Unacademy Electrochemistry Mega XII
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Aaryan KeshanUnacademy Electrochemistry Mega XII
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Aaryan KeshanPHYSICAL CHEMISTRY
MEGA-XII
ELECTROCHEMISTRY
" A SPECIALLY DESIGNED KIT FOR LEARNING."
THE KEY Basic principles of subjects. An outline of the topics to be
discussed in class lectures.
THE ATLAS Basic layout of subject. A route map correlating different
subtopics in coherent manner.
SHORT NOTES Important Formula (Summary)
EXERCISE I Introductory problems based on JEE to get first hand
experience of problem solving.
EXERCISE II A collection of good problems.
QUESTION BANK Test your objective skill.
EXERCISE III A collection of previous ten years JEE problems.
PHYSICAL CHEMISTRY NA (SODIUM SIR)
KEY CONCEPTS
ELECTROCHEMICAL CELLS
An electrochemical cell consists of two electrodes (metallic conductors) in contact with an electrolyte (an
ionic conductor).
An electrode and its electrolyte comprise an Electrode Compartment.
Electrochemical Cells can be classified as :
(i) Electrolytic Cells in which a nonspontaneous reaction is driven by an external source of current.
(ii) Galvanic Cells which produce electricity as a result of a spontaneous cell reaction
Note : In a galvanic cell, cathode is positive with respect to anode.
In a electrolytic cell, anode is made positive with respect to cathode.
ELECTROLYSIS
The decomposition of electrolyte solution by passage of electric current, resulting into deposition of metals
or liberation of gases at electrodes is known as electrolysis.
ELECTROLYTIC CELL
This cell converts electrical energy into chemical energy.
The entire assembly except that of the external battery is
known as the electrolytic cell
ELECTRODES
The metal strip at which positive current enters is called anode; anode is positively charged in electrolytic
cell. On the other hand, the electrode at which current leaves is called cathode. Cathodes are negatively
charged.
Anode Positive Loss of electron Positive
or oxidation current
takes place enters
Cathode Negative Gain of electron Current
or reduction leaves
takes place
ELECTROLYSIS OF MOLTEN SODIUM CHLORIDE
NaCl(molten) Na+ + Cl–
Reactions at anode (oxidation) : cathode (reduction)
–
2Cl Cl2(g) + 2e – : 2Na+ + 2e– 2Na(l)
There are two types of electrodes used in the electroytic cell, namely attackable and non - attackable. The
attackable elecrodes participitate in the electrode reaction. They are made up of reactive metals like Zn, Cu,
Ag etc. In such electrodes, atom of the metal gets oxidised into the corresponding cation, which is passed
into the solution. Thus, such anodes get dissolved and their mass decreases. On the other hand, non-
attackable electrodes do not participiate in the electrode reaction as they made up of unreactive elements
like Pt, graphite etc. Such electrodes do not dissolve and their mass remain same.
FARADAY’S LAWS OF ELECTROLYSIS:
(i) First law of electrolysis :
Amount of substance deposited or liberated at an electrode is directly proportional to amount of charge
passed (utilized) through the solution.
wQ
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W = weight liberated, Q = charge in coulomb
w = ZQ
Z = electrochemical equivalent
when Q = 1 coulomb, then w = Z
Thus, weight deposited by 1 coulomb charge is called electrochemical equivalent.
Let 1 ampere current is passed till ‘t’ seconds .
Then, Q = It w = ZIt
1 Faraday = 96500 coulomb = Charge of one mole electrons
One faraday is the charge required to liberate or deposit one gm equivalent of a substance at
corresponding electrode.
Let ‘E’ is equivalent weight then ‘E’ gm will be liberated by 96500 coulomb.
E E
1 Coulomb will liberate 96500 gm ; By definition, Z 96500
ItE
W 96500
When a gas is evolved at an electrode, then above formula changes as,
ItV e
V
96500
where V = volume of liberated gas, Ve = equivalent volume of gas.
Equivalent volume may be defined as:
The volume of gas liberated by 96500 coulomb at STP.
CURRENT EFFICIENCY :
charge actually used in electrolysis process
Current efficiency = charge passed through battery
× 100
(ii) Second law of electrolysis :
When same amount of charge is passed through different electrolyte solutions connected in series then
weight of substances deposited or dissolved at anode or cathode are in ratio of their equivalent
weights. i.e. w1/w2 E1/E2
QUALITATIVE ASPECTS OF ELECTROLYSIS
In the electrolysis process we have discussed above, we have taken molten salt as electrolyte, which
contains only one cation and anion. Now, if the electrolyte taken contains more than one cation and anion
(for example, aqueous solution of the ionic electrolyte), then the cation and anion that will get discharged
depends on the ability of cation to get reduced and the ability of anion to get oxidised.
