Electrochemistry 21p

Chemistry (Electrochemistry)
UNIT-5 Electrochemistry
Introduction
Electrochemistry is the branch of chemistry which deals with the relationship between electric
energy and chemistry energy.
It is broadly divided into two categories
(i) Production of chemical change by electrical energy and
(ii) Conversion of chemical energy into electrical energy.
1. CONDUCTANCE AND ITS APPLICATIONS
It is the reciprocal of the resistance (R) of the solution, i.e.,

1
C
R
Unit of C :
1
 ohm1  mho
ohm
S.I unit = –1  Siemen(s)
The Resistance of a wire is found to change as follows
R  
[where  = distance between the parallel electrodes in the conductivity cry.]
1
and R
A
[where A = Effective cross - section area of the electrode.]
Combining both

R
A
Removing the proportionality sign; we have

R   
A
Where  is constant of Proportionality and is called the specific resistance.
It is depends upon the nature of material
If A = 1 unit = 1cm2
 = 1 unit = 1cm
then
R
Thus specific resistance is defined as the resistance of a specimen 1 cm in length and 1cm2 cross-
section.
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Unit of Specific Resistance
R  A   cm2
     cm or m
 cm
Specific Conductance :
The resiprocal of specific resistance, i.e.1/is called specific conductance. This may be defined
as the conductance of one centimeter cube of material. It is denoted by  (Kappa)
Thus,
1 1  RA
    
 R A 
1  1
  C
R  A 

R

  C 
A
  C  Cell Cons tan t
Unit :
Since conductance is measured in –1, length in cm and area in cm2, hence
cm
K    2
  1cm1
cm
Equivalent Conductance : (eq)
The conductance of a volume of solution containing on equivalent mass of a dissolved substance
when placed between two parallel electrodes which are at a unit distance apart and large enough to
contain between them the whole solution.
  1000
 eq 
C SI Unit  sm2
C = normality of solution
 = specific conductance
Unit : ohm–1 cm2 eq–1
Molar Conductance : (m)

The conductance of a volume of solution containing one mole of dissolved solute when placed
between two parallel electrodes which are at a unit distance apart and large enough to contain between
them the whole solution.
  1000
m 
C
where – C = molarity
SI Unit = sm2 mol–1
The units of molar conductivity are ohm–1 cm2 mol–1 or S cm2 mol–1.
Relation between Molar conductivity (m) and Equivalent conductivity (eq):
 1 
eq =    m
n z


where,
n+ = number of cations
z+ = Chargeon a cation
For Example, in case of Al2(SO4)3
Al2(SO4)3  2 AI3+ + 3SO42–
 1 
 eq     m  Al2  SO 4 3 
 23
Variation of Conductivity and Molar Conductance with Dilution

 Upon dilution i.e, lowering concentration specific Conductance decrease while equivalent
and molar Conductance increase.
 For strong electrolytes, conductivity increase sharply with increase in concentration
(decrease on dilution). The strong electrolytes ionize completely in solution and therefore
concentration of ions increase in proportion to the increase in concentration of electrolyte.
 For weak electrolytes, conductivity increase but much more gradually on increasing
concentration
 Molar conductivity (m) of both strong and weak electrolytes increase on dilution. The
basic reason for this reverse trend in molar conductivity is that, the decrease in conductivity
is more than compensated by increase in values of 1/c on dilution.
m
C
Fig. : Variation of molar conductivity with concentration
For strong electrolyte, the variation of  m vs. c is almost linear in the dilute solution. The increase
in molar conductivity of strong electrolytes on dilution is attributed to the weakening of electrostatic
attraction between the oppositely charged ions as dilution increases inter-ionic distance.
On the other hand, for weak electrolytes, the increase in molar conductivity on dilution is slow in
higher concentration range but it increase vary rapidly in lower concentration range due to increase in
numbers of ions on dilution (because degree of ionization increase)
There at any concentration, when the molar conductance is say, m, the degree of dissociation
() will be given by
m

 m
2. TRANSPORT NUMBER
The fraction of the total current carried by anion is known as transport number, transference
number or Hittorf number may be denoted by sets of symbol like t+ and t– or tc or ta or nc and na
From this definition,
Current carried by cation

t+ = Total current
Current carried by anion

t– = Total current
evidently t+ + t– = 1
As we know that the current flow in the solution is directly proportional to velocity of ions so we
can say current is proportional to the mobility of ions
Current  mobility of ions
 (velocity)

