Electrochemistry

 Definitions
 It studies the relation between chemical and electrical phenomena
 It studies the electrode solution and the behavior of each electrode

 Types of Electrochemical Cells

1. Galvanic Cells or Voltic Cells
Chemical reactions lead to electric work (e.g. Daniel cell)
Zn / ZnSO4//CuSO4 / Cu
2. Electrolytic Cells Fork Ag
Electrical work leads to chemical reaction
Used in electrolytic painting (e.g. painting
a steel fork with silver)

 Types of Galvanic Cells

AgNO3

1. Chemical cell with liquid junction potential [L.J.P.]

The two electrodes separated by porous pot
e.g. Daniel cell
Porous pot
Metal-metal ion electrode Zn Cu
Half cell

Zn / ZnSO4 CuSO 4 /Cu

Separate between Porous Pot ZnSO4 CuSO4
Cell
Solid phase and
solution phase
 Note that every cell contains at least two electrodes (could even
contains four electrodes)
 The current produced when oxidation and reduction reactions occur
 2
2. Chemical cell with elimination of L.J.P.
Salt Bridge Salt Brigde
Zn Cu
Zn / ZnSO4//CuSO4 / Cu
 Salt bridge used to eliminate the L.J.P.
 It contains saturated solution of KCl or KNO3
or NH4NO3
 In that case the K+ ion is responsible for
transferring current ZnSO4 CuSO4
3. Chemical cell without L.J.P. Ag
Pt
H2
Gas electrode Metal-insoluble salt electrode

Pt / H2( g ) / HCl /AgCl(S) / Ag

Sparingly
Common Cation Common anion
soluble salt AgCl
HCl
 Types of Electrodes
1. metal-metal ion electrode
Zn / ZnSO4 , Cu / CuSO4
2. gas electrode
Pt / H2( g ) / HCl
3. metal-insoluble salt electrode
Ag / AgBr / KBr , Pb / PbSO 4 / H2SO4 , Hg / Hg2Cl 2 / KCl
4. redox electrode (oxidation reduction electrode)
Pt / Fe 2 / Fe 3 , Pt / Sn 2 / Sn 4
5. amalgam electrode
Zn / Hg / ZnSO4
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How does Galvanic cells give current
EX1 Daniel Cell

Zn / ZnSO4 CuSO 4 /Cu

Zn  Zn 2  2e  Oxidation
(Reducing agent)
Half Cell

Cu 2  2e  Cu Reduction
(Oxidizing agent)
Half Cell

Zn  Cu 2  Zn 2  Cu [Qxidn/Redn] Total Cell

Anode Cathode
e-
 The electrons transfere outside the cell from Zn Cu
-ve electrode (anode) to +ve electrode (cathode)
 Inside solution cations (Zn+2,Cu+2) transfefr to Zn+2
cathode and anions (SO42-)transfere to anode
SO4-2

Concn Zn+2 Cu+2 Conc

n

increase decrease

 Reduction System
In that system, the two half cells written in reduction form
E.g. Daniel cell
Cu 2  2e  Cu  1 Redn

- Zn 2  2e   Zn  2 Redn

Cu 2  Zn Cu  Zn 2 Total cell = 1-2

 4
EX2

Cd / Cd 2 // Sn 2 / Sn 4 / Pt
Metal-metal ion Redox
n
Oxd Redn
Anode Cathode
Chemical cell with elimination of L.J.P.
RER Sn 4  2e  Sn 2  1
LER - Cd 2  2e  Cd  2

TCR Sn 4  Cd Sn 2  Cd 2

EX3

Cd / Cd 2 // Fe2 / Fe 3 / Pt
Metal-metal ion Redox
n
Oxd Redn
Anode Cathode
Chemical cell with elimination of L.J.P.

RER Fe 3  e  Fe 2  1 *2
LER - Cd 2  2e  Cd  2

TCR 2Fe 3  Cd 2Fe 2  Cd 2

Ohm’s Law
Potential is directly proportional to intensity of current

E (volt )  i (ampere )
E
E  R *i
R

i
 5
Farady’s Law
 1st Law
The mass (m) of substance deposited at the electrode is proportional
to the quantity (Q) of electricity passed through solution
m Q
Q  it  nF Faraday Constant = 96500 C
current time No. of Faradays
 m  it
OR m  nF
nd
 2 Law
The mass (m) of substance deposited at the electrode is proportional
to the mass equivalent (e)
 m  ite
1
m  ite
F
OR mF  eit
Faraday: The quantity of electricity required to deposit
1 gm equivalent of substance
The 1 mole contains Avogadro’s No. (6.023*1023)
The charge of electron (e=1.602*10-19)
Quantity of electricity needs to deposit 1 mol is
= 6.023*1023 * 1.602*10-19 = 96500 Columbe
Note that
Equivalent weight = Molecular weight / Valency

Electrical Work We :-
We = Potential difference * quantity of electricity
=E* it
We  nFE
* Unit Joule
1 Cal = 4.18 Joule
1 Joule = 107 erg
 6
Gibbs Free Energy G:-
G  We  nFE

Standard Free Energy G0:-

G   nFE 

Electrode Potential E :-
The potential exist when metal immersed in a solution of its ions.
* E depends on
Type of electrode & Concentration of ions

Standard Electrode Potential E :-

The potential exist when metal immersed in a solution of its ions at unit
activity.