The ability of an ion to get oxidised or reduced depends upon the size, mass, positive charge, negative charge
etc. Thus, it is not possible to predict qualitatively that which ion would be discharged first, as one factor might
enhance the ability to discharge while the other factor may hamper it. This can only be predicted on the basis
of quantitative value assigned based on the cumulative effect of all the factors reponsible for an ion's ability to
discharge. The value is referred as standard potential, which is determined by keeping the concentration of ion
as 1 M, pressure of gas at 1 atm, and the measurement done at 25°C. For a cation, the standard reduction
potential (SRP) values are compared. The cation having higher standard reduction potential value is discharged
in preference to cation with lower SRP value provided the ions are at 1 M concentration. For an anion, the
standard oxidation potential (SOP) values are compared and anion having higher SOP is preferentially discharged,
if the concentration is 1 M for each of the ion. The SRP values at 25°C for some of the reduction half reactions
are given in the table below.
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S.NO. Reduction half cell reaction E° in volts at 25°C
1. F 2 + 2e– 2F – + 2.65
2. S 2O28 + 2e– 2SO 24 + 2.01
3. Co3+ + e– Co2+ + 1.82
4. PbO 2 + 4H+ + SO24 + 2e– PbSO 4 + 2H2O + 1.65
5. MnO 4 + 8H+ + 5e– Mn2+ + 4H2O + 1.52
6. Au3+ + 3e– Au + 1.50
7. Cl 2 + 2e– 2Cl – + 1.36
8. Cr2O27 + 14H+ + 6e– 2Cr3+ + 7H2O + 1.33
9. O 2 + 4H+ + 4e– 2H2O + 1.229
10. Br2 + 2e– 2Br– + 1.07
11. NO 3 + 4H+ +3e NO + 2H2O + 0.96
12. 2Hg2+ + 2e– Hg22 + 0.92
13. Cu2+ + I – + e– CuI + 0.86
14. Ag+ + e– Ag + 0.799
15. Hg22 + 2e– 2 Hg + 0.79
16. Fe3+ + e–
Fe2+ + 0.77
17. I 2 + 2e 2I –
– + 0.535
18. Cu+ + e– Cu + 0.53
19. Cu2+ + 2e– Cu + 0.34
20. Hg2Cl 2 + 2e– 2Hg + 2Cl – + 0.27
21. AgCl + e– Ag + Cl – + 0.222
22. Cu2+ + e– Cu+ + 0.15
23. Sn4+ + 2e– Sn2+ + 0.13
24. 2H+ + 2e– H2 0.00
25. Fe3+ + 3e– Fe – 0.036
26. Pb2+ + 2e– Pb – 0.126
27. Sn2+ + 2e– Sn – 0.14
28. AgI + e– Ag + I – – 0.151
29. Ni 2+ + 2e– Ni – 0.25
30. Co2+ + 2e– Co – 0.28
31. Cd2+ + 2e– Cd – 0.403
32. Cr3+ + e– Cr2+ – 0.41
33. Fe2+ + 2e– Fe – 0.44
34. Cr3+ + 3e– Cr – 0.74
35. Zn2+ + 2e– Zn – 0.762
36. 2H2O + 2e– H2 + 2OH– – 0.828
37. Mn2+ + 2e– Mn – 1.18
38. Al 3+ + 3e– Al – 1.66
39. H2 + 2e– 2H– – 2.25
40. Mg2+ + 2e– Mg – 2.37
41. Na+ + e– Na – 2.71
42. Ca2+ + e– Ca – 2.87
43. Ba2+ + 2e– Ba – 2.90
44. Cs+ + e– Cs – 2.92
45. K+ + e– – 2.93
46. Li + + e– Li – 3.03
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When solution of an electroyte contains more than one type of cations and anions at concentrations
different than 1 M, the discharge of an ion does not depend solely on standard potentials but also
depends on the concentration of ion in the solution. This value is refered as potential, called as reduction
potential for cation and oxidation potential for anion. The relation between reduction potential and
standard reduction potential is given by Nernst equation, as
RT [concentration of product ]
ERP = E° RP – ln
nF [concentration of reac tan t ]
where ERP = Reduction potential of cation and E° RP = Standard reduction potential of cation.
Thus, it is possible that a cation (A +) with lower standard reduction potential getting discharged in
preference to cation (B+) having higher standard reduction potential because their concentration might
be such that the reduction potential of A + is higher than that of B +.
When two metal ions in the solution have identical values of their reduction potentials, the simultaneous
deposition of both the metals will occur in the form of an alloy.
GALVANIC CELL
This cell converts chemical energy into electrical energy.
Galvanic cell is made up of two half cells i.e., anodic and cathodic. The cell reaction is of redox kind.