So t+ =   
 

t– =   
 
and t+ + t– = 1
Transport number can be determined by
(i) Hittorf’s method
(ii) moving boundary method
(iii) emt method
(iv) ionic mobility
Ionic Mobility
Ionic mobility is defined as the distance travelled by an ion per second under a potential gradient
of 1 volt per metre.
Ionic mobilities (+ or –) speed of ions (a or c)
Unit of ionic mobility is ohm–1 cm2 or v–1s–1 cm2.
Kohlrausch’s Law
According to this law “At infinite dilution when dissociation is complete, each ion makes a definite
contribution towards molar conductance of the electrolyte irrespective of the nature of the other ion with
which it is associated and that the molar conductance at infinite dilution for any electrolyte is given by
the sum of the contribution of the two ions.”
i.e.,        
where °+ = molar ionic conductance of cation at infinite dilution

°– = molar ionic conductance of anion at infinite dilution.
Calculation of Molar Ionic Conductance
By combining kohlrausch’s law with the result of transport number measurement, it has been
possible to calculate the molar ionic conductances at infinite dilution.
So t    / (   )

Since °  °, hence
 t     / (     )
But      m (Kohlrausch law)
 t    /  m
and t     /  m
Calculation of Absolute Ionic Mobilities

It has been experimentally found that ionic conductance is directly proportional to ionic mobilities.
+  +
–  –
where + and – are ionic mobilities of cations and anions.
+ = F+ where F = Faraday
– = F– = 96500 coutomb
Ionic velocity
Ionic mobility = Potential gradient
Ionic velocity (cm / sec)

= Potential difference(voit) / electrode separation
Applications of Knolrausch’s Law

(1) to determine degree of dissociation



(2) to determine the value of equivalent or molar conductance of weak electrolyte at infinite
dilution.
For example
Ex. Calculate molar conductivity of NH4OH given that molar conductivity of Ba(OH)2, BaCl2 and NH4Cl
are 523.28, 280.0 and 129.85 cm3 mol–1 respectively
Sol. °Ba(OH)2 = °Ba2+ + 2°OH– = 523.28 ...(1)
°BaCl2 = °Ba2+ + 2°Cl– = 280.00 ...(2)
+
°NH4Cl = °NH 4
+ °Cl = 129.80
–
...(3)
Multiply Eq.(3) by two and subtract from eq.(2)
°Ba2+ = 2°NH4+ = 280 – 2 × 129.8 ...(4)
2+ +
 °Ba – 2°NH 4
= 20.40 ...(5)
Now subtract eq.(5) from eq.(1)
2°NH4+ + 2°OH– = 502.88
502.88
 °NH4+ + °OH– = °NH4OH =
2
= 251.44 scm2mol–1
3. DEBEY-HUCKEL-ONSARGAR THEORY OF STRONG ELECTROLYTES
Onsagar utilize debye huckel theory to calculate the Conductivity of strong electrolyte and the
observed that the experimental value of molar conductance is very low as Compair to theoritical value
the following three factors are responsible for the lower value of molar conductance.
1. Asymetric Effect
According to debye huckel theory, ions in the solution are surrounded by opposite charged ion and
they formed ionic sphere the absence of external electric field. Ionic sphere is completelly symmetrical.
But when we apply external electrical field then ions move towards opposed charged electrode
and ionic sphere becomes asymmetric. Due to this mobility of ions decreases which decrease the molor
Conductivity.
+ –
– –
–
– –
– + – +
– –
–
– –
(a) Symmetric ionic sphere (b) Asymmetric ionic sphere

