and (-) decreases Ep increases

- When PO2, PH2 = 1 atm  Ep max : E = Ef

Appearance of H2 , O2 at electrodes
 Concentration polarization
Electrode potential shift because of the concentration
difference.

Consider an electrode: Mn+/M

RT
Initial (assume =1):     . ln C
0
nF
Electrochemical reaction: Mn+ +ne = M
RT
  
/ 0
. ln CS
nF
CS : concentration close to the electrode surface (Cs ≠ C)
 Concentration polarization
Electrode: Mn+/M
RT RT
 
0
. ln C   
/ 0
. ln CS
nF nF

IF the electrode is the cathode: IF the electrode is the anode:

Mn+ + ne = M M - ne = Mn+
 Cs < C  Cs > C

RT CS RT CS
C     
/
. ln 0  a     
/
. ln 0
nF C nF C
Overpotential ( /eta/ ):the
potential difference
(voltage) between thermodynamically determined
reduction potential and the potential at which the redox
event is experimentally observed

= Ef - Eelectrode
Reason:
The electrochemical process is relatively slow,
complex, multi-steps
Ex:
Electrolysis of CuSO4 with inert Pt electrode:
Ef = 1,3 V ; Eelectrode = 0,89 V  = 0,41 V
 Tafel equation

 = a + b.lgi
Where: : overpotential of hydrogen (V).
i: current density A/cm2
a: constant, depend on the
electrode material
RT
b  2 2,303. ln
nF
Electrode Solution, concentration a b
With n=1, T=25oC : b  0.166 material
at 25oC
 If i increases to 10 times,  Pb H2SO4 1,0N 1,533 0,118
increases by 0.166V
Hg H2SO4 5,0N 1,400 0,116
HCl 1,0N 1,390 0,119
KOH 0,1N 1,430 0,093
Zn H2SO4 1,0N 1,240 0,118
Pd KOH 0,1N 0,637 0,125
Pt trôn HCl 1,0N 0,100 0,130
Pt HCl 0,5N 0,073 0,028
 Theories for H2 overpotential

(Read textbook)

Combination theory (Tafel, 1905)

Slow discharge theory (Frumkin, 1933)

For explanation of Tafel’s equation

 Theories for H2 overpotential
The discharge of H3O+ ion to produce H2 are
complicated, consists of many steps.

- Diffusion: H3O+ diffuse to the electrode surface

- Dehydration: H 3O   H   H 2 O
- Discharge and H atom adsorption: H   1e  H and H  Me  Me | H

- Combination: 2 H  H 2 (ads.)

- H2 desorption: H 2 (ads.)  H 2 ( gas )

Roles of the overpotential
Disadvantage:
More voltage needed for the electrochemical
process
Advantages:
- Electroplating becomes possible for some
metals
- Electrolysis of NaCl using Hg cathode
becomes possible
- Charging the Lead- acid batteries becomes
possible
0 (Cu2+/Cu) = 0,337 V 0 (H+/H2) = 0V

Cathode
Electroplating
0 (Zn2+/Zn) = -0,76 V 0 (H+/H2) = 0V
0 (Ni2+/Ni) = -0,25 V 0 (H+/H2) = 0V
0 (Cr3+/Cr) = -0,74 V 0 (H+/H2) = 0V
Zn electroplating ???
Ni electroplating ???
Cr electroplating ???
0 (Pb2+/Pb) = -0,126 V 0 (H+/H2) = 0V

Charging of lead- acid battery???

PbSO4 + 2e = Pb + SO42-

2H+ + 2e = H2
Applications of electrolysis
Electro-metallurgy and electroplating
- Aluminium production: Electrolysis of Al2O3 – Cryolit (3NaF.AlF3)

- Metal separation and purification: metal production from mines: Cu,

Zn, Ca, Co, Fe, Mn, Cr, …

- Electroplating using complex compounds: [Ag(CN)2]- ; [Cu (NH3)4]2+

Organic synthesis
- Limit due to the complicated mechanism

Analytical method
- Volt-Ampere method – polarography method
 (cathod) Al3+ + 3 e− → Al

25 million
2-3 ton/year
ton/year
Electrolysis
1883 technology 2007
(http://peter-entner.com/E/Theory/PrincHH/PrincHH.aspx)
Polarography method

I (mA)

Ii

i U (V)

Application:
Qualitative analysis (based on i) , quantitative
analysis (based on Ii) of multi-component solution
Metal corrosion is the phenomenon
that metal is oxidized by the
environment. There are 2 types of
corrosion:

Chemical Electrochemical
corrosion corrosion
Chemical corrosion: The process
follows the standard kinetics of
heterogeneous reactions, not accompanied
by the appearance of electrical current

Ex:
Corrosion by dry gases: O2, H2S, SO2,.. ; or by
solvents: gasoline,…; or by other gas at high
temperatures.
Electrochemical corrosion: The
process follows the electrochemical
kinetics and accompanied by the formation
of microscopic cells.

Ex:
corrosion in the presence of electrolyte such as
in the humid air, the ground, ..
 Electrochemical corrosion
• $200 billion dollars (or 4% of the gross domestic product) is spent
in the United States each year to prevent or repair the damage done
by corrosion.

• Economically, one of the most important metals to corrode is iron

and one of its alloys, steel.
• Almost 20% of the iron and steel produced in the United States
each year is used to replace objects that have corroded.
(Source:http://science.jrank.org)
Electrochemical corrosion
28/4/1988, Boeing 737, Aloha airlines, a part of the plane
blown out at the height of 24000 feet, due to corrosion
1/8/2007, 35W St. Anthony Bridge across Mississippi River
16/4/2001, Explosion of Humber Estuary Refinery (England) due to gas
pipeline corrosion
Mechanism of electrochemical corrosion

(-) electrode of the cell- oxidation reaction:

Me – 2e  Me2+
(+) electrode of the cell- reduction reaction:
0.5 O2 + H2O + 2e  2OH-
In acidic environment: 0.5 O2 +2H+ + 2e  H2O
 Mechanism of electrochemical corrosion
Ex: corrosion of steel
Forming the microscopic cells in humid environments:
(-) Fe Fe2+ H2O O2, Fe (+)
(-) Fe Fe2+ H2O O2, Fe (+)

(-) Fe – 2e = Fe2+ 0 (Fe2+/Fe) = - 0,44 V

(+) 0,5O2 + 2H+

+ 2e = H2O 0 (H2O/H+,O2) = 1,23 V

0,5O2 + H2O + 2e = 2OH- 0 (OH-/O2) = 0,40 V

 Methods for protection of metal corrosion

Coating Environment cathodic

- By organic compound:
Treatment protection
painting Control the corrosion of a
- Reduction of oxidative agents
- By metal/ metals: plating metal surface by making
(O2) : heating , blower , ..
(electroplating) Zn, Ni, Cr, … it the cathode of an
- Add inhibitors to reduce the
- By oxides: Al2O3 film,… electrochemical cell.
corrosion rate

- Sacrificial anode
- Impressed current systems
 Sacrificial anode
(-) ZnZn2+ H2O O2,Fe (+)

0 (Zn2+/Zn)= -0,76 V

0 (Fe2+/Fe)= -0,44 V
Impressed current systems

- +

(-)Me
(+)Pt

Cathode Anode