Oxidation takes place at anode and reduction at cathode. It is also known as voltaic cell. It may be
represented as shown in Fig. Zinc rod immersed in ZnSO4 behaves as anode and copper rod immersed in
CuSO4 behaves as cathode.
Oxidation takes place at anode:
Zn Zn2+ + 2e– (loss of electron : oxidation)
Reduction takes place at cathode:
Cu2+ + 2e– Cu (gain of electron ; reduction)
Over all process:
Zn(s) + Cu2+ Cu(s) + Zn2+
In galvanic cell like Daniell cell; electrons flow from anode (zinc rod) to the cathode (copper rod) through
external circuit; zinc dissolves as Zn2+ ; Cu2+ ion in the cathode cell picks up two electron and become
deposited at cathode.
SALT BRIDGE
Two electrolyte solutions in galvanic cells are seperated using salt bridge as represented in the Fig. salt
bridge is a device used to maintain electrical neutrality in both half cell. Saturated solution of salt like KCI,
KNO3, NH4Cl and NH4NO3 etc. in agar-agar gel is used in salt bridge. Salt bridge contains high concentration
of ions viz. K+ and NO3 at the junction with electrolyte solution. Thus, salt bridge carries whole of the current
across the boundary ; more over the K+and NO3 ions have same speed. Hence, salt bridge with uniform and
same mobility of cations and anions completes the electrical circuit & permits the ions to migrate.
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
Representation of a cell (IUPAC conventions ): Let us illustrate the convention taking the example of Daniel cell.
(i) Anodic half cell is written on left and cathodic half cell on right hand side.
Zn(s) | ZnSO4 (sol) || CuSO4 (sol) | Cu(s)
(ii) Two half cells are separated by double vertical lines: Double vertical lines indicate salt bridge or any type of
porous partition.
(iii) EMF (electromotive force) may be written on the right hand side of the cell.
(iv) Single vertical lines indicate the phase separation between electrode and electrolyte solution.
Zn | Zn2+ || Cu2+ | Cu
(v) Inert electrodes are reprsented in the bracket
Zn | ZnSO4 || H+ | H2, Pt
CONCEPT OF ELECTROMOTIVE FORCE (EMF) OF A CELL
Electron flows from anode to cathode in external circuit due to a pushing effect called or electromotic force
(e.m.f.). E.m.f. is some times called as cell potential. Unit of e.m.f. of cell is volt.
EMF of cell may be calculated as :
Ecell = reduction potential of cathode Reduction potential of anode
Similarly, standard e.m.f. of the cell (E°) may be calculated as
E°cell = Standard reduction potential of cathode Standard reduction potential of anode
SIGN CONVENTION OF EMF
EMF of cell should be positive other wise it will not be feasible in the given direction .
Zn | ZnSO4 || CuSO4 | Cu E = +1.10 volt (Feasible)
Cu | CuSO4 || ZnSO4 | ZnE = 1.10 volt (Not Feasible)
NERNST EQUATION
Walter Nernst derived a relation between cell potential and concentration or Reaction quotient.
G = G° + RT ln Q ..(1)
where G and G° are free energy and standard free energy change; ‘Q’ is reaction quotient.
Let n, Faraday charge is taken out from a cell of e.m.f. (E) then electrical work done by the cell
may be calculated as,
Work done = Charge x Potential = nFE
From thermodynamics we know that decrease in Gibbs free energy of a system is a measure of
reversible or maximum obtainable work by the system if there is no work due to volume expansion
G = nFE and G° = nFE°
Thus from Eq. (i),we get nFE = -nFE° + RT lnQ
0.0591
At 25°C, above equation may be written as E Eo – log Q
n
Where ‘n’ represents number of moles of electrons involved in process.
E, E° are e.m.f. and standard e.m.f. of the cell respectively.
In general , for a redox cell reaction involving the transference of n electrons
aA + bB cC + dD, the EMF can be calculated as:
0.0591 [C]c [D] d
ECell = E°Cell – log
n [ A] a [B]b
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Prediction and feasibility of spontaniety of a cell reaction.
Work done by the cell = nFE;
It is equivalent to decrease in free energy G = –nFE
Under standard state G0 = –nFE0 (i)
(i) From thermodynamics we know, G = negative for spontaneous process. Thus from eq.(i) it is
clear that the EMF should be +ve for a cell process to be feasible or spontaneous.
(ii) When G = positive, E = negative and the cell process will be non spontaneous.
(iii) When G = 0 , E = 0 and the cell will attain the equilibrium.
Reactions G E
Spontaneous (–) (+)
Non- spontaneous (+) (–)
Equilibrium 0 0
Standard free energy change of a cell may be calculated by electrode potential data.