2. Electrophoretic Effect
Another factor that slows down the motion of the ions at higher concentrations arises from the
tendency of the ionic sphere associated with molecules of water of hydration to move in a direction
opposite to that in which the central ion is moving. Thus a positive ion, for example, which migrates
towards the cathode has to make its way through the medium (water) which, it self, is moving with the
negative ionic sphere towards the positive electrode, similarly. A negative ion has to move towards the
anode through the medium (water) associated with positive ionic atmosphere which is moving towards
the negative electrode.
These counter currents slow down the ions in the same way as counter currents in a steam slow
down a swimmer, this effect is known as electrophoretic effect.
3. Viscous Effect
The third factor which affect the mobility of ions is the viscous effect. It arises from the viscous
drag of the solvent on the movement of ions. The ion tend to move in the direction of the applied electric
field. This electrical force is opposed by the fractional viscous drag exerted by the solvent. The greater
is the viscous drag, and hence the smaller is the ionic mobility and the conductance.
1
Conduc tan ce  mobility of ions 
Vis cos ity
In 1926, Debye, Huckal and onsager worked out mathematically the magnitude of asymmetry and
electrophoretic effect in term of such factors as valency of ions, ionic concentration and dielectric
constant and viscosity of the medium for uni-univalent electrolytes, such as KCl, which furnish two
univalent ions, the following equation was derived:
 82.4 8.20  105  

 m   m   1/ 2
 m  c
 (r T)  (r T)1/ 2 
where r and  are the dielectric constant and coefficient of viscosity of the medium, respectively
at the absolute temperature T and C is the concertration of the solution in moles per litre this equation
is known as the Debye-Huckel Onsager equation.
for a given solvent and at a given temperature, the above equation may be expressed as
 m   m  (A  Bm ) c
82.4
where  A = ( T)1/ 2 
r
8.20  105
B =
(r T)1/ 2
If the equation is correct, then by plotting molar conductance (m) against the c , a straight line
should be obtained
HCl
K Cl
m Ag
NO
3
N aN
O3
c
Fig. : Verification of Debye-Huckel Equation
If a solution is at infinite dilution i.e., if c is almost zero, then the second term on the right hand
side of the equation becomes negligible and
m  m
Electrochemical Cell
An electrochemical cell is a device capable of either deriving electrical energy from chemical
reactions or facilitating chemical reactions through the introduction of electrical energy.
Electrochemical cells are of two types
Electrochemical
Cells
Electrolytic Cells Galvanic Cells

G = (+)ve G = (-)ve
i. Electrotytic Cell
In an electrolytic cell, the reactions that occurs in a non-spontaneous one. Therefore, it is used
to convent the electrical energy to the chemical energy.
In fact, a chemical reaction is carried out with the help of an electrical current.
ii. Galvanic Cell
In a galvanic cell, the reaction that occurs is spontaneous. So it is used to transform the chemical
energy to the electrical energy.
Infact, an electrical current is produced as a result of some spontaneous chemical reaction finally,
we can conclude that electrolytic cell is a device to convert electrical energy into chemical energy where
in the galvanic cell, the reverse of this process takes place.
4. GALVANIC CELL
In the galvanic cell, electric current is generated as a result of some spontaneous reaction that
takes place in the cell.
such a cell, usually, consist of two electrodes. The electrode at which oxidation occurs is called
the anode while the electrode at which reduction occurs is called the cathode.
(flow of electrons)
e– Current e–
– flow +
Zn-electrode Salt bridge Cu-electrode
(Anode) (cathode)
ZnSO4 Cotton CuSO4

