MLP 3 (ELECTRICHEMISTRY)

1.Electrochemistry is the branch of chemistry which deals with the relationship between electrical energy and
chemical energy and inter-conversion of one form into another.

2. An electrochemical cell consists of two metallic electrodes dipped in electrolytic solutions. The cells are of
two types:
(a) Electrolytic cells (b) Galvanic cells

3. A galvanic cell consists of two half cells. Each half cell contains an electrolytic solution and a metallic
electrode. The electrode at which- oxidation takes place is called an anode and the electrode at which reduction
takes place is called the cathode. The half-cells are separated from each other by means of a porous pot or a salt
bridge.

4. The passage of current from one electrode to the other indicates the existence of potential difference
between them. This difference of potential which causes current to flow from the electrode of higher negative
potential is called the electromotive force (emf).

5. Electrical energy = Emf (volts) x Quantity of electricity (coulombs)

6. The potential of SHE is assigned an arbitrary value of zero. E° = 0 V. It is used as a reference electrode for
measuring the standard electrode potentials. .

7. When the elements are arranged in order of their standard electrode potentials, a series known as
electrochemical series is obtained.

8. Standard emf of a cell,

E0cell =E0cathode – E0anode = E0Riglit – E0Left

9. ΔG° = -nFE0cell

If E0cell is positive, ΔG° would be negative and reaction would be spontaneous. If E0cell is
negative, ΔG° would be positive and the reaction would be non-spontaneous.
10. A species with higher standard reduction potential has greater tendency to accept electrons to undergo
reduction or vice versa.

11. The potential of an electrode in contact with its ions in solution varies with the concentration of the ion.
Thus, for a redox reaction,

12. For an electrochemical cell for which the overall reaction is

13. The equilibrium constant, A of cell can be relate to standard emf of cell

14. Resistance is the measure of obstruction to the flow of current.

𝑙
𝑅 𝛼 or 𝑅 = 𝜌 𝑙
𝐴
𝐴

where ρ= specific resistance or resistivity. Unit of R is ohm.

15. Resistivity is defined as the resistance of a conductor of 1cm length and having an area of cross-section
equal to 1cm2.
𝐴𝑅
𝜌=
𝑙
unit of resistivity is ohm-cm

16. Conductance (G) is reciprocal of resistance, i. e. G= 1/R

Unit of conductance is ohm-1 or mho or Siemen(S).

17. Specific conductance or Conductivity (𝑘) is reciprocal of specific resistance.

The reciprocal of resistivity is called conductivity. The conductivity, “k” of an electrolytic solution depends on
the concentration of the electrolyte, nature of solvent and temperature and it is defined as the conductance of a
solution having unit volume.OR
Specific conductance or conductivity is defined as the conductance of a solution taken in a cell whose
electrodes are at unit distance apart from each other and each having an area equal to 1 cm 2.
1 𝑙 𝑙
𝑘 = 1⁄𝜌 = ∗ = 𝐺 ∗
𝑅 𝐴 𝐴
Unit of specific conductance is ohm-1 cm-1 or S cm-1.

Cell constant- Cell constant = l/A

Where, l = distance between twoelectrode
A= cross-section area of electrode

18. Molar conductance (Λm) is defined as the conductance of the volume of solution which contains one mole
of the solute and is placed between two parallel electrodes which are one centimeter apart and having sufficient
area to hold the whole of the solution.
Unit of molar conductance is Ω-1 cm2 mol-1 or S cm2 mol-1
19.
ҡ∗1000
Λm = 𝐶 S cm2 mol−1
 Where C = concentration of solution in moles per liter (or Molarity).
20. The electrical conductance through metals decreases with increase in temperature.
21. The electrolytic conductance increases with increase of temperature.
22. Effect of Dilution on
(а) Equivalent conductance: The value of equivalent conductance increase with dilution and attains a
maximum value at infinite dilution.
(b) Specific conductance: The value of specific conductance decreases with dilution as the number of
current carrying particles i.e., ions present per cm3 of solution decreases on dilution.
(c) Molar conductance: The value of molar conductance increases with dilution and finally attains a
maximum value at infinite dilution.
23. Variation of molar conductance with concentration:
(a) Strong electrolytes:

(b) Weak electrolytes:

24. According to Kohlrausch law of independent migration of ions, the limiting molar conductivity of an
electrolyte can be expressed as the sum of the contributions of the cation and the anion of the electrolyte.

where v+, v– are the number of cat ions and anions per unit formula of the electrolyte respectively; λ0+, and λ0– are
the limiting molar conductivities of the cation and anion respectively.

