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Electrochemistry, Kalra Sir's Notes
Electrochemistry, Kalra Sir's Notes
3. DANIEL CELL converts the chemical energy liberated during the redox reaction to electrical
energy and has an electrical potential equal to 1.1 V . when concentration of Zn2+ and Cu2+ ions is
unity. Such a device is called a galvanic or a voltaic cell.
4. GALVANIC CELL is an electrochemical cell that converts the chemical energy of a spontaneous redox
reaction into electrical energy. In this device the Gibbs energy of the spontaneous redox reaction is
converted into electrical work which may be used for running a motor or other electrical gadgets like
heater, fan, geyser, etc.
5. If an external opposite potential becomes greater than Eocell of the reaction gets reversed and
electrochemical cell now functions as an electrolytic cell.
6.
8. STANDARD HYDROGEN ELECTRODE (SHE) :It consists of a platinum wire sealed in a glass tube, The
wire is coated with finely divided platinum black. Platinum black catalyze the reaction 2H+(aq) + 2e- →
H2(ag) Pure hydrogen gas at 1 atmosphere pressure is bubbled through HCl solution containing H + ions
at 1.0M concentration continuously over platinum black electrode. The temperature is 298K. It is
assigned a value of zero for it electrode potential and is used as reference electrode.
9. NERNST’S EQUATION : It is a relationship that relates electrode potential and concentration of metal
2.303RT
ion. Ecell E cell
0
log
nF
2.303RT
At T = 298 K substituting R=8.314 F= 96500 C, [ 0.059 ]
F
0.0591 [Pr oducts]n
Ecell E log Q Where Q =Reaction Quotient, Quotient Q=
n [Re ac tan ts]n
,n=number of electrons
3
+2 +3 2.303RT Mg 2
Example: Mg /Mg // Cr /Cr Ecell E 0
Cell log 2
6F Cr 3
10. Relation between E0cell and Equilibrium constant Kc : At equilibrium Q = Kc and Ecell = 0
2.303RT E cell nF E cell n
E cell E cell log K C , log K c
nF 2.303RT 0.059
QUESTIONS BASED ON NERNST EQUATION, EQUILLIBRIUM CONSTANT,& GIBBS ENERGY
1. Define Electrochemical cell.What happens when applied external opposite potential becomes greater
than Eocell of electrochemical cell.
2. Explain the working of the galvanic cell by taking an example.
3. Explain the function of the salt bridge.
4. Which reference electrode is used to measure the electrode potential of other electrodes?
5. Write the Nernst equation for the cell reaction in the Daniel cell. How will the ECell be affected when
concentration of Zn2+ ions is increased?
6. Consider a cell given belowCu|Cu2+|| Cl—|Cl2,Pt Write the reactions that occur at anode and cathode
7. A galvanic cell has electrical potential of 1.1V. If an opposing potential of 1.1Vis applied to this cell, what
will happen to the cell reaction and current flowing through the cell?
1. Write the Nernst equation and emf of the following cells at 298K:
a) Mg(s)/Mg2+(0.001M)//Cu2+(0.0001)/Cu(s); EoCu2+/Cu = +0.34V, EoMg2+/Mg = -2.36
b) Fe(s)/Fe2+(0.001M)//H+(1M)/H2(g)/Pt(s) EoFe2+/Fe= -0.44 V
c) Zn/Zn2+(0.1M)//Cd2+(0.01)/Cd; EoZn2+/Zn = -0.76V , EoCd2+/Cd = -0.40V
d) Cu/Cu2+(2M)//Ag+(0.05M)/Ag ; EoCu2+/Cu = +0.34V , EoAg+/Ag = + 0.80V
e) Mg(s)/Mg2+(10-3M)//Cu2+(10-4M)/Cu(s); EoCu2+/Cu = +0.34V, EoMg2+/Mg = -2.36
f) Zn/Zn2+(2M)//Cu2+(0.5M)/Cu; EoZn2+/Zn = -0.76V , EoCu2+/Cu = 0.34V
g) Sn/Sn2+(0.050M)//H+(0.020M)/H2(g)/Pt(s) EoSn2+/Sn= - 0.14V
h) Sn/Sn2+(0.04M)//H+(0.02M)/H2(g)/Pt(s) EoSn2+/Sn= - 0.14V
i) Pt(s)/Br2(l)/Br-(0.010)// H+(0.030M)/H2(g)/Pt(s)
2. Calculate the emf of the cell at 25oC for the following :
a) Mg(s) + 2Ag+(0.0001M) Mg+2(0.130M) + 2Ag(s). if Eocell =3.17V.