Solution Plug Solution
Fig. : Daniell Cell

Consider, a copper rod dipping in a solution of copper sulphate and zinc rod dipping in a solution
of zinc sulphate as in the daniell cell. The two rods are connected through an ammeter and the two
solutions are connected through a salt bridge i.e., an inverted U. Shaped gains tube filled with a solution
of KCl.
As soon as the circuit is closed, current starts flowing which is indicated by deflection in the
ammeter. The flow of current is accompanied by the following Processes:
at anode  Zn(s)  Zn2+(aq)+2e– (oxidation)
at cathode  Cu2+(aq) + 2e–  Cu(s) (reduction)
Net cell reaction  Zn(s) + Cu2+(aq)  Zn2+(aq) + Cu(s)
Since in the present case electrons are generated at the zinc electrode and consumed at the
copper electrode, the flow of electrons, that is, the flow of electricity, in the cell is form the zinc electrode
to the copper electrode. With the Passage of time, the concentration of Zn+2 ions increases and that of
Cu2+ decreases. This pushes the cell reaction in the backward direction. Ultimately a state of equilibrium
is reached and the cell stops producing electricity.
Important Points
 Galvanic cell consists of two half-cells. The reactions occurring in half cells are called
half-cell reactions. The half-cell in which oxidation occurs is called oxidation-half-cell and
the reaction taking place in it called oxidation-half cell reaction.
Similarly, the half cell in which reduction occurs is called reduction-half-cell and the reaction
taking place in it is called reduction-half-cell reaction
 The electrode where oxidation occurs is called anode and the electrode where reduction
occurs is termed cathode
 Electrons flow from anode to cathode in the external circuit
 Chemical energy is converted into electrical energy
 The net reaction is the sum of two half reactions.
Representation of An Electrochemical Cell

The following universally accepted conventions are followed in representing an electrochemical
cell :
(i) The anode (negative electrode) is written on the left hand side and cathode (Positive
electrode) on the right hand side.
(ii) A verticle line (|) or semicolon (;) indicated a contact between two phase
The anode of the cell is represented by writing metal first and them the metal ion present
in the electrolyte solution
for example -
Zn | Zn2+ or Zn ; Zn2+
(iii) The molar concentration or activity of the solution is written in brackets after the formula
of the ions
for example -
Zn | Zn2+ (1M) or Zn ; Zn2+ (1M)
(iv) The cathode of cell is represented by writing the cation of electrolyte first and then metal
for example
Cu2+ | Cu or Cu2+; Cu or Cu2+ (1M) |Cu
(v) The double vertical lines in the middle represents the salt bridge which separates the two
half cells.
for example:
Zn | Zn2+ || Cu2+ | Cu
The daniall cell can be represented as
Zn | ZnSO4(aq) || CuSO4(aq.) | Cu+
Anode Salt bridge Cathode
(oxidation) (Reduction)
5. ELECTRODE POTENTIAL AND FREE ENERGY
A potential difference develops between the electrode and the electrolyte is called electrode
potential. Thus the tendency of an electrode to gain or lose electrons when it is in contact with its own
ions in the solution is called electrode potential.
It is of two types :
(i) Oxidation potential : The potential difference arise due to loss of electrons is called
oxidation potential.
The half cell is which oxidation takes place is called anode and it has negative potential
with respect to the solution.
for example -
2
Fe(s) 
 Fe (aq)  2e

 
(ii) Reduction potential : The Potential difference arises due to gain of electron is called
reduction potential.
The half cell in which reduction takes place is called cathode and its has positive potential
with respect to the solution.
for example -
Cu2 (aq)  2e 

 Cu(s)


It is not possible to measure the absolute value of the single electrode potential directly.
Only the difference in potential between two electrode can be measured experimentally.
It is therefore, necessary to couple the electrode with another electrode whose potential
is known. This electrode is termed as reference electrode.
The emf of the resulting cell is measured experiment.
EmF of the cell  EAnode  ECathode
Knowing the value of reference electrode, the value of other electrode can be determind
Determination of H, G and S of a Cell Reaction
1. Free energy (G)
Suppose in a particular cell reaction, n is the number of electrons liberated at one electrode (or
taken up at the other electrode). Then, evidently, n faradays (nf) of electricity will be generated in the
complete cell reaction. If, for the sake of simplicity, the EMF of the cell, viz, Ecell is denoted by E,
then
The free energy is related to cell EMF in the following manner :
G  nFE
G can be negative if E is Positive.
when E is positive, the cell reaction is spontaneous.
Entropy (H) : According to Gibbs-Helmholtz equation
 ( G) 
G  H  T  
 T  P
and G = – nFE
  
then nFE  H  T  ( nFE)
 T P
 E 
or nFE  H  nFT  
 T  P
 H  E 
or E  T 
nF  T P
Entropy (S) : According to thermodynamic, we know that
 G 
 T   S
 