Applications: (i)Calculation of degree of Dissociation of Weak Electrolytes:

 = Λ mc / Λ m 

Λ mc = molar conductivity of solution at any concentration

Λ m = limiting molar conductivity

(ii)Determining the solubility of sparingly soluble salts

Solubility = k x 1000 / Λ mmol L-1 where „k‟ is the conductivity

(iii) Calculation of Dissociation Constant of Weak Electrolyte

K = C2 / (1- )

Also  = Λ m c / Λ m 

K = C(Λ m) 2 / Λ m (Λ m - Λ mc)

25. Faraday’s laws of electrolysis:

(a) First law: The amount of a substance deposited or liberated at an electrode is directly proportional to the
quantity of electricity passed through the electrolyte. Mathematically,

where m = mass of substance deposited or liberated.

(b) Second law: When the same quantity of electricity is passed through solutions of different electrolytes, the
weight of different substances deposited or liberated at the respective electrodes are proportional totheir
chemical equivalent weights.
26.Equivalent weight of metal= Atomic mass of the metal / no. of electron required to reduce to cation to
the metal

27. The charge on one mole of electrons is approximately equal to 96500 coulombs. This quantity of electricity
is called Faraday constant (F).

28. Products of electrolysis

NaCl (molten) Cathode : Na+(l) + e– → Na(s) Anode : Cl–→ ½Cl2+e–

NaCl (aq) Cathode : H2O (l ) + e– → ½H2(g) + OH– Anode : Cl–→ ½Cl2+e–
H2SO4(dil) Cathode : H+ + e-→ ½ H2 Anode: 2H2O(l )→ O2(g) + 4H+(aq) + 4e–
H2SO4(conc) Cathode : H+ + e-→ ½ H2 Anode: 2SO4 2– (aq) → S2O82– (aq) + 2e–
AgNO3(aq)-Ag electrodes Cathode : Ag+(aq) + e-→ Ag(s) Anode: Ag(s) → Ag+(aq) + e-
AgNO3(aq)- Pt electrodes Cathode : Ag+(aq) + e-→ Ag(s) Anode: 2H2O(l )→ O2(g) + 4H+(aq) + 4e–
CuCl(aq)- Pt electrodes Cathode : Cu+(aq) + e-→ Cu(s) Anode: 2H2O(l )→ O2(g) + 4H+(aq) + 4e–

29. Electrochemical series: The arrangement of elements in the order of increasing reduction potential values is
called electrochemical series.

Applications of electrochemical series:

1. Calculation of EMF of the cell E 0 cell = E0 cathode – E 0 anode

2. Predicting feasibility of the reaction : A redox reaction is feasible if electron releasing species is present at a
position lower in the series as compared to electron accepting species.
3. Comparison of relative reducing or oxidising power of the elements: The reducing character of the elements
increases down the series and its oxidising character decreases.

4. To predict the reaction of a metal with dilute acids to liberate hydrogen gas : Metals which lie above
hydrogen in the electrochemical series can reduce H+ ions to hydrogen. Corrosion of metals is an
electrochemical phenomenon. In corrosion metal is oxidized by loss of electrons to oxygen and formation of
oxides.

Anode(Oxidation): 2Fe(s) → 2Fe2+ + 4e-

Cathode(Reduction): O2(g)+ 4H +(aq)+4e - →2H2O

Atmospheric Oxidation: 2Fe2+(aq)+2H2O(l)+1/2O2 (g) → Fe2O3(s)+ 4H + (aq)

30. Concentration cell- If two electrodes of the same metal dipped separately into two solution of the same
electrolyte having different concentration and the solutions are connected through salt bridge, such cell are
known as concentration cells

In these cells, oxidation takes placeon the electrode with lower concentration(C1) while reduction takes
placewith higher concentration (C2)

Eg. H2| H+(C1) ||H+(C2) | H2;Cu | Cu2+(C1) || Cu2+ (C2) | Cu

Ecell= 0.0591/n log C2 /C1

-------------------------------------------------------------------------------------------------------------------------------
Case based questions
Q1. Read the passage given bellow and answer the following question. ( 1*4=4)

The working of a galvanic cell is quite simple. It involves a chemical reaction that makes the electric energy available as the
end result. During a redox reaction, a galvanic cell utilizes the energy transfer between electrons to convert chemical energy
into electric energy.