Substituting the value of E0 (i.e., standard reduction potentialof cathode- standard reduction potential of
anode) in eq. (i) we may get G0.
Let us see whether the cell (Daniell) is feasible or not: i.e. whether Zinc will displace copper or not.
Zn | (s) | ZnSO4 (sol) || CuSO4 (sol) | Cu(s)
E0 0.76volt ; E 0 0 .34volt
Zn 2 / Zn Cu 2 / Cu
E 0 cell E 0 E0
Cu 2 / Cu zn 2 / Zn
= 0.34 –(–0.76) = +1.10 volt
Since E0 = +ve , hence the cell will be feasible and zinc will displace copper from its salt solution. In the other
words zinc will reduce copper.
THERMODYNAMIC TREATMENT OF NERNST EQUATION
Determination of equilibrium constant : We know, that
0.0591
E Eo – log Q ..(i)
n
At equilibrium, the cell potential is zero because cell reactions are balanced, i.e. E = 0
From Eq. (i), we have
0.0591 nE 0
0
0 E logK eq or K eq anti log
n 0.0591
Heat of Reaction inside the cell: Let n Faraday charge flows out of a cell of e.m.f. E, then
G = nFE (i)
Gibbs Helmholtz equation (from thermodynamics ) may be given as,
G
G = H + T T (ii)
p
From Eqs. (i) and (ii), we have
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nFE E
nFEHT HnFT T
T p p
E
H nFEnFT
T p
Entropy change inside the cell : We know that G = H - TS or G = H TS ...(i)
where G = Free energy change ; H = Enthalpy change and S = entropy change.
According to Gibbs Helmoholtz equation,
G
GH T ....(ii)
T p
From Eqs. (i) and (ii), we have
G G E
TST or S or SnF
T p T p T p
E
where T is called temperature coefficient of cell e.m.f.
p
DIFFERENT TYPES OF HALF-CELLS AND THEIR REDUCTION POTENTIAL
(1) Gas-Ion Half Cell :
In such a half cell, an inert collector of electrons, platinum or graphite is in contact with gas and a solution
containing a specified ion. One of the most important gas-ion half cell is the hydrogen-gas-hydrogen ion half
cell. In this half cell, purified H2 gas at a constant pressure is passed over a platinum electrode which is in
contact with an acid solution.
H+(aq) + e– 1/2 H2 (g)
0.0591 (pH2 )1/ 2
EH | H EHo | H – log
2 2 1 H
(2) Metal-Metal Ion Half Cell:
This type of cell consist of a metal M in contact with a solution containing Mn+ ions.
Mn+(aq) + ne– M(s)
o 0.0591 1
E Mn | M EM n
|M
– log n
n M
(3) Metal-Insoluble Salt - Anion Half Cell:
In this half cell, a metal coated with its insoluble salt is in contact with a solution containing the anion of the
insoluble salt. eg. Silver-Silver Chloride Half Cell:
This half cell is represented as Cl–/AgCl/Ag. The equilibrium reaction that occurs at the electrode is
AgCl(s) + e– Ag(s) + Cl–(aq)
0.0591
E Cl– | AgCl | Ag E oCl– | AgCl | Ag – log [Cl – ]
1
potential of such cells depends upon the concentration of anions. Such cells can be used as Reference Electrode.
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(4) Oxidation-reduction Half Cell:
This type of half cell is made by using an inert metal collector, usually platinum, immersed in a solution
which contains two ions of the same element in different states of oxidation. eg. Fe2+ - Fe3+ half cell.
Fe3+(aq) + e– Fe2+(aq)
o 0.0591 Fe2
EFe3 | Fe2 EFe 3
| Fe 2
– log 3
1 Fe
CONCENTRATION CELL
The cells in which electrical current is produced due to transport of a substance from higher to lower
concentration. Concentration gradient may arise either in electrode material or in electrolyte. Thus there are
two types of concentration cell .
(i) Electrode concentration cell
(ii) Electrolyte concentration cell
Electrode Gas concentration cell :
Pt, H2(P1) | H+(C) | H2(P2), Pt
Here, hydrogen gas is bubbled at two different partial pressures at electrode dipped in the solution of same
electrolyte.