Electromotive Force Ecell (e.m.f.):-

The difference between the two electrodes potential.
Ecell = ER – EL (Reduction System only)

Ex.
Zn / ZnSO4 // CuSO4 / Cu
R Cu 2  2e   Cu
L Zn 2  2e   Zn

T Cu 2  Zn  Cu  Zn 2

 Ecell = ER – EL
 ECu 2 /Cu  E Zn 2 / Zn
* Note :- EReduction = - EOxidation
i.e. if E Zn 2
/ Zn = -0.77 volt
 E Zn / Zn 2 = 0.77 volt
 7
Equilibrium Constant Keq :-

G   RT lnKeq
active mass of products
Keq 
active mass of reactants
active mass = [ ]n
Note: active mass of pure metal = 1
Ex.
Zn / ZnSO4 // CuSO4 / Cu
R Cu 2  2e   Cu
L Zn 2  2e   Zn

T Cu 2  Zn  Cu  Zn 2
[Zn 2 ]
Keq 
[Cu 2 ]
Type of Reaction

G Ecell We Type of reaction

-ve +ve +ve Spontaneous
+ve -ve -ve Non Spontaneous
0 0 0 Equilibrium

Electrochemical Rules
1. The electrode which undergoes oxidation is Anode and will be written at
the left hand side of the cell,
the electrode which undergoes reduction is Cathode and will be written
at the right hand side of the cell

2. The reduction reaction of the RHS will be written first, then the
reduction reaction of the LHS of the cell, so the total cell reaction will
be (Right-Left)
Similarly Ecell  ER - EL
And Ecell
0
 ER0 - EL0
 8

3. If the Ecell has a +ve sign, G will be –ve and the cell will be spontaneous
If the Ecell has a -ve sign, G will be +ve and the cell will be non
spontaneous
If the Ecell is zero, G will be zero and we will have equilibrium

4. EReduction  - EOxidation
EReduction
0
 - EOxidation
0

That is to say E Zn 2
/ Zn
 E Zn / Zn 2
And E Zn
0
2
/ Zn
 E Zn
0
/ Zn 2
5. E depends on Type of electrode & Concentration of ions

6. G   nFE 
G   RT lnKeq
RT
E 0  lnK eq
nF
0
0.0592
E0  logK
n
T= 298 K R = 8.314 J F = 96500 C ln = 2.303 log

7. Electrons must be transferred at the external circuit from anode to

cathode

8. Cations transferred to cathode and anaions transferred to anode

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Thermodynamic Treatment of Electrode Potential
(Nernst Equation)
 For any reaction like
aA  bB  lL  mM
(a L )l (a M ) m
K 
(aA ) a (aB )b
 The Free Energy Change for Total Cell Reaction is
(a L )l (a M ) m
G  G  RT ln


(aA ) a (aB ) b
 Note
G  nFE , G   nFE 

 So
aPdt
 nFE  nFE  RT ln


aRe act
 Divide by( - nF)
RT a
E E  ln Pdt Nernst Equation
nF aRe act
 Some Notes
1) At Equilibrium G  0
G   RT lnK eq
2) R = 8.314 J , F = 96500 C , ln = 2.303 log , and at 25 C

0.0591 a prod .
E E   log
n a react .
3) n is No. of electrons
4) E is e.m.f of the cell, and E is the standard electrode potential
5) a is the activity where
a  c
*  is activity coefficient
* C is the concentration
* a = 1 for solid state, pure metal and pure liquid
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Standard Cell S.C.
That cell which has 1- Constant and known e.m.f.
2- Constant Concentration
Examples:-
 Weston Standard Cell

Cd(12.5%) in Hg / CdSO4 (S) / CdSO4 (Sat) / Hg2SO4 (S)/ Hg

Metal-metal ion electrode Metal-metal ion electrode

CdSO4
(Sat Soln)
Hg 2
2  2e  2Hg


Cd 2  2e   Cd
CdSO4 Hg2SO4
Cd  Hg 2
2  Cd 2
 2Hg (Solid) (Solid)
Hg
Cd/Hg
Oxidn Redn
E=1.0183 V
 Note both CdSO4 and Hg2SO4 are soluble salts
 The concentration remains constant in the cell due to
 Increase of Cd2+ due to oxidation of Cd doesn’t effect on the
overall concentration of the CdSO4 solution (Saturated Solution)
 Decrease of Hg+ due to reduction to Hg doesn’t effect on the
overall concentration of the Hg2SO4 (Solid)
 This cell is reversible cell due to if it is connected to battery with
E < 1 V so it is not affected, but if E > 1 V (e.g. 2 V) so it will be
reversed

 Clark’s Cell
Zn(10%) in Hg / ZnSO4 (S) / ZnSO4 (Sat) / Hg2SO4 (S) / Hg

 Note that the cell is similar to the Weston cell in all things, except
you must change the Cd by Zn
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Method of Measuring Ecell
( Poggendorf Compensation Method)
2V