 ( G) 
or  T   S
 
  ( nFE)
or  T   S
 
 E 
nF    S
 T 
 E 
or S  nF  
 T 
S  nF  Temperature Coefficient
E  E2  E1 
Temperature Coefficient = T   T  T 
 2 1 
Nernst equation :
For a general reaction -
m1A  m2B  

 n1x  n2 y  ....

 ...(i)
the Gibbs free energy change is given by the equation
anx1  any2
G  G  2.303RT log10

...(ii)
amA1  aBm2
G  G  2.303RT log10

Pr oduct 
or ...(iii)
Re ac tan t 
The free energy change of a cell reaction is given by
G  nFEcell 
and 
G  nFEcell  ...(iv)
on substituting these values in equation (iii)
nFEcell  nFEcell

 2.303 RT log10
Pr oduct 
Re ac tan t 
Ecell  Ecell
 2.303RT
log10
Pr oduct 
or nF Re ac tan t 
This equation is known as Nernst equation.
Putting the value of R = 8.3143k-1 mol-1, F = 96500c, and T = 298 k
we get
Ecell  E cell
0.0591
log10
Pr oduct 
n Re ac tan t 
Let us assume a redox reaction takes place as -
ox  ne 
 Re d


then, the potential of the electrode is given by
Ecell  Ecell 
0.0591
log10
Re d
n ox 
Equilibrium Constant
At equilibrium
G = 0
and Ecell = 0
So
0 = G° + RT lnKeq
G G
or In K eq  or log10 Keq =
RT RT
 G 
or Keq = Antilog  RT 
 
 nFE 
or Keq = Antilog  RT   G  nFE
 
 n  E cell 
or K eq  Antilog  
 0.0591 
Classification of Electrode
Electrode
Metal-Metalion Metal-insoluble Redox

Gas electrode Other
electrode Metal electrode electrode
+2
SHE Zn/Zn Calomel electrode
+2
Cl2- electrode Cu/Cu Ag/AgCl electrode Quin-hydrin Glass electrode
+2 electrode
O2- electrode Fe/Fe
+3 Pb/PbSO4 electrode DMF
Fe/Fe
+
Ag/Ag
1. Gas electrode
A. Standard Hydrogen Electrode (SHE) : The gas and its ions are involved in the half cell
reaction. The gas can be introduced or evolved at the electrode. Let us consider the following reaction :
Oxidation  2H  2e 
H2 (g) 
Anode
H2(g)
(at 1 atm)
Pt foil
Solution
H+ ions
Fig. : The hydrogen electrode

Representation : Pt | H2 | H+(aq)
Half cell reaction :
1
H  e  


 H2
2
or 2H  2e  
 H2


Electrode Potential :
EH /H  EH  /H 
0.0591
log
P
2 2
n R
0.0591 PH
or E H  / H  E H  / H  log  2 2
2 2
2 [H ]
0.0591 1
or EH / H  EH  / H  log  2
2 2
2 [H ]
0.0591
or EH /H  EH  /H  log [H ]2
2 2
2
0.0591
or EH /H  EH  /H  2  log [H ]
2 2
2
EH /H  EH  /H  0.0591 log [H ]

