CHAPTER 2:

ELECTROCHEMICAL
CELLS & ELECTRODES
Trần Thụy Tuyết Mai, PhD.
Email:TUYETMAI@HCMUT.EDU.VN

Division of Physical Chemistry – Faculty of Chemical Engineering

HCMC University of Technology - VNU-HCM 1
 CONTENT
1. Electrochemical cells
2. Thermodynamics of electrochemical cells and electrodes
3. Classification of cells and electrodes
4. Junction (diffusion) potential
5. Measurement of emf (electromotive force)
6. Electrochemical sources

P.W.Atkins, “Physical Chemistry”, Oxford University press, 2004.

2
1. Electrochemical cells

3
 ELECTROCHEMICAL CELLS
What reaction would occur if a Zn bar was immersed in a CuSO4 aqueous solution?
Zn + CuSO4  ZnSO4 + Cu H298, rxn. = -210.84 kJ,  G0298= -209.9 kJ = -50710 cal

An electrochemical cell consists of two

electrodes, or metallic conductors, in
contact with an electrolyte, an ionic
conductor (which may be a solution, a liquid,
or a solid). An electrode and its electrolyte
comprise an electrode compartment.

Chemical
energy
Electrochemical
cell
Electrical energy
Anodic zone Cathodic zone

4
 A galvanic cell is an
electrochemical cell that
produces electricity as a
result of the spontaneous
reaction occurring inside it.

An electrolytic cell is an
electrochemical cell in which
a non-spontaneous
reaction is driven by an
external source of current.

To converse chemical energy to electricity, we need to set up both

oxidation and reduction occur parallel at 2 different electrodes/electrolyte
solutions and let electron flow transfer from anode to cathode.
7
 NOTATIONS
 :without diffusion potential
(-) Zn ZnSO4  CuSO4  Cu (+)
 : Electrode – solution, electrode’s components
Half reaction:
Anode (-) : Zn  Zn2+ + 2e ; oxidation
Catode (+) : Cu2+ + 2e  Cu; reduction
In the case of there is a diffusion potential between two contacted
electrolytes
(-) Zn ZnSO4 CuSO4  Cu (+)

When electrodes/ electrolytes were composed with various
components, using “,” to notice the components:
 (-) Pt  H2  H+ || Fe3+, Fe2+| Pt (+)
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 ELECTRICAL DOUBLE LAYER (EDL) &
ELECTRODE POTENTIAL ()
• Cations from the metal
surface will transfer to the
solution and will leave e-  electrolyte electrolyte
the surface has (-) charge
 attract cations 
blocking the transfer of the
cations. At equilibrium:
“EDL”

+M > +solution +M < +solution

Electrode potential: potential difference only appears on the
contact surface between contact electrode and electrolytes.
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 ELECTRODE POTENTIAL ()
- EDL  an electric potential jump between
electrode and solution. The electric potential jump
depends on: electrode, solvent, ionic
concentration, temperature.

- The potential difference is called the

electromotive force (emf), E, of the cell.

- To measure the electrode potential 

standard electrode as reference electrode.

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 HOW TO MEASURE
ELECTRODE POTENTIAL (  )

Electrode potential, , is the

electromotive force of a cell built of
two electrodes:
•on the left-hand side of the cell diagram
is the standard hydrogen electrode (SHE;
oH+/H2 = 0 V), and
•on the right-hand side is the electrode in
question (working electrode).
Ecell = right − left (SHE) = electrode

Electrode potential () = electromotive

force (emf) (E) of the cells

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 Standard electrode potential table

o298 of Ox/Red at standard conditions

(a=1, @ 25 0C)
o(2H+/H2) = 0 V
o298 (Zn2+/Zn)= -0.7628V < 0
 2H+ + Zn = H2 + Zn2+
o298 (Cu2+/Cu)= +0.337V > 0
 H2 + Cu2+ = 2H+ + Cu

2H+ + 2e  H2 0V

12
oxidation reduction

13
 ELECTRIC POTENTIAL JUMPS
& ELECTROMOTIVE FORCE

E =  (electric potential jumps)

Electrochemical cell :
M1L1L2M2
E E = M2/M1 +M1/L1+L1/L2+L2/M2
M2

M1 M2
L1/L2 : liquid junction potential (diffusion potential) often
L1 L2
small and negligible (1 – 2 mV)

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 Electromotive force
Consider cell: (A) : (-) M2  M1  L1  L2  M2 (+)
And 2 cells: (B): (-) M0  L0  L1  M1  M0 (+)
(C): (-) M0  L0  L2  M2  M0 (+)
EA= M2/M1+M1/L1+L2/M2
EB= M0/L0+L1/M1+M1/M0 EC- EB = EA
EC= M0/L0+L2/M2+M2/M0
If M0  L0 is the standard electrode (H2H+): EB= (-) và EC= (+)
Therefore: EA= (+) - (-) (Without diffusion potential)