A C D B

Cell G

S.C.
1-Determine the length at balance of unknown cell (AC)
2-Determine the length at balance of standard cell (AD)
(The balance is at zero galvanometer)
3-Using the relation
Known
Unknown Ecell AC

ESC AD
Known Known

So Ecell can be determined

 E.g. the e.m.f. of the Daniel cell measured to be 1.09 V

Reversible and Irreversible Cells

 For the cell (Daniel cell)
Zn / ZnSO4 // CuSO4 / Cu
 If Ecell > Ebattery  Cu 2  Zn  Cu  Zn 2 (1)
 If Ecell < Ebattery  Cu  Zn 2  Cu 2  Zn (2)
 Due to reaction (1) is opposite to reaction (2) So This is Reversible
Cell
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 For the cell
Zn / H2SO4 / Ag
 If Ecell > Ebattery
2H   2e   H2
Zn 2  2e   Zn

2H   Zn  H2  Zn 2  (1)

 If Ecell < Ebattery The cell become

H   e   21 H2
Ag   e   Ag

H   Ag  21 H2  Ag  (2)
 Due to reaction (1) is not opposite to reaction (2) So This is
Irreversible cell

Types of Reversible Electrodes

2. Metal – Metal ion Electrode

Ex. Ag / Ag+ , Zn / Zn2+ , Cu2+ / Cu

Zn 2  2e   Zn
RT 1
E Zn  E Zn0 2  / Zn  ln
2F a Zn
2
/ Zn
2

 Note that the activity of metal is 1

3. Gas Electrode
Ex. Pt / H2 , H+ , Pt / O2 , OH- , Pt / Cl2 , Cl-
H   e   21 H2
RT (PH )
12

EH  E H0 / H  ln 2

F aH

/ H2 2

 13
Note:
 At 25 C, 1 atm and the activity of hydrogen ion be 1 , the cell called
Standard Hydrogen Electrode
 E H  / H2  0
0
(By Definition)
4. Metal – Insoluble Salt Electrode
Ex. Pb/PbSO4 (S) /H2SO4 , Hg/Hg2Cl2/KCl , Ag /AgCl (S) /HCl
PbSO 4 (S )  2e   Pb  SO42
RT aPb  aSO 2
E Pb E 0
 ln 4

2F aPbSO
2
/ Pb Pb 2 / Pb
4

RT
E Pb  E Pb0 2 / Pb  ln aSO
2F
2 2
/ Pb 4

 Note that the activity of solid is 1

5. Oxidation – Reduction (Redox)Electrode
Ex. Pt / Fe2+ / Fe3+ , Pt / Sn2+ / Sn4+ , Pt / Q , H2Q , H+
O OH

+2H+ + 2e-

O OH

Quinone (Q) Hydroquinone (H2Q)

RT aH Q
EQ / H Q  E 0
 ln 2

2 Q / H2Q
2F aQ  (aH )2 

RT 1
EQ / H Q  EQ0/ H Q  ln
2 2
2F (aH )2 

 Note that the activity of Quinone is equal to that of Hydroquinone

6. Amalgam Electrode
Ex. Zn / Hg /ZnSO4
RT 1
E Zn  E Zn0 2  / Zn  ln
2F a Zn
2
/ Zn
2
 14
Types of Galvanic Cells
i. Chemical Cell: With two different electrodes
 With liquid junction potential: Zn / ZnSO4 CuSO4 / Cu
 With elimination of L.J.P.: Zn / ZnSO4 // CuSO4 / Cu
 Without L.J.P. : Pt / H 2 / HCl / AgCl /Ag

ii. Concentration Cell: With two identical electrodes

 In this types of cells the e.m.f. is result from difference in
concentration

a) Electrode Concentration Cell

 The e.m.f. is result from difference in Conc. between two electrodes
Ex.
Pt / H2 (P=5 atm) / HCl / H2 (P=1 atm) /Pt
L.E.R H   e   21 H2 (5atm)
R.E.R H   e   21 H2 (1atm)
T.C.R
1
2 H2 (5atm)  21 H2 (1atm)

Standard Conditions
Solid phase must be pure
Gas phase must be pure
Liquid phase must be at unit activity
The Cell at 25 C & 1 atm
b) Electrolyte Concentration Cell
 The e.m.f. is result from difference in Conc. between two electrolytes
(Solutions)
i. With liquid junction potential
Ex.(1)
Ag / AgNO3 (a1) AgNO3 (a2) / Ag
R.E.R Ag a  e   Ag
2

L.E.R Ag a  e   Ag
1

T.C.R Ag a 2
 Ag a1
 15
So
RT (a1 )
E Cell  E R  E L   ln
F (a2 )
Note :
 Two Identical Electrodes So
E 1  E 2  0
 n = 1 (One electron)

Ex.(2)
Pt / H2 (1 atm) / HCl (a1) HCl (a2) /H2 (1 atm) / Pt

ii. Without L.J.P.