2 2
EH /H  0.0591 PH  E  0.0v

2
PH   log[H ] or log[H ]  PH

The potential of hydrogen electrode depends on PH of the solution and we can use it for
the PH determination
B. Chlorine Electrode :
Representation = Pt Cl2(1atm ) Cl (aq)


electrode reaction -
1
Cl2  e  
 Cl
2
0.0591 Cl 
ECl / Cl
 ECl

/ Cl
 log  1/ 2 
2 2
1 PCl2
1
ECl / Cl
 ECl

/ Cl
 0.0591 log  PCl2  1atm
2 2
[Cl ]
2. Metal-metal Ion Electrode

Representation - m/mn+
mn+ + ne–  M
M(metal)
++
M (aq)
0.0591 a
Em / mn   Em / mn  log m
n am
0.0591 1
Em / mn   Em / mn  log
n am 
for example - Zn/Zn+2, Cu/Cu+2
3. Metal Insoluble Metal Electrode

A. Calomel Electrode :
Representation - Hg|Hg2Cl2(s)|Cl–(aq)
Hg2Cl2 (s)  2e   2Hg  2Cl
0.0591 2
Ecal  Ecal

 log Cl 
2
Ecal  Ecal  0.0591 log Cl 
from equation we can say that potential of calomel electrode is depends on Concentration
of Cl–
Conc.KCl Ecal
0.1N 0.338V
1.0N 0.280Volt
saturated 0.24Volt
If we use saturated KCl solution in calomel electrode then it is called saturated calomel
electrole.
Calomel electrode is used as reference electrode, in PH determination and in polarography.
Pt wire
KCl Solution
Hg2Cl2 Paste
Hg
B. Ag/AgCl2 Electrode :
Representation - Ag | AgCl | Cl–
AgCl + e–  Ag + Cl–
0.0591
E  E  log Cl 
1
4. Redox Electrode
Quinhydrone electrode :
Another important but a slightly different type of oxidation-reduction electrode is the so called
quinhydrone electrode which consists of a Pt wire placed in a solution containing hydroquinone
(QH2) and quinone (Q) in equimolar amounts
Pt wire
H+ions
Q+QH2
Representation -
Pt | Q, QH2 | H+
O OH
+
+ 2H + 2e
–
O OH
Quinone or Hydroquinone
Q  2H  2e  
 QH2


electrode potential -
0.0591 1
E  E  log 2
2 H 
0.0591 2
E  E  log H 
2
or E = E° + 0.0591 log [H+]
 PH = – log[H+]
So –PH = log[H+]
E  E  0.0591 PH
So we can say, the Potential of quinhydron electrode is depends on PH of the solution.

So we can use it for the determination of PH
6. CONCENTRATION CELLS WITH AND WITHOUT TRANSPORT
The cell in which EMF arises not due to any Chemical reaction but due to transfer of matter from
one half cell to the other because of a difference in the concentration of the species involved.
These are called concentration.
Concentration cells are of two types, viz.,
1. Electrode-Concentration cells
2. Electrolyte-Concentration cells
1. Electrode-Concentration Cells
The concentration cells in which electrode of the same material, having different concentration,
are dipped in the solution of same electrolyte are called electrode concentration cells.
A. Gas Concentration Cells :
Representation -
Pt ; H2(p1) | Solution of H+ ions, say, HCl | H2(p2) ; Pt
The reaction Occurring are:
R.H.E : 2H+ + 2e–  H2(p2) Reduction
+
L.H.E : H2(p1)  2H + 2e –
Oxidation
Overall reaction H2(p1)  H2(p2)
and EMF of cell,
0.0591
E  E  log (p2 / p1 )
2
Since, by defination E° = 0, we have

E = – 0.02955 log p2 /p1
E  0.02955 log(p1 / p2 )
when p2 < p1, the EMF is positive so that the whole process is spontaneous, being
equivalent to the expansion of H2 gas.
B. Amalgam Electrode Concentration Cells :
Representation -
Hg – Pb(C1), PbSO4 (Soln.) Hg – Pb(C2)
The electrode reactions are :
R.H.E. : Pb2+ + 2e–   Pb(C2) Reduction
L.H.E. : Pb(C1)  Pb2+ + 2e– Oxidation
overall reaction Pb(C1)  Pb(C2)
The EMF of the cell is given by -
0.0591
E log C2 / C1  E  0
2
or E  0.02955 log C1 / C2
Here, too if C2 < C1, the EMF is Positive so that the whole process is spontaneous i.e.
lead will go spontaneously from the higher concentration amalgam to the lower
concentration amalgam.
Electrolyte Concentration Cells
The concentration cell in which the activity of electrode are same but electrolyte solution have
different activity is known as electrolyte concentration cell.
Now we explain it by the following example:
Zn Zn2 Zn2 Zn
a1 a2
Now the cell reaction can be written as -