Galvanic cell utilizes the ability to separate the flow of electrons in the process of oxidization and reduction, causing a half
reaction and connecting each with a wire so that a path can be formed for the flow of electrons through such wire. This flow of
electrons is essentially called a current. Such current can be made to flow through a wire to complete a circuit and obtain its
output in any device such as a television or a watch.

Give the answer following question

Q1.What is the electrochemical cell?

(a) change chemical energy into heat energy

(b) change heat energy in to chemical energy
(c) change electric energy in to chemical energy
(d) change chemical energy in to electricenergy

Q2. When the salt bridge is removed from a cell, its voltage
(a) will increase
(a) will decrease to half
(c) will decrease to zero
(d) will not change

Q3.What is the direction of current flow in this galvanic cell

(a) Cu electrode to Ag electrode
(b) Ag electrode to Cu electrode
(c) both side
(d) none of these

Q4.How many coulombs of electricity flow in this galvanic cell?

(a) 96500 C (b)48250 C (c) 193000 C (d)2895 C
Q2. Read the passage given bellow and answer the following question. (1 *4=4)
Different metals have different reactivities with chemical reagents. The metals that form positive ions by losing electrons more
readily. A more reactive metal displaces a less reactive metal from salt solution. Such reactions are called displacement
reactions. Consider an example, if a small amount of zinc is dipped in copper sulphate solution, zinc is displaced from copper
sulphate. The blue colour of copper sulphate fades and colourless zinc sulphate solution is obtained. Therefore, zinc is more
reactive than copper.

Note: In the following questions a statement of assertion followed by a statement of reason is given. Choose the
correct answer out of the following choices.
(a) Both assertion and reason are true and the reason is the correct explanation of assertion.
(b) Both assertion and reason are true and the reason is not the correct explanation ofassertion.
(c) Assertion is true but the reason is false.
(d) Assertion is false but reason is true.

(i)Assertion: Reactivity Series is an arrangement of element based ontheir reactivity.

Reason: Reactivity Series is used to separate elements based on their reactivity.
(ii) Assertion: Auric chloride (AuCl3) solution cannot be stored in a vessel made of copper, iron, nickel,
chromium, zinc or tin.
Reason: Gold is a very precious metal.
(iii) Assertion: Zinc displaces copper from copper sulphate solution.
Reason: The E0 of zinc is −0.76 V and that of copper is +0.34 V.
(ivAssertion: F2 is stronger oxidizing agent than Cl2.
Reason: oxidation potential of F2 is greater than that of Cl2.

MCQ(1 marks)
Q.1. On electrolysis of dilute sulphuric acid using platinum electrodes, the product obtained at the anode
will be

(a)hydrogen

(b)oxygen

(c)hydrogen sulphide

(c)sulphur dioxide

Q.2.Which reaction is not feasible?

(a) 2KBr + I2 → 2KI + Br2

(b) 2KI + Br2 → 2KBr + I2

(c) 2KBr + Cl2 → 2KCl + Br2

(d) 2H2O + 2F2 → 4HF + O2

Q.3. Without losing its concentration ZnCl2 solution cannot be kept in contact with

(a) Au

(b) Al

(c) Pb

(d) Ag

Q.4. Λ0 m (NH4OH)is equal to ______________.

(a) Λ0 m (NH4OH) + Λ0 m (NH4Cl) - Λ0(HCl)

 (b) Λ0 m (NH4OH) + Λ0 m (NaCl) - Λ0(NH4Cl)

(c) Λ0 m (NH4Cl) + Λ0 m (NaOH) - Λ0(NaCl)

(d) Λ0 m (NH4Cl) + Λ0 m (NaCl) - Λ0(NaOH)

Q.5.In the electrolysis of aqueous sodium chloride solution which of the half cell reaction will occur at

anode?