Emf. of a electrochemical cell is equal to potential of (+) electrode

subtract potential of (-) electrode (without diffusion potential)
tuyetmai@hcmut.edu.vn
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 2. Thermodynamics of
electrochemical cells and electrodes

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 ELECTRIC WORK

• Electrical work for conversion of 1 mole reactants:

A’max = q.E = n.F.E
• @ const. T, P, applying 2nd thermodynamic law for
reversible process: G = - A’max
n: number of electrons interchange
G = - n.F.E E: electromotive force of cell (V)
F (= 96500 C/mol) : Faraday’s constant
G (J/mol)
1 J = 1 W.s = 1 V.(A.s) = 1 V.C
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EFFECT OF CONCENTRATION ON E & 
(NERNST EQUATION)
Rxn. in cell:
aA + bB = dD + lL

aDd .aLl
 G  RT ln K a  RT ln( a b )  nFE @ 298 K:
a A .aB
0.059 aLl .aDd
RT
ln K a  const  E0 E  E0  lg a b
nF 2 a A .aB

RT a Ll a Dd
E  E0  ln a b (NERNST equation) Daniel cell
nF a A aB
0.059 aZn2
E0: emf at ai = 1 E  (E
0
Cu2 / Cu
E 0
Zn2 / Zn
) lg
2 aCu2
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 NERNST EQUATION
( EFFECT OF CONCENTRATION ON  )

Rxn. on electrode:
Ox + ne  Kh

RT akh
  o
T ln
nF aox 0.059 akh
@ 298 K   o
298  lg
n aox
0: electrode potential at ai= 1
0298 checked in Data section

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 EFFECT OF TEMPERATURE
G = H - T.S

PT Gibbs - Helmholtz :
(G ) (G )
G  H  T.  n.E.F  H  T.
T P T P

H T (nFE) H E
E    T.
n.F n.F T P n.F T P

H dE
E T
n.F dT
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 EFFECT OF TEMPERATURE
S = ST2 – ST1

For cell emf’s temp. dE S emf’s temp. coefficient

coefficient :
 is proportional to the
dT nF entropy change

For electrode:
d S
emf’s temp.  In the narrow temp. range  d/dT = const.
coefficient dT nF

d
 
o
T
o
298  (T  298)
dT
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22
 LUTHER RELATION
Considering on M metal have 2
cations of Mh+ và Mn+
Mh+ + he  M (1) G1 = -hFh
ne

Mn+ + ne  M (2) G1 = -nFn

Mh+ + (h-n)e  Mn+ (3) G1 = -(h-n)Fh/n

rxn. (3) = rxn. (1) – rxn. (2)
 G3 = G1 - G2

 (h  n).F . h / n  h.F . h  n.F . n

(h-n).h/n = hh - nn (Luther relation)

Using to define h/n if we know h - n

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25
TYPE 1:
Reversible cationic /anionic electrodes consist of metal (or non-metal)
in a solution containing its ion.
Reversible cationic electrode: Mn+M: Mn+ + ne = M
RT aM
M n  o
 ln
/M M n / M nF a M n
RT
M n  o
 ln aM n
/M M n / M nF
Reversible anionic electrode: AAn-: A + ne = An-
RT a n
 A/ A n  o
 ln A
A / An  nF aA
RT
 A/ A n  o
 ln a n
A / An  nF A 26
EXAMPLE

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TYPE 2 Metal coated by an insoluble salt immersed in a
solution containing the anion of the salt
• Notation: An-  MA  M

 RXN. on the electrode: MA + ne = M + An-

RT
 Nernst equation:  MA/ M , A  
n
o
MA / M , An
 ln a An
nF
Electrode Ag-AgCl: Cl-  AgCl  Ag
Half rxn. : AgCl + e = Ag + Cl-

 AgCl / Ag ,Cl   AgCl


o

/ Ag ,Cl
 0,059 lg aCl 

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 Calomel electrode:
Cl-  Hg2Cl2  Hg, Pt
Half rxn on electrode:
Hg2Cl2 + 2e = 2Hg + 2Cl-

0.059
 Cal   o
Cal  2
lg aCl   0.2678  0.059 lg a
Cl 
2

Besides normal hydrogen electrode (NHE), calomel and silver

chloride electrodes are considered as typical reference electrodes.

tuyetmai@hcmut.edu.vn 29
 TYPE 3
A metal coated by two insoluble salts with common anion in a
solution containing cation of the second salt.
M’n+  M’A, MA  M TMA < TM’A