Ex.
Pt / H2 / HCl (a1) / AgClS / Ag / Ag / AgClS / HCl(a2)/ H2 / Pt

 For Right Cell Reaction

R.E.R H a  e   21 H2
2

L.E.R AgCl  e   Ag  Cl a 2

T.C.R Ha  Cl a  Ag  H2  AgCl

2

2
1
2
1

 For Left Reaction

R.E.R AgCl  e   Ag  Cl a 1

L.E.R Ha  e  H2

1
 1
2

T.C.R
1
2
H2  AgCl  Ha  Cl a  Ag 1 1
2

 For All Reaction 1 + 2

H a  Cl a  H a  Cl a
2 2 1 1

HCl a  HCl a 2 1

RT (aHCl )1 RT (a  a  )1
E Cell   ln  ln
F (aHCl )2 F (a  a  )2
 16
 a  a   (a  ) 2

 a    c
 a  is mean activity
   is mean activity coefficient
 So
RT (a  )
2
2RT (a  )1
E Cell  ln   ln
1

F (a  ) 2
F 2
(a  )2

Reference Electrodes
 Electrodes with known potential and Conc.

1) Standard Hydrogen Electrode ( gas electrode)

Pt / H2 (1 atm), H+ (a=1)
Pt
H   e   21 H2
 Standard Hydrogen Electrode has H2
EH 

/ H2
0 1 atm
 Determination of pH
pH = - Log [ H+ ]
HCl
Pt / H2 (1 atm)/ H+ // KCl /Hg2Cl2(S) / Hg
S.H.E. Calomel Electrode

R.C.R Hg2Cl 2  2e   2Hg  2Cl 

L.C.R 2H   2e   H2

T.C.R Hg2Cl 2  H2  2Hg  2Cl   2H 

ECell  ER  EL  ECal  EH 
/ H2

RT PH
ECell  ECal  E H  ln 2
/ H2
2F (aH )2


 17
 Note P = 1 atm , So at 25 C

ECell  ECal  E H 
/ H2
 0.0591 log aH 
 0.0591 pH
 So
ECell  ECal
pH 
0.0591

2) Calomel Electrode ( metal – insoluble salt electrode )

Hg / Hg2Cl2 (S) / KCl
Hg2Cl 2  2e   2Hg  2Cl  KCl
Soln
 There are three types
Electrode Conc. ECal (V)
1-Decimal Calomel Electrode 0.1 M KCl 0.3338 capilary
Hg2Cl2
tube
2-Normal Calomel Electrode 1 M KCl 0.2800
Hg
3-Saturated Calomel Saturated KCl 0.2415 Cu wire
Electrode

3) Ag / AgCl Electrode (metal – insoluble salt electrode )

Ag / AgCl(S) / HCl Ag
(a=1)

AgCl  e   Ag  Cl 
E Ag


/ Ag
 0.222 V Cl-
4) Quinhydron Electrode (Redox electrode)
Ag plate +
Pt / Q , H2Q , H+
past of AgCl
Q  2H   2e   H2Q
O OH

+2H+ + 2e-

O OH
 18
 Determination of pH
RT 1
EQ / H Q  EQ0/ H Q  ln
2 2
2F (aH )2

EQ0/ H Q  0.6991
2

RT
EQ / H Q  0.6991  ln aH
F

2

 EQ / H2Q  EQ0/ H2Q  0.0591 pH

e.g.
Hg / Hg2Cl2 (S) / Tested Solution / Q , H2Q / Pt
of H+
ECell  EQ / H Q  ECal2

ECell  EQ / H Q  0.0591 pH  ECal

2

EQ / H Q  (ECell  ECal )

 pH  2

0.0591
5) Glass Electrode Ag wire
Ag / AgCl(S) / 0.1 N HCl / Glass
EG  EG  0.0591 pH
 Determination of pH Ag/AgCl
Ag / AgCl(S) , HCl (0.1) / Glass / Soln / Calomel Elec. H+ H+ 0.1 N
HCl
ECell  ECal  EG  ECal  EG  0.0591 pH
ECell  EG  ECal
 pH 
0.0591
 The Glass must be
1. High conductivity
2. Act as semipermeable
3. Low melting point
 e.m.f produced due to difference in H + Conc. In and Out Bulb
 e.m.f is proportional with H+ Conc. Out bulb in range (1 – 9)
 In high alkaline solutions (pH > 9) special glass must be used
 19
Electrochemical Series

Au Ag Cu H Ni Zn Mg

Easily reduced Easily oxidized

Oxidation power
increases
Interchange in
solutions

Ionic Strength
 It is a property of the total solution
I  1
2  i i
C Z
i
2

Where Ci is Concn of each ion present in solution

Zi is valance of the ion
 Calculate I for 0.005 M KCl solution
I  1
2 0.005 * (1) 2
 0.005 * (1)2   0.005
 Calculate I for 0.001 M CaCl2 solution
I  1
2 0.001 * (2) 2
 2 * 0.001 * (1)2   0.003
 Calculate I for 0.005 M KCl and 0.001 M CaCl 2 solution
I  0.005  0.003  0.008
 For any solution containing MAXB
I  1
2 AB 2
 BA2  * C
Ionic Activity
 Ideal Solutions: there is no interaction between molecules
a m Molality
 Non ideal Solutions: there is interaction between molecules
a  m Activity Coefficient
0  1
 If  = 1 so it is ideal solution that is at infinite dilution (very dilute
solutions)
 20
Solved Examples
1. calculate the quantity of electricity in coulomb to ppt 63.5 gm of Cu from
CuSO4 solution , the atomic mass of Cu is 63.5
At mass 63.5
Eq mass = =
Valancy 2
mF = eIt
mF 63.5 * 96500
It =  
e 63.5 Coulomb
2