b) Ni(s) + 2Ag+ (0.002M) Ni+2(0.160M) + 2Ag(s),Given Eocell =1.05 V
c) 2Cr(s) + 3Fe2+(0.1M) 2Cr3+(0.01M) + 3Fe(s) EoCr3+/Cr= - 0.74V , EoFe2+/fe= - 0.44V
3. The emf of the cell Zn/Zn2+(0.1M)//Cd2+(M1)/Cd has been found to be 0.3035 V at 298K.Calculate the
value of M1. EoZn2+/Zn = -0.76V, EoCd2+/Cd = - 0.40V.
4. Calculate the potential for half cell containing .10M K2Cr2O7(aq),0.20MCr3+(aq) and 1.0x 10-4 H+ (aq) ,The
half cell reaction is Cr2O72-(aq) + 14 H+ (aq) + 6e- 2Cr3+(aq) + 7H2O(l) and the Standard cell potential
E0cell = 1.33V
5. How would you determine the standard electrode potential of the system Mg 2+|Mg?
6. Calculate the potential of hydrogen electrode in contact with a solution whose pH is 10.
7. A Zinc rod is dipped in 0.1M solution of ZnSO4.The salt is 95% dissociated at this dilution at
298K.Calculate the electrode potential.
3. Resistance: The electrical resistance is represented by the symbol ‘R’ and it is measured in ohm (Ω). The
electrical resistance of any object is directly proportional to its length, l, and inversely proportional to
l l
its area of cross section, A. R or R ( ) Where is the constant which depends upon the
A A
nature of conductor. It is called specific resistance or resistivity. Unit is ohm-cm
4. The resistivity for a substance is its resistance when it is one metre long and its area of cross section is
one m2.
5. Conductance : The ease with which carried flows through conductor is called its conductance. It is
1
reciprocal of the resistance G .The SI unit of conductance is siemens, represented by the symbol
R
‘S’ and is equal to ohm–1 ( 1 ) (also known as mho) .
6. Specific Conductance or Conductivity : of any conductor is the reciprocal of specific resistance and is
denoted by (Greek work Kappa) .The SI units of conductivity are Sm–1 but quite often, κ is expressed
in S cm–1. Conductivity of a material in S m–1 is its conductance when it is 1 m long and its area of cross
1 1 l
section is 1 m2. It may be noted that 1 S cm–1 = 100 S m–1. = = GG* The
R A
quantity l/A is called cell constant denoted by the symbol, G*. It depends on the distance between the
electrodes and their area of cross-section and has the dimension of length–1 and can be calculated if we
l
know l and A. (G*(cell constant) = ) The conductivity of a solution at any given concentration is the
A
conductance of one unit volume of solution kept between two platinum electrodes with unit area of
cross section and at a distance of unit length.
7. Superconductivity: Certain materials called superconductors by definition have zero resistivity or
infinite conductivity. Earlier, only metals and their alloys at very low temperatures (0 to 15 K) were
known to behave as superconductors, but nowadays a number of ceramic materials and mixed oxides
are also known to show superconductivity at temperatures as high as 150 K.
8. Molar Conductivity : It is defined as the conducting power of all the ions produced by one gram mol of
an electrolyte in a solution. m In the above equation, if κ is expressed in Sm–1 and the
C
concentration, c in mol m then the units of Λm are in Sm2mol–1
–3
(Sm -1 )
m (Sm 2 mol -1 )
1000( Lm 3 ) Molarity(molL1 )
If we use Scm–1 as the units for κ and molcm–3, the units of concentration, then the units for Λm
are Scm2 mol–1.