(a) Na+ (aq) + e–Na (s) ; E0cell = –2.71V

(b) 2H2O (l) O2 (g) + 4H+ (aq) + 4e–; E0cell = 1.23V

(c) H+ (aq) + e– ½ H2 (g); E0cell = 0.00 V

𝟏
(d) Cl - (aq) Cl2(g) + e-E0cell = 1.36 V
𝟐

Q.6. conductivity cell containing electrodes made up of

(a) Gold
(b) Silver
(c) Platinized platinum
(d) Copper

Q7.For a certain redox reaction, E° is positive. This means that

(a) ΔG° is positive, K is greater than 1

(b) ΔG° is positive, K is less than 1
(c) ΔG° is negative, K is greater than 1
(d) ΔG° is negative, K is less than 1

Q.8.The cell reaction of the galvanic cell.

Q9. If limiting molar conductivity of Ca2+ and Cl– are 119.0 and 76.3 S cm2 mol-1, then the value of limiting
molar conductivity of CaCl2 will be
(a) 195.3 S cm2 mol-1
(b) 271.6 S cm2 mol-1
(c) 43.3 S cm2 mol-1
(d) 314.3 S cm2 mol-1

Q.10 The emf of the cell:

Ni / Ni2+ (1.0 M) // Au3+ (1.0 M) / Au (E° = -0.25 V for Ni2+/Ni; E° = 1.5 V for Au3+/Au) is
(a) 1.25 V
(b) -1.25 V
(c) 1.75 V
(d) 2.0 V
Assertion and Reason Type Questions (1 marks)

Note : In the following questions a statement of assertion followed by a statement of reason is given. Choose the
correct answer out of the following choices.

(i) Both assertion and reason are true and the reason is the correct explanation of assertion.
(ii) Both assertion and reason are true and the reason is not the correct explanation of assertion.
(iii) Assertion is true but the reason is false.
(iv) Assertion is false but reason is true.

Q.1. Assertion : Copper sulphate can not be stored in zinc vessel.

Reason : Zinc is less reactive than copper.

Q.2.Assertion: Copper reacts with hydrochloric acid and liberates hydrogen from the solution of dilute
hydrochloric acid.

Reason: copper is below hydrogen in the electrochemical series.

Q.3.Assertion: A small amount of acid or alkali is added before electrolysis of water.

Reason: Pure water is weak electrolyte.

Q.4.Assertion: K and Cs are used in photoelectric cells.

Reason: K and Cs emit electrons on exposure to light.

Q.5.Assertion: The resistivity for a substance is its resistance when its is one meter long and its area of
cross section is one square meter.

Reason: The SI unit of resistivity are ohm meter (Ωm)and ohm centimeter (Ω cm).

SHORT ANSWER TYPE QUESTION(2 marks)

Q.1.Write the electrolytic product of CuSO4 solution using Cu-electrode?

Q.2.Is it possible to measure single electrode potential?

Q.3.State Kohlrausch law of independent migration of ions.

Q.4.What is the free energy change for (a) galvanic cell (b) electrolytic cell?
Q.5.The conductivity of metals decreases while that of electrolytes increases with increases in temperature.
Why?

Q.6.In fig. (1), identify the nature of electrolyte A& B. In which case it is not possible to obtain value of
limiting molar conductance?
Q.7.In the button cell widely used in watches & in other devices; the following reaction takes place;

Zn(s) + Ag2O(s) + H2O(l) Zn2+(aq) + 2Ag(s)

Determine E0cell& ∆rGo for the reaction? Given, E0Ag+/Ag = 0.344V & E0Zn2+/Zn = -0.76V

Q.8At what pH of HCl solution will hydrogen gas electrode show electrode potential of −0.118 V? H2 gas
is bubbled at 298 K and 1 atm pressure.

Q.9.The molar conductance at infinite dilution for sodium acetate, hydrochloric acid & sodium chloride
are 91.0,425.9 & 126.4 Scm2mol-1 respectively at 298 K. Calculate the molar conductance of acetic
acid at infinite dilution.