Cell process : 1/ 2H2 (p1)H ( c )e (Anode process)
H (c )e 1/ 2H2 (p 2 )
1/ 2H2 (p1) 1/ 2H2 (p 2 )
1/ 2
2.303RT p 2
E log
F p1
2.303RT p 2 0.059 p
or E log p , At 250C , E log 1
2F 1 2F p2
For spontanity of such cell reaction, p1 > p2
Electrolyte concentration cells:
Zn(s) | ZnSO4 (C1) || ZnSO4 (C2) | Zn(s)
In such cells, concentration gradient arise in electrolyte solutions. Cell process may be given as,
ZnsZn2 C1 2e (Anodic process)
Zn2 (C 2 ) 2e Zn(s)
(Over all process)
Zn2 (C 2 ) Zn2 (C1 )
From Nernst equation, we have
2.303RT C1 2.303RT C 2
E0 log or E log
2F C2 2F C1
For spontanity of such cell reaction, C2> C1
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TYPES OF BATTERIES
1. Primary Batteries 2. Secondary Batteries
PRIMARY BATTERIES :
DRY CELLS AND ALKALINE BATTERIES
Zinc serves as the anode, and the cathode is a graphite rod placed
down the center of the device. These cells are often called "dry
cells" because there is no visible liquid phase. However, water is Anode (–)
(zinc inner case)
present, so the cell contains a moist paste of NH4Cl, ZnCl2 and
MnO2. The moisture is necessary because the ions present must Cathode (+)
be in a medium in which they can migrate from one electrode to (graphite rod)
the other. The cell generates a potential of 1.5 V using
Paste of MnO2,
the following half-reactions
NH4Cl and
Anode, (Oxidation) : Zn (s) Zn2+(aq) + 2 e– carbon
Cathode, (reduction) : MnO2 + NH4+ + e– MnO(OH) + NH3
LeClanche cells were widely used because of their low cost, but they have several disadvantages. If current
is drawn from the battery rapidly, the gaseous products cannot be consumed rapidly enough, so the cell
resistance rises, and the voltage drops. In addition, the zinc electrode and ammonium ions are in contact in
the cell, and these chemicals react slowly. Recall that zinc reacts with acid to form hydrogen. The ammonium
ion, NH4+(aq), is a weak Bronsted acid and reacts slowly with zinc. Because of this reaction, these voltaic
cells cannot be stored definitely. When the zinc outer shell deteriorates, the battery can leak acid and
perhas damage the appliance in which it is contained.
At the present time alkaline batteries are used, the chemistry of alkaline cells is quite similar to that in a
Leclanche cell, except that the material inside the cell is basic (alkaline). Alkaline cells use the oxidation of
zinc and the reduction of MnO2 to generate a current, but NaOH or KOH is used in the cell instead of the
acidic salt NH4Cl.
Cathode, (reduction) : 2MnO2(s) + H2O() + 2e– Mn2O3(s) + 2OH–(aq)
Anode, (Oxidation) : Zn(s) + 2OH–(aq) ZnO(s) + H2O() + 2 e–
Alkaline cells, which produce 1.54V (approximately the same voltage as the Leclanche cell), have the further
advantage that the cell potential does not decline under high current loads because no gases are formed.
Mercury Cell
Mercury cell, suitable for low current devices like hearing aids, watches, etc. consists of zinc-mercury
amalgam as anode and a paste of HgO and carbon as the cathode. The electrolyte is a paste of KOH and
ZnO. The electrode reactions for the cell are given below :
Anode : Zn(Hg) + 2OH– ZnO(s) + H2O + 2e–
Cathode : HgO + H2O + 2e– Hg() + 2OH–
The overall reaction is represented by
Zn(Hg) + HgO(s) ZnO(s) + Hg()
The cell potential is approximately 1.35 V and remains constant during its life as the overall reaction does
not involve any ion in solution whose concentration can change during its life time.
SECONDARY OR RECHARGEABLE BATTERIES
The lead storage battery is probably the best known – 'car battey' +
rechargeable battery in figure. The 12 V version of this Pb
cathode
battery contains six voltaic cells, each generating about H2SO4(aq) plates
with
2V. The lead storage battery can produce a large initial PbO2
Pb
current, an essential feature when anode
plates
starting an automobile engine.
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
When the cell supplied electrical energy, the lead anode is oxidixed to lead (II) sulfate, an insoluble substance
that adheres to the electrode surface. The two electrons produced per lead atom move through the external
circuit to the cathode, where PbO2 is reduced to Pb2+ ions that, in the presence of H2SO4, also form lead (II)
sulfate.
Anode, (oxidation) : Pb(s) + SO42–(aq) PbSO4(s) + 2e–
Cathode, (reduction) : PbO2 (s) + 4H+(aq) + SO42– (aq) + 2e– PbSO4(s) + 2 H2O()
--------------------------------------------------------------------------------------------
Overall cell reaction : Pb(s) + PbO2(s) + 2H2SO4(aq) 2PbSO4(s) + 2H2O()
B + –A
+ – + – + –
2 2 2 2 2 2
A B
– – – VB–VA=12 volts
+ + +
A The battery consists of
six two-volt cells connected
in series.