2. A quantity of electricity passed in CuSO4 solution and ppted 6.35 g, the

same amount of electricity is passed in another solution and ppted 3.7 g of
metal what is the equivalent mass of that metal
63.5
Eq of Cu =
2
m1 m2
=
e1 e2
6.35 3.7
=  e2  g
63.5 e2
2
3. If 14300 Col are passed in a solution of metal sulphate, the mass of
cathode increases by 6.35 g. calculate the amount of electricity needed to
ppt (At mass = 63.5)
a. 8.2 g of metal
b. 31.7 g of metal
c. The valance of the metal
mF = eIt
m1 F = e It 1
m2 F = e It 2
m1 It 1

m2 It 2
 21
6.35 14300
   It 2  C
8.2 It 2
6.35 14300
   It 3  C
31.7 It 3
mF 6.35 * 96500
e= =  e=
It  14300
At mass 63.5
e= =  Valancy =
Valancy Valancy
4. How long it takes to produce 25 g of chromium from a solution of CrCl 3 by
passing a current of 2.75 ampere (At mass = 52)
mF = eIt
 52 
25 * 96500 =   2.75 t t = sec
 3 
5. What is the equivalent mass of metal if a current 0.5 ampere will cause
0.13 g of metal to ppt in 40 min
mF = eIt
0.13* 96500 = e* 0.3* 40 * 60 e = g
6. Calculate the electrode potential of Cd in the cell
Cd / CdSO4 (1 M) // KCl (1 M) / Hg2Cl2 / Hg
If Ecell = 0.683 volt and Ecal = 0.28 volt
And calculate the G of the left reaction
Ecell = ER - EL
Ecell = Ecal - ECd ++ /Cd
0.683 = 0.28 - ECd ++ /Cd
ECd ++ /Cd = -0.4 volt
That cell is chemical cell with elimination of L. J. P. Contains metal-metal ion
electrode (Cd / CdSO4), And metal-insoluble salt electrode KCl / Hg2Cl2 / Hg
R Hg2 Cl2 + 2e - 2Hg + 2Cl -
L Cd ++ + 2e - Cd
T Hg2 Cl2 + Cd 2Hg + 2Cl - + Cd ++
 22
RT a
E = E 0- Ln Prod
nF aReact
aHg  aCl -  aCd ++ 
2 2
0.0591
-0.4 = E 0 - Log
2 a
Hg2 Cl2  a Cd 
E 0 = -0.4
RT 0.0591
E0= LnKeq = LogKeq  Keq 
nF n
G 0 = -nE 0F  G 0  
We = nFE  We  

7. For a cell Zn/Zn++ (0.5 M)//Cd++ (0.1 M)/Cd, EZn/Zn

0
= 0.768 and ECd/Cd
0
++ = -0.4
++

Calculate Ecell , the left E, and write the type of cell and each electrode
EZn++/Zn
0
= -0.768 ECd0 ++ /Cd = 0.4
Ecell
0
= ER0 - EL0
Ecell
0
= ECd0 ++ /Cd - EZn++/Zn
0
= 0.4 - -0.768  
R Cd ++ + 2e - Cd
L Zn ++ + 2e - Zn
T Zn + Cd ++ Zn ++ + Cd
RT a
E = E 0- Ln Prod
nF aReact
0.0591 0.5
E = E 0- Log  E 
2 0.1
That cell is chemical cell with elimination of L. J. P. and the electrodes are
both metal-metal ion electrode
For left cell
Zn ++ + 2e - Zn
RT a
E = E 0- Ln Prod
nF aReact
 23
0.0591 a
EZn++ /Zn = EZn0 ++ /Zn - Log Zn
2 aZn++
0.0591 1
EZn++ / Zn = -0.768 - Log
2 0.5
8. Calculate the equilibrium constant for the reaction
2Fe +3 + Sn +2 2Fe +2 + Sn +4
If EFe0 +3
/Fe +2
= 0.77 and ESn0 +2 /Sn+4 = -0.15 , at 25 C, construct the cell for such
reaction
Reduction (Right)

2Fe +3 + Sn +2 2Fe +2 + Sn +4

Oxidation (Left)

Pt/Sn+2/Sn+4 //Fe+3 /Fe+2/Pt

ESn0 +4 /Sn+2 = 0.15 EFe0 +3 /Fe+2 = 0.77
Ecell
0
= ER0 - EL0
Ecell
0
= ESn0 +4 /Sn+2 - EFe0 +3 /Fe+2 = 0.15 - 0.77   -0.62
So the cell in that direction is non spontaneous and must be reversed
RT 0.0591
E0= LnKeq = LogKeq  Keq 
nF n