Q.10.(a) Following reactions occur at cathode during the electrolysis of aqueous sodium chloride solution:
Na+(aq) + e-1 ——-> Na(s) E° = – 2.71 V
H (aq) + e ——–> 1/2H2(s)
+ -1
E° = 0.00 V
On the basis of their standard reduction electrode potential (E°) values, which reaction is feasible at
the cathode and why?
(b) Why does the cell potential of mercury cell remain constant throughout its life?

SHORT ANSWER TYPE QUESTION(3marks)

Q.1.How would you explain the sharp increase in molar conductivity of a weak electrolyte on dilution?
How is the molar conductivity related to degree of dissociation of a sparingly soluble salt?

Q.2.How many moles of electrons are required to

i) Reduce 1 mole of MnO4- to Mn2+.
ii) Produce10.0 gm of Al from molten Al2O3.

Q.3 Depict the Galvanic cell in which the reaction

Zn(s) + 2Ag+(aq) Zn2+(aq) + 2Ag(s)
takes place. State the reaction taking place at each of its electrode & also state the carriers of current
within this cell.

Q.4. Predict if the reaction between the following is feasible.

(a) Fe3+(aq) and I-(aq)
(b) Ag (s) and Fe3+ (aq)
Given standard potentials :
E01/2I2, I- = 0.541V , E0Ag+, Ag = 0.80 V and E0 Fe3+,Fe2+= 0.77V

Q.5.Calculate the equilibrium constant of the reaction ;

Zn + Cd2+ Zn2+ + Cd

Given, E0cell =0.36V

Q.6.Conductivity of 0.00241m acetic acid is7.896*10-5 Scm-1.Calculate it’s molar conductivity & if λ∞m
for acetic acid is 390.5 Scm2mol-1.What is it’s dissociation constant.

Q.7.Calculate E°cel1 and ∆rG° for the following reaction at 25 °C:

A2+(aq) + B+(aq) ——–> A3+(aq) + B(s)
Given Kc=1010, 1F=96500 C mol-1

Q8.The EMF of the following cell is found to be 0.20 v at 298 K

Cd | Cd2+ (?) || Ni2+ (2.0 M) | Ni
What is the molar concentration of Cd2+ ions in the solution?
E0Cd2+/ Cd = - 0.40 V, E0Ni2+/ Ni = - 0.25

Q9. Calculate the standard cell potentials of galvanic cell in which the following reactions take place:

2Cr(s) + 3Cd2+ (aq) → 2Cr3+(aq) + 3Cd

Calculate the ∆rG0 and equilibrium constant of the reactions
Q.10 (A) What is salt bridge and write its function?
(b)What does the negative value of standard electro potential indicate?

LONG ANSWER TYPE QUESTION(5marks)

Q.1.(a) What is the conductivity? Why does the conductivity of a solution decrease with dilution?
(b) The resistance of a conductivity cell containing 0.001M KCl solution at 298 K is 1500 Ω. What is the cell
constant if the conductivity of 0.001 M KCl solution at 298 K is 0.146×10−3Scm−1?

Q.2. Consider figure given below and answer the questions (i) to (vi):

(i) Write the direction of electron flow.

(ii) Is silver plate anode or cathode?
(iii) What will happen if salt bridge is removed?
(iv) When will the cell stop functioning?
(v) How will concentration of Zn +2 ions and Ag+ ions be affected when the cell functions?
(vi) How will the concentration of Zn +2 ions and Ag+ ions be affected after the cell becomes ‘dead’?
Q.3. (a) What is the molar conductivity? Write its units.
(b)The conductivity of 0.20 mol L-1 solution of KC1 is 2.48 X 10-2 S cm-1. Calculate its molar
conductivity and degree of dissociation (a). Given λ(K+) = 73.5 S cm2 mol-1 and λ(Cl-) = 76.5 S
cm2 mol-1.
Q4. (a) State Kohlrausch law of independent migration of ions. Write an expression for the molar conductivity
of acetic acid at infinite dilution according to Kohlrausch law.
(b) Calculate Λ ° for acetic acid.
Given that Λ° (HC1) = 426 S cm2 mol-1
Λ° (NaCl) = 126 S cm2 mol-1
Λ° (CH3COONa) = 91 S cm2 mol-1
Q5.(i) Write the formulation for the galvanic cell in which the reaction.