at anode - Zn  Zn2+ + 2e–
at cathode - Zn+2  Zn
Zn+2(a2)  Zn+2(a1)
Cell potential -
0.0591 a
E  E  log 1
n a2
E° = 0 and n = 2
0.0591 a
E log 2
2 a1
A. Electrolyte Concentration Cells with Transference
These cells consist of two identical electrodes imerged into two solutions of the same electrolyte
at difference concentration.
In these cells liquid junction potential is obtained and the potential of the cell effected by the
transport no. of opposite ion of the electrolyte salt.
for example :
Pt | H2 | HCl | HCl | H2 |Pt
1atm 1atm
1
at anode : H – e–  H+(a1)
2 2
1
at cathode : H  e 
 H2
(a2 ) 2
Net cell reaction - H+(a2)  H+(a1)

RT a2
Ecell  t Cl ln a2 > a1
nf a1
Ag | AgCl | HCl | HCl | AgCl | Ag

(s) (a1 ) (a2 ) (s)
at anode - Ag – e– + Cl–(a1)  AgCl

at cathode - AgCl + e–  Ag + Cl–(a2)
Net cell reaction - HCl(a1)  HCl(a2)
RT a1
E cell  tH ln a1 > a2
nf a 2
The cell potential of above cell in term of their mean activity -
2
RT  a  (1) 
Ecell  t H ln  
nf  a  (2) 
RT a  (1)
E cell  2t H ln
nf a  (2)
RT r  (1).C1
Ecell  2tH ln
nf r  (2).C2
RT (r  m)1
Ecell  2tH ln
nf (r  m)2
RT (r  )1 RT m1
E cell  2t H ln  2t H ln
nf (r  )2 nf m 2
B. Concentration cell without Transference

This cell is setup by combining two chemical cell without transference which differ in their
electrolyte concentration.
for example :
Ag | AgCl(s) | HCl | H2 | Pt | HCl | AgCl | Ag

(a1 ) 1atm (a2 ) (g)
Zn | ZnSO 4 || CuSO 4 | Cu | CuSO4 || ZnSO 4 | Zn

(a1 ) (a1 ) (a2 ) (a2 )
at anode - Ag – e + Cl–  AgCl
1
H+ + e–  H
2 2
Ag  HCl 1
(a1 )  AgCl + H
2 2
1
At cathode H2  AgCl  Ag  HCl
2 1atm (a2 )
Net cell reaction HCl(a1)  HCl(a2)
RT a1
Ecell  ln a1 > a2
nf a2
7. POLAROGRAPHY
 Polarography is an instrumental technique and consists in the measurement of applied

potential versus current flow in solutions.
 In polarography DMF (Dropping Murcury electrode) is used as a working electrode or
polarisable electrode.
 The Curve which show current voltage relationship is known as polarogram
 In this technique potential difference is imposed between polarisable electrode i.e, DMF
and non polarisable electrode i.e, reference electrode then electrochemical reaction takes
place due to which current flows by this current voltage curves are obtained which are
known as polarogramis from these curves, nature and behavior of substance can be
interpreted
C Limiting current
D
i
diffusion current (id)
Residual
A
current B
V E½ (halfwave potential)
Fig. : Polarogram
The polarogram divided into three parts :
1. From A to B (Residual current) : In this region theoretically no current should flow but
practically a small current flow through the cell i.e., from zero applied potential to
decomposition potential of species. This current is known as residual current and is
regarded as sum of two components
(A) Condensor or charging current which is flow due to charging of double layer at the
surface of each Hg drop.
(B) Faradic current which flows due to the reduction of traces of impurities present in
the solution.
2. From B to C (Diffusion current) : Current flows in this region is known as diffusion
current. At point B the potential of working electrode becomes equal to the decomposition
of metal ion. Curve BC is called polarographic curve or polarographic wave. At any point
between BC, the no. Of metal ions approaching the indicator electronic surface from the
bulk of the solution are greater than the no of ions deposited on the electrode.
3. From C to D (Limiting current) : Current flow in this region is called limiting current. C
is the point where current is no longer increases linearly with applied voltage. At point C
the formation of metal ions from the bulk of solutions becomes equal to their rate of
deposition on working electrode.
Half Wave Potential