B Each component cell is
composed of several
negative and positive
electrodes made of pure
PbO2
spongy lead and lead oxide,
respectively; the electrodes,
connected in parallel, are
Pb (spongy) immersed in a dilute solution
plates in a solution of sulfuric acid.
of H2SO4 and H2O
Nickel - Cadmium ("Ni - Cad") batteries, used in variety of cordless appliances such as telephones, video
camcorders, and cordless power tools, are lightweight and rechargeable. The chemistry of the cell utilizes
the oxidation of cadmium and the reduction of nickel (III) oxide under basic conditions. As with the lead
storage battery, the reactants and products formed when producing a current are solids that adhere to the
electrodes.
Anode, Oxidation : Cd(s) + 2 OH– Cd(OH)2(s) + 2e–
Cathode, reduction : NiO(OH) (s) + H2O() + e– Ni(OH)2(s) + OH–(aq)
FUEL CELLS
An advantage of voltaic cells is that they are small and portable, but their size is also a limitation. The
amount of electric current produced is limited by the quantity of reagents contained in the cell. When one of
the reactants is completely consumed, the cell will no longer generate a current. Fuel cells avoid this
limitation because the reactants (fuel and oxidant) can be supplied continuously to the cell from an external
reservoir.
In a Hydrogen - Oxygen fuel cell, hydrogen is pumped onto the anode of the cell, and O2 (or air) is directed
to the cathode where the following reactions occur :
Cathode, (reduction) : O2(g) + 2 H2O() + 4e– 4OH–(aq) E° = 1.23 V
Anode, (Oxidation) : +
H2(g) 2H (aq) + 2 e – E° = 0 V
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
porous porous
anode e cathode
external circuit
H2 fuel + O2
H
electrolyte
NaOH (aq) H2O, excess air
+ – + –
2 H2 4H + 4e 4 H + O2 + 4e 2 H2O
CORROSION CELLS AND REACTIONS
Corrosion can be defined as the deterioration of materials by chemical processes. Of these, the most
important by far is electrochemical corrosion of metals, in which the oxidation process M M+ + e– is
facilitated by the presence of a suitable electron acceptor, sometimes referred to in corrosion science as a
depolarizer.
In a sense, corrosion can be viewed as the spontaneous return of metals to their ores; the huge quantities of
energy that were consumed in mining, refining, and manufacturing metals into useful objects is dissipated by
a variety of different routes.
The special characteristic of most corrosion processes is that the oxidation and reduction steps occur at
separate locations on the metal. This is possible because metals are conductive, so the electrons can flow
through the metal from the anodic to the cathodic regions. The presence of water is necessary in order to
transport ions to and from the metal, buty a thin film of adsorbed moisture can be sufficient. A corrosion
system can be regarded as a short-circuited electrochemical cell in which the anodic process is something
like
Fe(s) Fe2+ (aq) + 2 e–
and the cathodic steps can be any of
O2 + 2H2O + 4e– 4 OH–
H+ + e– 1/2 H2(g)
M2+ + 2 e– M(s)
where M is a metal. Which parts of the metal serve as anodes and cathodes can depend on many factors,
as can be seen from the irregular corrosion patterns that are commonly observed.
CONTROL OF CORROSION
Since both the cathodic and anodic steps must take place for corrosion to occur, prevention of either one will
stop corrosion. The most obvious strategy is to stop both processes by coating the object with a paint or
other protective coating. Even if this is done, there are likely to be places where the coating is broken or does
not penetrate, particularly if there are holes or screw threads.
A more sophisticated approach is to apply a slight negative charge to the metal, thus making it more difficult
for the reaction M M2+ + 2e– to take place.
SACRIFICIAL COATINGS
One way of supplying this negative charge is to apply a coating of a more active metal. Thus a very common
way of protecting steel from corrosion is to coat it with a thin layer of zinc; this process is known as
galvanizing. The zinc coating, being less noble than iron, tends to corrode selectively. Dissolution of this
sacrificial coating leaves behind electrons which concentrate in the iron, making it cathodic and thus inhibiting
its dissolution.
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
Zn
2+ O2
2+
Fe
zinc zinc tin
–
e
iron iron
Sacrifical coating Noble coating
The effect of plating iron with a less active metal provides an interesting contrast. The common tin-plated can
(on the right) is a good example. As long as the tin coating remains intact, all is well, but exposure of even
a tiny part of the underlying iron to the moist atmosphere initiates corrosion. The electrons released from the
iron flow into the tin, making the iron more anodic so now the tin is actively promoting corrosion of the iron!
You have probably observed how tin cans disintegrate very rapidly when left outdoors.