Cu (s) + 2Ag+ (aq) Cu2+ (aq) + 2Ag (s) take place. Identify the cathode and anode
reactions in it
(ii) Write Nernst equation and calculate of emf of the cell.
Sn (s) | Sn+2 (0.04 M) || H+ (0.02 M) || H2 (g) (1 bar) | Pt (s)
Given EO Sn2+/ Sn = - 0.14

ANSWERS

Answers of Case based question

Answer Q1.
(i) d , (2) C, (3) B, (4) C
Answer Q2.
(i) a , (2) b, (3) a, (4) C

ANSWERS OF MCQ

(1) b,(2) a, (3) b, (4) c, (5) d, (6) c, (7) c, (8) d, (9) b, (10) c

Answers of Assertion and Reason Type Questions (1 marks)

(1) c,(2) d, (3) a, (4) a, (5) b,

ANSWERS OF SHORT ANSWER TYPE QUESTION (2 marks)

Ans1. CuSO4 Cu2+ + SO42-

At Cathode; Cu2+ (aq) + 2e- Cu(s)

At Anode; Cu(s) Cu2+ + 2e-

Ans2. NO,Oxidation or reduction can not take place alone. Moreover, Electrode potential is a
relative
tendency and can be measured with Respect to a reference electrode only.

Ans3. Kohlrausch law of independent migration of ions 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.
λ° (NaCl) = λ°Na+ + λ°Cl–
 Ans4. (a) ∆rG<0, (b) ∆rG> 0

Ans5.With increase in temperature, the K.E. of metal cation increases and obstructs the free flow of electrons decreasing

the conducts of metal while in case of electrolytes, increased temperature increases the mobility of ions this increases the

conductance of ions.

Ans6. .A = strong Electrolyte B = weak Electrolyte

In case of B , it is not possible to get an exact value of limiting molar conductance .

Ans7. E0cell = E0cathode - E0anode

= 0.344 - (- 0.76) = 1.104V

∆G = -nFEcell = -2*96500*1.104 J = -213072 J

Ans8.Writing electrode reaction as reduction reaction,

H+ + e- → 1/2 H2
Applying Nernst equation
Ecell = E0cell – 0.0591/n log 1/[H+]
- 0.188 = 0 - 0.0591/1 pH
pH = 0.118 / 0.0591
= 2

Ans9. λ∞m(CH3COOH) = λ∞m(CH3COONa) + λ∞m(HCl) - λ∞m(NaCl)

= 91.0+425.9-126.4
= 390.5 Scm2mol-1

Ans10. (a) H+( aq) + e- → H2(g) will take place at cathode because it has higher
reduction potential.
(b) It is because ions are not involved in net cell reaction.

SHORT ANSWER TYPE QUESTION (3marks)

Ans1. There is sharp increase in the molar conductivity of a weak electrolyte on dilution because at
very low concentration, its degree of dissociation rise sharply due to increase number of ions
in the solution .
Relation between molar conductivity and degree of dissociation of a sparingly soluble salt,
α = ˄cm / ˄0m

Ans2. i) MnO4- + 5e- Mn2+

 Hence,5 moles of electrons are required for conversion of MnO 4- to Mn2+.

ii) Al3+ + 3e- Al(s)

since, 1 mole or 27 gm of Al is produced by 3 mole of e-
10 gm will produce 3*10/27
= 1.11 mole of e-

Ans3. Cell representation;

Zn(s)/ Zn2+(aq) || Ag+(aq)/Ag(s)
Cell reaction;
At anode, Zn(s) Zn2+ + 2 e-
At cathode, Ag+ + e- Ag(s)
The carriers of current within this cell are from silver to zinc

Ans4. A reaction feasible if emf of the cell reaction is positive.

(a) Fe3+ (aq) + I-(aq) Fe2+ (aq) + ½ I2
E cell =E Fe3+,Fe2+ - E01/2I2, I-
0 0

= 0.77 – 0.54 = 0.23 (feasible)

(b) Ag (s) + Fe3+ (aq) Ag+(aq) + Fe2+(aq)
0 0 0
E cell =E Fe3+,Fe2+ - E Ag+, Ag
=0.77 – 0.80 = - 0.03 V (Not feasible)

Ans5. For the reaction at equilibrium, Ecell = 0.