(Scm -1 ) 1000( Lcm 3 )
m (Scm 2 mol-1 )
Molarity(molL1 )
9. Limiting molar conductivity :When concentration approaches zero, the molar conductivity is known as
limiting molar conductivity and is represented by the symbol 0
10. Conductivity of a solution decrease with dilution because on dilution the number of ions per unit
volume decreases.so the conductivity decreases
MAHENDRA KALRA …….Kalra1977@gmail.com 9462305605
2020 CHEMISTRY SIMPLY THE BEST…………………ENJOY CHEMISTRY
11. Variation of molar conductivity with dilution (concentration is decreased) : The increase in
conductivity of strong and weak electrolyte upon dilution is due to different reasons:
a) FOR STRONG ELECTROLYTES molar conductivity increases slowly with dilution because in strong
electrolytes the dissociation of the electrolyte in to ions is almost complete however interionic
forces are quite strong. Upon dilution ionic attractions are reduced. This leads to increase in ionic
mobility thus molar conductivity increases with dilution(or decrease in concentration)
b) FOR WEAK ELECTROLYTES molar conductivity increases Steeply with dilution because in weak
electrolytes the dissociation of electrolyte into ions is comparatively less.Dilution helps in
dissociation of electrolyte .As a result more ions are formed and corresponding value of
conductivity also increases .This increase quite large.
Molar conductivity versus c1/2 for acetic acid (weak electrolyte) & KCl (Strong electrolyte) in
aqueous solution
12. Kohlrausch’s Law : The law states that limiting molar conductivity of an electrolyte can be represented
as the sum of the individual contributions of the anion and cation of the electrolyte. (i)
NaCl (Na ) (Cl )
(ii) CaCl 2 (Ca 2 ) 2 (Cl ) (iii) Al 2 ( SO 4 ) 3 2 ( Al 3 ) 3 ( SO 4 ) 2
(iv) 0CH 3COOH 0CH 3COONa 0 HCl 0 NaCl
(v) 0 NH 4Cl 0 NaOH 0 NaCl
0
NH 4OH
13. Application of Kohlrausch’s Law 1.Calculation of limiting molar conductivity 2. Calculation of degree
of dissociation : Degree of Dissociation is ratio of molar conductivity at a specific concentration ‘C’ to
cm
limiting molar conductivity. It is denoted by 3. Calculation of dissociation constant
0m
c 2 c2
Ka =
(1 ) ( )
QUESTIONS BASED ON CONDUCTIVITY MOLAR CONDUCTIVITY, CELL CONSTANT, KOHLRAUSCH LAW AND ITS
APPLICATION
1. Define conductivity,molar conductivity &. limiting molar conductivity.
2. Distinguish between Electrical conductance & Electrolytic (ionic conductance)
3. Express the relation among the cell constant ,the resistance of the solution in the cell and the
conductivity of the solution .How is the conductivity of a solution related to its molar conductivity.
4. The resistance of 0.01M NaCl solution at 25oC is 200ohm.The cell constant of the conductivity cell is
unity .calculate the molar conductivity of the solution.
5. The conductivity of 0.20M solution of KCl at 298 K is 0.0248SCm-1.Calculate its molar conductivity.
6. The Molar conductivity of a 1.5M solution of an electrolyte is found to be 138.9 SCm 2 mol-1 . Calculate
the conductivity of this solution.
7. The resistance of conductivity cell containing 0.001M KCl at 298K is 1500 ohm. What is cell constant if
conductivity of 0.001M KCl at 298K is 0.146X 10-3Scm-1.
8. When a certain conductance cell was filled with 0.1M KCl solution it has resistance of 85 ohm at
25oC.When the same cell was filled with an aqueous solution of 0.052Maof unknown electrolyte the
resistance was 96ohm. Calculate the molar conductivity of electrolyte. The conductivity of 0.1 M
solution of KCl is 1.29 x 10-2Scm-1.
MAHENDRA KALRA
MAHENDRA KALRA …….Kalra1977@gmail.com 9462305605
2020 CHEMISTRY SIMPLY THE BEST…………………ENJOY CHEMISTRY