CATHODIC PROTECTION
A more sophisticated strategy is to maintain a continual negative electrical charge on a metal, so that its
dissolution as positive ions is inhibited. Since the entire surface is forced into the cathodic condition, this
method is known as cathodic protection. The source of electrons can be an external direct current power
supply (commonly used to protect oil pipelines and other buried structures), or it can be the corrosion of
another, more active metal such as a piece of zinc or aluminum buried in the ground nearby.
CONDUCTANCE
Conductors
Metallic Conductors Electrolytic Conductors
1. Charge carries by e¯ 1. Charge carries by ions
2. No chemical changes 2. Decomposition of electrolyte takes place.
3. No transfer of mass 3. Transfer of mass takes place
4. Resistance is because of 4. Resistance is because of collision
collision of electrons with fixed of ions with solvent molecules & because
metal atoms. of interionic force of attraction
5. Conductance decreases with increase 5. Conductance increases with increase
in temp in temp
Factors Affecting Electrolytic Conductance :
1. Solute – Solute interactions (Inter – lonic force of attraction)
2. Solute – Solvent lnteraction (Hydration / Solvation of lons)
3. Solvent solvent interaction (Viscosity)
4. Temperature
All three factors decreases with increase in temperature so electrolytic conductance increases
Both metallic and electrolytic conductors obey Ohm's law
i.e. V = IR
where V = Potential difference in volt; I = Current in ampere ; R = resistance in Ohm
We know, resistance is directly proportional to length of conductor and inversely proportional to cross sectional
area of the conductor.
l l
R or R ( = Specific resistance )
A A
Specific resistance is the resistance of a conductor having lengths of 1 cm and corss sectional area of 1 cm2.
Unit of R is ohm and unit of specific resistance is ohm cm
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
Reciprocal of resistance is called as conductance and reciprocal of specific resistance is called as specific
conductance.
1 1A A
or C
R l l
where C = conductance ohm1 ; = specific conductance ohm1cm1 .
Mho and siemens are other units of conductance
l
C
A
Specific conductance = Cell constant × Conductance
SPECIFIC CONDUCTANCE IS CONDUCTANCE OF 1 CM3 OF AN ELECTROLYTE SOLUTION.
In case of electrolytic solution, the specific conductance is defined as the conductance of a solution of
definite concentration enclosed in a cell having two electrodes sof unit area separated by 1 cm apart.
1. Equivalent Conductance
Equivalent conductance is the conductance of an electrolyte solution containing 1 gm equivalent of electrolyte.
It is denoted by .
=× V
( = ohm1 cm1 × cm3 = ohm1 cm2)
Usually concen ration of electrolyte solution is expressed as C gm equivalent per litre.
1000
Thus, V
C
1000
{Volume having 1 gm equivalent electrolyte in the solution} Thus,
C
2. Molar Conductance
Molar conductance may be defined as conductance of an electrolyte solution having 1 gm mole
electrolyte in a litre. It is denoted by m .
m=×V
Usually concentration of electrolyte solution is expressed as ‘M’ gm mole elecrtrolyte per litre.
1000 1000
Thus, V . Hence, m
M M
Relation between and m : m= n ×
0
DETERMINATION OF 0m OR
A plot of m vs C as found experimentally is as shown below graphically..
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
The m vs C plot of strong electrolyte being linear it can be extrapolated to zero concentration. Thus,
m values of the solution of the test electrolyte are determined at various concentrations the concentrations
should be as low as good.
m values are then plotted against C when a straight line is obtained. This is the extrapolated to zero
concentration. The point where the straight line intersects m axis is 0m of the strong electrolyte.
However, the plot in the case weak electrolyte being non linear, shooting up suddenly at some low concentration
and assuming the shape of a straight line parallel to m axis. Hence extrapolation in this case is not
possible. Thus, 0 of a weak electrolyte cannot be determined experimentally. It can, however, be done with
the help of Kohlrausch's law to be discussed later.
Kohlrausch's Law of Independent Migration of Ions
Kohlrausch determined 0 values of pairs of some strong electrolytes containing same cation say KF and
KCl, NaF and NaCl etc., and found that the difference in 0 values in each case remains the same:
0 0 0 0
m (KCl) – m (KF) = m (NaCl) – m (NaF)
He also detemined 0 values of pairs of strong electrolytes containing same anion say KF and NaF, KCl and
NaCl etc.and found that the difference in 0 values in each case remains the same.
0 0 0 0
m (KF) – m (NaF) = m (KCl) – m (NaCl)
This experimental data led him to formulate the following law called Kohlrausch's law of independent migration
of ions.
At infinite dilution when dissociation is complete, every ion makes some definite contribution towards molar
conductance of the electrolyte irrespective of the nature of the other ion which with 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. Thus,
0
m = 0 0
Where 0 is the contribution of the cation and 0 is the contribution of the anion towards the molar conductance
at infinite dilution. These contributions are called molar ionic conductances at infinite dilution. Thus, 0 is the
molar ionic conductance of cation and 0 is the molar ionic conductnace of anion, at infinite dilution. The
above equation is, however, correct only for binary electrolyte like NaCl, MgSO4 etc.