Therefore, Ecell= E0cell – (0.059/n)log Kc
E0cell = (0.059/n)logKc
0.36=(0.059/2)log Kc
logKc = 0.36*2/0.059 = 12.183
Kc = Antilog 12.183
= 1.52*1012
Ans6. λm = Κ*1000/C
= 7.896*10-5*1000/0.00241
= 32.76 Scm2mol-1
Now, α = λcm/ λ∞m
= 32.76/390.5 = 0.0839

Since, Κ = C α2/(1- α)
= 0.00241*(0.0839)2/(1-0.0839)
= 1.85*10-
Ans7.
Ans8.The cell reaction -
Cd + Ni2+ Cd2+ + Ni
0 0 0
E cell = E cathode - E anode
= - 0.25 – (- 0.40) = 0.15 V
Ecell = E0cell – 0.0591/n log [Cd2+]/[ Ni2+]

0.20 = 0.15 - 0.0591/2 log [Cd2+]/[2]

log [Cd2+] = - 1.690 + 0.3021 = 1.3879

[Cd2+] = antilog (- 1.3879) = 0.0409 M

Ans9 .EoCell = E0 cathode – E0 anode = -0.40 – (- 0.74) = + 0.34 V

∆rG0 = -n FEocell = - 6 * 96500 * 0.34 = -196860 CV mol-1

= -196.86 kJ mol-1
∆rG0 =-2.303 RT log Kc

- 196860 = - 2.303 * 8.314 *298 log Kc

log Kc = 34.5014
Kc = Antilog 34.5014 =3.192*1034

Ans10. (a)A salt bridge is a U-shaped tube containing concentrated solution of an inert
electrolyte like KCl, KNO3, K2SO4 etc.
The function of the salt bridge -
1. It allows the movement of ions from one solution to other without mixing of the
two solutions.
2 . Thus whereas electrons flow in the outer circuit in the wire the inner circuit is
completed by the flow of ions from one solution to the other through the salt
bridge.
3. It helps to maintain the electrical neutrality of the solution in the two half
cells.
(b) Negative value of E0cell means ∆rG will be positive, and the cell will not work.
LONG ANSWER TYPE QUESTION (5marks)
Ans1.(a)Conductance of one cm3(per unit volume)of solution of an electrolyte is called the conductivity. On dilution,
the number of ions per unit decreases. Hence, the conductivity decreases
Cell constant = Conductivity/Conductance
= Conductivity*Resistance
= 0.146*10-3*1500
= 0.219 cm-1

Ans2.

(i)Electrons move from Zn to Ag.

(ii) Ag is the cathode.
(iii) Cell will stop functioning.
(iv) When ECell= 0.
(v) Concentration of Zn+2 ions will increase and concentration of Ag+ ions will decrease.
(vi) When ECell= 0, equilibrium is reached and concentration of Zn+2 ions and Ag+ ions will not change.

Ans3.(a)The conductance of 1 mole solution of an electrolyte is known as molar conductance. It is denoted by Λm.

Λm= k*1000/c
The unit of molar conductivity is Ω-1cm2mol-1

(b)

Where M Concentration

Ans.4. The law states that molar conductivity of an electrolyte at infinite dilution (zero concentration)can be
represented as the sum of the individual contribution of the anion and cation of the electrolyte at infinite dilution
Ans5. (i) Cu (s) Cu2+ (aq) + 2e - ( At anode)

2 Ag+ (aq) + 2e - 2Ag(s) ( At cathode)

Cu is acting as anode and Ag is acting as anode.

(ii) Sn (s) Sn2+ (aq) + 2e -
+ -
2H (aq) + 2e (H2)(g)
…………………………………………………………………
Sn (s) + 2H+ (aq) Sn2+ (aq) + (H2) (g

Ecell = Eocell – 0.0591/n log [Sn2+] / [H+]2

= (E0H+ / H2 – E0Sn2+/ Sn) - 0.0591/n log [Sn2+] / [H+]2
= [0 – (- 0.14)] - 0.0591/n log 0.04 / (0.02)2
= 0.14 – 0.0591
= 0.0809 v