Ca2+CaCO3, PbCO3Pb
Reaction: PbCO3 + Ca2+ + 2e = Pb + CaCO3

R.T
  0
Pb 2 / Pb
 . ln aPb 2
n.F
TPbCO3  aPb 2 .aCO 2 ; TCaCO3  aCa2 .aCO 2 R.T
3 3
  
'0
. ln aCa2
TPbCO3 n.F
aPb 2  aCa2
TCaCO3

tuyetmai@hcmut.edu.vn 30
 GAS ELECTRODES
• An inert metal in contact with
both a gas and its ion

H2 gas electrode: H+  H2  Pt
2H+ + 2e = H2

2
RT a H 
H 
/ H2
  Ho  / H  ln
2
2 F PH 2
0.059
25 C   H  / H
o
 0.059 pH  lg PH 2
2
2
http://slideplayer.com/slide/9300791/

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 GAS ELECTRODE

Điện cực oxy: OH-  O2, Pt RT PO2

O2 + 2H2O + 4e = 4OH-
OH 
/ O2
 o
OH  / O2
 ln 4
4 F aOH 

Điện cực Clo: Cl-  Cl2, Pt RT PCl2

Cl   o
Cl  / Cl2
 ln 2
Cl2 + 2e = 2Cl- / Cl2
2 F aCl 

tuyetmai@hcmut.edu.vn 32
 AMALGAM ELECTRODES:
• Amalgam of a metal in a solution containing its ion.
Mn+  M, Hg; Mn+ + ne = M(Hg)
RT aM ( Hg )
M n
/ M , Hg
 o
M n / M , Hg
 ln
nF a M n
Cadimi amalgam electrode: Cd2+  Cd, Hg

Electrode rxn.: Cd2+ + 2e = Cd(Hg) Cadimi amalgam electrode

(Cd 12.5%) is used to make
RT aCd ( Hg )
Cd 2  o
Cd 2 / Cd , Hg
 ln Weston battery, which has
/ Cd , Hg
2F aCd 2 constant E and is used in emf
measurement.
tuyetmai@hcmut.edu.vn 33
 REDOX ELECTRODES
• An inert metal (often Pt) in a solution containing both oxidative and reductive forms

Ox , Red  Pt
Phản ứng điện cực: Ox + ne = Red
RT aKh
 Re dox   o
Re dox  ln
nF aOx
Simple redox electrode: Fe3+ ,Fe2+  Pt
RT aFe 2
 Fe 3 / Fe 2 , Pt   3 2 
o
ln
Fe / Fe , Pt F aFe 3

tuyetmai@hcmut.edu.vn 34
 COMPLEX REDOX ELECTRODE
Electrode: MnO4-, H+ , Mn2+  Pt Electrode rxn.: MnO4- + 8H+ + 5e = Mn2+ + 4H2O
8RT RT aMn2
 MnO , H
 
/ Mn2 , Pt
 o
MnO4 , H  / Mn2 , Pt
 ln aH   ln
4
5F 5F aMnO
4

o OH
C6H4O2,H+C6H4(OH)2,Pt : + -
+ 2H + 2e =
(Quinhydrone electrode)
o OH
Quinone (Q) Hydroquinone (Hq)

RT aHq
Quinh   o
Quinh  ln
2 F aQ aH2  RT
Quinh   o
Quinh  ln aH 
RT RT aHq F
Quinh   o
Quinh  ln aH   ln
F 2 F aQ (As indicator electrode for pH measurement)
tuyetmai@hcmut.edu.vn 35
36
GLASS ELECTRODE

aH  a H  aM 
tt    0.059 lg
o
tt K tt
aH 
tt
aH  .aH 
tt

pH = 10 – 12 aH  (a  aH  )
K tt

tt    0,059 pH
o'
tt
aH  aH 
tt

Alkaline medium

tt    0,059 lg aM
o ''
tt 

tt    0,059 pH
o '''
tt
tuyetmai@hcmut.edu.vn 39
4. Junction (diffusion) potential

40
 kt: exist in loaded circuits, at interface of the two electrode solutions

Reason: velocities of ions are different  an electrical double layer appears  an

electric potential jump  junction (diffusion) potential
. .
Ex: (-) Ag  AgNO3 (a’) : AgNO3(a’’) Ag (+) ( a’ < a’’)

(-)Ag (+)Ag
- AgNO3 diffuse from (+) to (-) (because F
of concentration difference) kt
- +
- Velocity of NO3- > velocity of Ag+ 
- +
t+
NO3- moves faster through the
membrane  (-) charges, left of the t- - +
membrane has (+) charges  kt - +
- +
-kt is often small (< 0.1V) AgNO3’(a’) AgNO3(a” )

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 Eload  E  df

   RT a ''
df  ln 

   F a '


If t- > t+ - > +  df > 0 Eload > E

If t- < t+ - < +  df < 0 Eload< E
If t- = t+ - = +  df = 0 Eload= E

42
 Methods to avoid df
- Use salt bridge:
an agar form of concentrated salt
containing cation and anion which
have similar velocity. Ex: KCl, KNO3,
NH4Cl, NH4NO3, ...