9. Write the cell reactions of the following cells

a. Pt/H2(1 atm)/HCl/Cl2(1 atm) /Pt
R Cl2 + 2e - 2Cl -
L 2H + + 2e - H2
T Cl2 + H2 2Cl - + 2H +
Chemical cell without L.J.P. and the electrodes are both gas electrodes

b. Ag/AgBr/KBr/Hg2Br2/Hg
 24
R Hg2 Br2 + 2e -
2Hg + 2Br -

L AgBr + e - Ag + Br - *2
T Hg2 Br2 + 2Ag + 2Br - 2Hg + 2Br - + 2AgBr
Hg2 Br2 + 2Ag 2Hg + 2AgBr
Chemical cell without L.J.P. and the electrodes are both metal-insoluble
salt electrodes
c. Zn + CuSO4 ZnSO4 + Cu
Oxidation (Left)

Zn + CuSO4 ZnSO4 + Cu
Reduction (Right)

R Cu ++ + 2e - Cu
L Zn ++ + 2e - Zn
T Cu ++ + Zn Cu + Zn ++
Zn/ZnSO4//CuSO4/Cu
Chemical cell with elimination of L.J.P. and the electrodes are both
metal-metal ion electrodes

d. AgCl + H2 HCl + Ag
1
2

Reduction (Right)

AgCl + 21 H2 HCl + Ag
Oxidation (Left)

Pt/H2/HCl/AgCl/Ag
Chemical cell without L.J.P. and the electrodes are gas electrode and
metal-insoluble salt electrodes
e. H2 + O2 H2O
1
2
Pt/H2/H+/H2O/O2/Pt
Chemical cell without L.J.P. and the electrodes are both gas electrodes
f. Na + H2O NaOH + 21 H2
Na in Hg/Na+//H+/H2/Pt
 25
Chemical cell without L.J.P. and the electrodes are amalgam
electrode and gas electrode
g. Cl2 + 2Br 2Cl - + Br2
-

Pt/Br2/Br-//Cl-/Cl2/Pt
Chemical cell with elimination of L.J.P. and the electrodes are both gas
electrodes

h. AgCl  1 / 2H 2  HCl  Ag
1 / 2 H 2  H   e Oxidn (Left)
AgCl  e  Cl   Ag Redn (Right)
So the cell is
Pt / H2 / HCl / AgCl /Ag

i. H 2  I 2  2 HI
H 2  2e  2 H  Oxidn (Left)
2I   I 2 Redn (Right)
So the cell is
Pt / H2 / HI / I2 /Pt

j. Na  H 2O  NaOH  1 / 2H 2
Na  OH   NaOH  e Oxidn (Left)
H   e  1 / 2 H 2 Redn (Right)
So the cell is
Na / H2O / H2 / Pt

10. the solubility of AgBr is 2*10-6 at 25 C, calculate e.m.f of the cell
AgBr Ag + + Br -
KSP = S 2
RT 0.0591
E0= LnK = Log 2 * 10 -6   E0
nF 1
 26
11.The E of the Pt / Fe / Fe half cell is 0.77 V, Calculate e.m.f of this half cell if
3+ 2+

a(Fe3+) = 0.2 and a(Fe2+) = 0.05

3  2
Fe  e  Fe n=1

EFe 3
/ Fe 2
 0.77 V
E  E   0.05916 n  loga prod. areact. 
E  0.77  0.05916 1log0.05 0.2 = 0.806 V
12. Write the left and right half cell reactions and the total cell reaction of the following
cells. And deduce which electrode is +ve
a) Cd / Cd2+ // KCl / Hg2Cl2 / Hg

R.E.R Hg2Cl2  2e  2Cl   2Hg ER  0.2676 V

L.E.R Cd 2  2e   Cd

ECd 2
/ Cd
 0.403 V
T.C.R Hg2Cl2  Cd  2Cl   2Hg  Cd 2

ECell  ER  EL  0.6706 V (+ve) So R.E is +ve
+ 3+ 2+
b) Pt / Tl , Tl // Cu / Cu

R.E.R Cu 2  2e   Cu

ECu 2
/ Cu
 0.337 V
L.E.R Tl 3  2e   Tl  ETl 3 / Tl   1.25 V
T.C.R Cu 2  Tl   Cu  Tl 3

ECell  ER  EL  0.913 V (-ve) So L.E is +ve

13. Calculate the e.m.f and G for following cells, deduce if it written spontaneous or not
a) Ni / Ni2+ (a=0.01) // Cl- (a=0.2) / Cl2 (P=1)/Pt

R.E.R Cl2  2e   2Cl  ECl / Cl  1.36 V

2

L.E.R Ni 2  2e   Ni ENi 2 / Ni  0.25 V

T.C.R Cl2  Ni  2Cl   Ni 2

ECell  ER  EL  1.61 V
0.05916 (aCl ) 2 (a Ni2 )
ECell E  
log  1.71 V
2 PCl2
G  nFECell  2  96500 1.71  330 kg/mol
** G is –ve and ECell is +ve So reaction is spontaneous as written
b) Sn / Sn2+ (a=1) // Pb2+ (a=0.001) / Pb
 27
E 
Sn2 / Sn
 0.136 V E 
Pb 2 / Pb
 0.126 V
T.C.R Pb 2  Sn  Pb  Sn 2