The polarographic wave at which the current is half of the diffusion current is called half wave
potential this is independent on the concentration and has exact thermodynamic significance.
It can be represented as :
id id
i 2 2
V
The Half wave potential can be define by the following equation -
0.0591 i
Eapp  E½  log .... (1)
n (id  i)
if i  id 2
0.0591 id 2
then Eapp  E½  log
n id  id 2
or Eapp  E½
Equation (i) is known as equation of polarographic wave and it represents the relationship between
applied potential and current.
log i Slope = – 0.0591

id-i n
Intercept = E½
Eapp

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Chemistry (Electrochemistry)

1. CONDUCTANCE AND ITS APPLICATIONS

It is the reciprocal of the resistance (R) of the solution, i.e.,

Unit of Specific Resistance

Molar Conductance : (m)

Relation between Molar conductivity (m) and Equivalent conductivity (eq):

Variation of Conductivity and Molar Conductance with Dilution

Current carried by cation

Current carried by anion

where °+ = molar ionic conductance of cation at infinite dilution

So t    / (   )

But      m (Kohlrausch law)

Calculation of Absolute Ionic Mobilities

Ionic velocity (cm / sec)

Applications of Knolrausch’s Law

3. DEBEY-HUCKEL-ONSARGAR THEORY OF STRONG ELECTROLYTES

(a) Symmetric ionic sphere (b) Asymmetric ionic sphere

 82.4 8.20  105  

Electrolytic Cells Galvanic Cells

ZnSO4 Cotton CuSO4

Fig. : Daniell Cell

Representation of An Electrochemical Cell

5. ELECTRODE POTENTIAL AND FREE ENERGY

Cu2 (aq)  2e 

EmF of the cell  EAnode  ECathode

Entropy (S) : According to thermodynamic, we know that

m1A  m2B  

the Gibbs free energy change is given by the equation

G  G  2.303RT log10

on substituting these values in equation (iii)

then, the potential of the electrode is given by

Metal-Metalion Metal-insoluble Redox

Fig. : The hydrogen electrode

EH /H  EH  /H  0.0591 log [H ]

EH /H  0.0591 PH  E  0.0v

PH   log[H ] or log[H ]  PH

Representation = Pt Cl2(1atm ) Cl (aq)

2. Metal-metal Ion Electrode

for example - Zn/Zn+2, Cu/Cu+2

3. Metal Insoluble Metal Electrode

Hg2Cl2 (s)  2e   2Hg  2Cl

Ecal  Ecal  0.0591 log Cl 

So we can say, the Potential of quinhydron electrode is depends on PH of the solution.

6. CONCENTRATION CELLS WITH AND WITHOUT TRANSPORT

Since, by defination E° = 0, we have

Now we explain it by the following example:

Now the cell reaction can be written as -

Net cell reaction - H+(a2)  H+(a1)

Ag | AgCl | HCl | HCl | AgCl | Ag

at anode - Ag – e– + Cl–(a1)  AgCl

B. Concentration cell without Transference

Ag | AgCl(s) | HCl | H2 | Pt | HCl | AgCl | Ag

Zn | ZnSO 4 || CuSO 4 | Cu | CuSO4 || ZnSO 4 | Zn

at anode - Ag – e + Cl–  AgCl

Net cell reaction HCl(a1)  HCl(a2)

 Polarography is an instrumental technique and consists in the measurement of applied

Half Wave Potential

log i Slope = – 0.0591

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