- Make double cells:

(-) Ag, AgCl  HCl(a’) : HCl(a’’) AgCl,Ag (+)

.

(-) Ag,AgCl  HCl(a’)H2, Pt, H2 HCl(a’’) AgCl,Ag (+)

43
5. Measurement of emf

44
 Measurement of emf
AC
Ex  .Ew
AC '
Ew: a known, highly stable emf cell
(Weston cell)

Weston cell:
(-) Cadimi amalgam electrode
(+) Hg electrode type 2

Temperature coefficient: 5.10-5 V/oC (very small value)

(-) Cd(Hg) (12,5%)CdSO4 ,CdSO4 .8/3H2O (r)Hg2SO4  Hg,Pt (+) 45

 Applications
pH measurement

Determination of activity coefficients ()

Determination of solubility product (T)

46
 pH measurement

Principle: measurement of emf of a cell consists:

- A known  electrode: Calomel, or silver chloride electrode
(reference electrode)
- A electrode which potential depends on pH: Hydrogen
electrode, quinhydron electrode, glass electrode (indicator
electrode)

47
(-)Hg, Hg2Cl2 | KCl || H+ (x)| glass electrode (+)
E  tt  cal  tt0  0.059 pH  cal

tt0  cal  E
pH 
0.059

Advantage: no chemicals needed.

Disadvantage: fragile due to the very thin glass membrane
(0.01 – 0.03mm).

48
 Determination of activity coefficients ()

Ex: Determination  of HCl with molarity m.

Consider a cell: (-) Pt, H2 (1 atm) | HCl (m) | Hg2Cl2, Hg (+)

Reaction: Hg2Cl2 + H2 = 2Hg + 2HCl

2
NERNST equation: R.T a R.T
E  E0  . ln HCl  E 0  ln aHCl
2F PH2 F
R.T R.T
 E0  ln a2HCl  E 0  2 ln(  .  .m)
F F

R.T R.T
E  E 2 0
ln(  .m)  2 . ln(  )
F F

49
 R.T R.T
E  E 2
0
ln(  .m)  2 . ln(  )
F F
- If Eo is known: Measure E  calculate 
- If Eo is unknown:
R.T R.T
E2 ln(  .m)  E 0  2 . ln(  ) =Y
F F
If m  0 :   1 then Y  Eo

Plot Y-m , extrapolate at m= 0  Eo

50
 Determination of solubility product (T)

Ex: Determination T AgCl

Consider a cell: (-) Ag, AgCl | HCl | Cl2, Pt (+)

Reaction: 1
Cl 2  Ag  AgCl 
2
E   Cl
2 / Cl
   AgCl / Ag ,Cl   0
Cl2 / Cl  
 0.059 lg aCl    AgCl
0
/ Ag , Cl 
 0.059 lg aCl  
Besides:  0
AgCl / Ag , Cl 
 0
Ag  / Ag
 0.059 lg TAgCl

E  Cl
0
 2 / Cl 
  Ag
0

/ Ag

 0.059 lg TAgCl

Cl0 2 / Cl 
 1.358V ; Ag
0

/ Ag
 0.799V ; Emeas. = 1.136V  TAgCl = 1.77x10-10

51
6. Electrochemical sources

52
- Primary cells/ batteries: one-time use
(non- rechargeable)
Ex: dry cell: La Clanché (Zn-C)

- Secondary cells/ batteries: rechargeable

Ex: Lead acid, NiCd, NiMH, Li-ion

- Fuel cell/ batteries: Working continuously

Ex: Hydrogen – oxygen cell, …

53
 Primary cells/ batteries

(-) Zn  NH4Cl (20%), ZnCl2  MnO2, C (+)

(-) Zn – 2e = Zn+2 Eo = 1,6 V

(+) 2MnO2 + H2O + 2e = Mn2O3 + 2OH-

54
Secondary cells/ batteries

55
(-) Pb  PbSO4  H2SO4 (25-30%)  PbO2  Pb (+)

(-) Pb + SO42- – 2e  PbSO4

(+) PbO2 + 4H+ + SO42- + 2e  PbSO4 + 2H2O

Eo = 2.037 V

56
 Hydrogen Fuel Cell
(-) Ni  H2  KOH (30-40%)  O2  Ni (+)

(-) 2H2 + 4OH- – 4e  4H2O

(+) O2 + 2H2O + 4e  4OH-

Eo = 1.23 V

57