ECell  ER  EL  0.01 V
0.05916 (a 2 )
ECell  E   log Sn  0.079 V G  nFECell  15.2 kg/mol
2 (aPb 2 )
(+ve) So reaction non spontaneous

14. For the following cell

Ag / AgClS / Cl-(a=0.005) // Fe3+(a=0.1) / Fe2+(0.02) / Pt
E(Ag/AgCl)=-0.22 V , E(Fe2+/Fe3+)=-0.77
a) Write the left, right and total cell reactions
b) What is the type of electrodes and cell
c) Calculate ECell

a) R.E.R Fe 3  e   Fe 2 EFe 3 / Fe2  0.77 V

L.E.R AgCl  e   Ag  Cl 

E AgCl / Ag 
 0.22 V
Fe 3  Ag  Cl   AgCl  Fe 2 ECell  ER  EL  0.55 V
  
T.C.R
b) Right is Redox Electrode
Lift is Metal-Insoluble salt Electrode
Cell is Galvanic Chemical Cell with elimination of l.j.p
0.09516 aFe 2
c)
E  E  log
1 aFe3  a Ag 
15. A solution with pH 5.8 , Calculate the e.m.f of the cell formed from saturated Calomel
electrode and
a) Hydrogen electrode b) Quinhydrone electrode
ECal=0.242 V , EQun=0.6991

a) pH  ECell  ECal  / 0.0591

ECell=

b) pH  E 

Q / H 2Q  ECell  ECal / 0.0591 
ECell=
 28
16. A solution with pH 4 gives e.m.f 0.4765 V with Hydrogen/Calomel. Calculate the pH
of solution give e.m.f 0.7243 V with the same cell.

** pH  ECell  ECal  / 0.0591

ECal=0.2396 V

** pH  ECell  ECal  / 0.0591  8.201

17. The e.m.f of Quinhydrone / Calomel cell is 0.0042 V. Calculate the pH of buffer
solution (ECal=0.242 V , EQun=0.6991)

** pH  E 

Q / H 2Q E
Cell E
Cal / 0.0591
pH =

18. The cell Pt/H2(P=1 atm),HCl/AgCl/Ag has e.m.f 0.332 V at 25C.

a) Write the left, right and total cell reactions
b) What is the type of electrodes and cell
c) Calculate pH of solution (E(Ag/AgCl)=-.02225)

a) R.E.R AgCl  e   Ag  Cl 

E AgCl / Ag 
 0.2225 V
L.E.R H   e   1 / 2H 2
T.C.R AgCl  1 / 2H 2  Ag  Cl   H 
b) Right is Metal-Insoluble salt Electrode
Lift is Gas Electrode

 
Cell is Galvanic Chemical Cell without l.j.p

c) pH  ECell  EAgCl / Ag  / 0.0591

pH =

19. The e.m.f of the cell Ag/AgCl/HCl(0.1M)/Buffer(pH=4)/KCl/Hg 2Cl2/Hg is 0.112 V at

25C. When the buffer changed by unknown solution the e.m.f was 0.3565 V at same
temp. Calculate the pH of unknown solution.

** pH  E 
Cell E E
G

Cal / 0.0591
 E E

G Cal 
** pH  E 
Cell GE E

Cal / 0.0591  8.65
 29
20. Calculate ECell, K, G, W. for the reaction at 25C.
3  2
2Feaq  2I aq  2Feaq  I 2 ( E(I-/I2)=-0.53 V , E(Fe2+/Fe3+)=-0.77 V)

** R.E.R is 2Fe 3  2e  2Fe 2 EFe 3 / Fe2  0.77 V

** L.E.R is 2I   e  I 2 EI / I  0.53 V
2
- 3+ 2+
** The cell is Pt/I2/I //Fe /Fe /Pt

** ECell  ER  EL  1.3 V
** Complete

21. Calculate ECell, K, G, W. for the reaction at 25C.

3
2Feaq  Sn 2  2Feaq
2
 Sn 4 (E(Sn2+/Sn4+)=-0.15 V, E(Fe3+/Fe2+)=0.77)
** The cell is Pt/Sn2+/Sn4+//Fe3+/Fe2+/Pt

**

ECell  ER  EL  EFe

3
/ Fe 2  E 4

Sn / Sn2
 0.92 V
** Complete

22. The e.m.f of cell Ag/AgNO3(0.1 M,=0.72)//KCl(0.1 M,=0.78)/AgClS/Ag is 0.403 V.

Calculate solubility product of AgCl at 25C.
RT a Ag  in AgNO3
** ECell  ln  a Ag  in AgNO3 
nF a Ag  in AgCl

** K SP  a Ag   aCl 

23. The e.m.f of the cell Ag/AgClS//KCl(a=0.1)/Hg2Cl2/Hg at 25C is 0.0455 V

a) What is the type of electrodes and the cell
b) Calculate the activity of the Ag ion in saturated solution
(E(Ag/AgCl)=-0.8 V , E(Cal)=0.33 V)
a) The two electrodes are Metal – Insoluble Metal Electrodes
The cell is Galvanic Chemical cell with elimination of l.j.p

b) R.E.R Hg2Cl2  2e   2Hg  2Cl  ECal  0.33 V

L.E.R 2 AgCl  2e   2 Ag  2Cl 

E AgCl / Ag 
 0.8 V
T.C.R Hg2Cl2  2 Ag  2Hg  2 AgCl
ECell  ECal  E AgCl / Ag  0.0455 V
 E AgCl / Ag  0.285 V
 30
0.05916
E AgCl / Ag  E AgCl

/ Ag  log( a Ag  ) 2 (aCl ) 2
2
2  0.05916
0.285  0.8  log a Ag   aCl
2 2
 a Ag  
24. Deduce whether Cu will be oxidized by HCl where E(Cu2+/Cu)=0.34
** i.e if the following reaction is spontaneous ?
CuS  2HCl  CuCl2  H 2
**

ECell  ER  EL  0  0.34  0.34 V
** E is –ve so reaction is non-spontaneous

25. Deduce whether Fe will be oxidized by HCl where E(Fe2+/Fe)=-0.41

** i.e if the following reaction is spontaneous
FeS  2HCl  FeCl 2  H 2 ERed

**

ECell  ER  EL  0  (0.41)  0.41 V
** E is +ve so reaction is spontaneous +Ve

26. Deduce whether Fe will reduce Fe3+ to Fe2+

** i.e if the following reaction is spontaneous H2 0.0
3 2
FeS  2Fe  3Fe
FeS  Fe 2  2e  oxidation –(-0.409) -Ve
2Fe 3  2e   2Fe 2 reduction 0.7701
E=1.179 +ve so spontaneous reaction

27. If E(Cu2+/Cu)=0.34 V and E(Cu+/Cu)=0.52 V. Calculate E(Cu2+/Cu+)

** Cu
2
 2e   Cu

ECu 2
/ Cu
 0.34 V G1  nE  F  0.68 F
** Cu   e   Cu

ECu 
/ Cu
 0.52 V G2  nE  F  0.52 F
** Cu 2  e   Cu 
GRe

c  G2  G1  nE F  (0.52  0.68) F  0.16 F
  

 ECu

2
/ Cu
 0.16 V
 31
28. If E(Fe3+/Fe2+)=0.771 V and E(Fe2+/Fe)=-0.44 V. Calculate E(Fe3+/Fe)

** Fe
3
 e   Fe 2 EFe 3 / Fe2  0.771 V G1  nE  F  0.771 F
** Fe 2  2e   Fe EFe 2 / Fe  0.44 V G2  nE  F  0.88 F
** Fe 3  3e   Fe
GRe

c  G2  G1  nE F  (0.88  0.771) F  1.651F
  

 EFe 3 / Fe  0.55 V
29. For the Galvanic cell Pb/PbSO4(S)/K2SO4(L)//CuSO4(L)/Cu
a) Name the type of cell : Chemical cell with elimination of l.j.p
b) Write the type of each electrode : R is Metal – Metal ion
L is Metal – Insoluble Metal
c) Write the half and total cell reactions
R Cu 2  2e   Cu
L PbSO4  2e   Pb  SO42
T Cu 2  Pb  SO42  Cu  PbSO4
d) If E(Pb2+/Pb)=-0.36 V and E(Cu/Cu2+)=-0.34 V. Calculate E(Cell)

ECell  ER  EL  ECu

2
/ Cu
 E 
Pb 2 / Pb
 0.7 V
e) Is this cell as written spontaneous?
E(Cell)=+ve so spontaneous

30. The e.m.f of the cell Pt/H2(1 atm)/HCl(aq)/Hg2Cl2(S)/Hg is 0.39 V at 25C. Calculate
i) The pH of the HCl if E(Cell)=0.29 V at 25C.
pH  ECell  ECell

/ 0.0591
ii) Write the half and total cell reactions for this cell
R Hg22   2e   2Hg
L 2H  2e   H2
T Hg22   H2  2Hg  2H
iii) What are the types of electrodes for this cell?
R is Metal – Insoluble metal electrode & L is Gas electrode
iv) Name the type of cell: Galvanic chemical cell with elimination of l.j.p

31. a)Devise the cell in which the total cell reaction is

1 2 Cl2 (g)  Br (aq)  Cl  (aq)  1 2 Br2 (g)
 32
Pt/Br2(g)/Br-(aq)//Cl -(aq)/Cl2(g)/Pt
b) Write the type of the two electrodes
The two electrodes are gas electrodes

32. i) Calculate the e.m.f of the cell

Pt/Tl+(a=1)/Tl3+(a=1)//Cl-(a=1)/Hg2Cl2(S)/Hg
if E( Hg /Hg2Cl2)=-0.27 V and E( Tl+/Tl3+)=-1.25 V at 25C.
R Hg2Cl2  2e   2Hg  2Cl  EHg

2Cl2 / Hg
 0.27 V
L Tl3   2e   Tl  ETl

3
/ Tl 
 1.25 V
ECell

 ER  EL  -0.98 V
ii) Calculate the standard change in Gibbs free energy
G   nFE  n=2
iii) Evaluate the equilibrium constant for this reaction
logKeq  nE  0.05916
iv) Comment on results of E and G
E = -Ve and G=+ve so non-spontaneous reaction
v) Write the type of the above cell
Galvanic chemical cell with elimination of l.j.p