Application of Kohlrausch's law :
0
(1) Determination of m of a weak electrolyte:
0 0
In order to calculate m of a weak electrolyte say CH3COOH, we determine experimentally m values of the
following three strong electrolytes:
(a) A strong electrolyte containing same cation as in the test electrolyte, say HCl
(b) A strong electrolyte containing same anion as in the test electrolyte, say CH3COONa
(c) A strong electrolyte containing same anion of (a) and cation of (b) i.e. NaCl.
0
m of CH3COOH is then given as:
0 0 0 0
m (CH3COOH) = m (HCl) + m (CH3COONa) – m (NaCl)
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
Proof:
0m(HCl) = 0H .....(i)
Cl
0m( CH = 0 .....(ii)
3 COONa) CH3 COO Na
0m(NaCl) = Na Cl
0 0
.....(iii)
Adding equation (i) and equation (ii) and subtracting (iii) from them :
0 0 0
0m(HCl) + m(CH3COONa ) – m(NaCl ) 0 0m(CH
(H ) ( CH3COO – ) 3 COOH)
(2) Determination of degree of dissociation () :
No. of molecules ionised m
= total number of molecules dissolved 0
m
(3) Determination of solubility of sparingly soluble salt
The specific conductivity of a saturated solution of the test electrolyte (sparingly soluble) made in conductivity
water is determined by the method as described above. From this the specific conductivity of conductivity
0
water is deducted. The molar conductance of the saturated solution is taken to be equal to m as the
saturated solution of a sparingly soluble salt is extremely dilute. Hence from equation (4).
0 1000
m = ,
C
where C is the molarity of solution and hence the solubility.
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
SUMMARY
(A) ELECTROLYTIC CELL
1. Electrode Product
ELECTROLYTE ANODE Product CATHODE Product
1. NaCl (Molten) with Pt electrode Cl2(g) Na()
2. NaCl (aq) with Pt electrode Cl2(g) H2(g)
3. Na2SO4 (aq) with Pt electrode O2(g) H2(g)
4. NaNO3 (aq) with Pt electrode O2(g) H2(g)
5. AgNO3 (aq) with Pt electrode O2(g) Ag
6. CuSO4 (aq) with Inert electrode O2(g) Cu
7. CuSO4(aq) with Copper electrode Cu dissolve Cu
2. Quantitative aspect of electrolysis
At mass W1 E1
(i) W = Zit (ii) Z (iii)
nF W2 E 2
actual ch arg e
(iv) Current efficiency = 100
Ch arg e passed through battery
(B) GALVANIC CELL
Zn(s) | Zn 2 (aq) || Cu 2 (aq) | Cu(s)
(–) ()
Anode Cathode
E ocell E oOP ERP
o
Ecell = EOP + ERP
1. Nernst's equation
0.0591
Ecell Eocell – log Q
n
0.0591 [ Zn2 ]
E cell E ocell – log
2 [Cu 2 ]
2. Cell Thermodynamics
(i) G = –nF Ecell
o
(ii) Gº = –nF Ecell
n Eocell
(iii) Equilibrium constant : K log K =
0.0591
E
(iv) Temp. cofficent of cell =
T P
E
(v) Heat of reaction inside the cell H = nFE + nFT
T P
E
(vi) Entropy change inside the cell S = nF
T P
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
3. Different Type of Electrode
NAME OF ELECTRODE ANODE CATHODE
1. Hydrogen electrode Pt, H2(g) | H+(aq) H+(aq) | H2(g), Pt
0.0591 [H ] 2 0.0591 PH
E OP E oOP – log o
ERP ERP – log 2 2
2 PH2 2 [H ]
2. Metal-metal ion electrode M(s) | M+n (aq) M+n(aq) | M(s)
0.0591 o 0.0591 1
E OP E oOP – log[Mn ] ERP ERP – log n
n n [M ]
3. Calomel electrode Hg, Hg2Cl2 | Cl– (aq) Cl– (aq) | Hg2Cl2, Hg
0.0591 1 0.0591
E OP E oOP – log o
ERP ERP – log [Cl – ] 2
2 [Cl – ] 2 2
4. Redox electrode Pt | Fe+2 (aq), Fe+3(aq) Fe+3 (aq), Fe+2 (aq) | Fe(s)
0.0591 [Fe 3 ] 0.0591 [Fe 2 ]
E OP E oOP – log ERP EoRP – log
1 [Fe 2 ] 1 [Fe 3 ]
5. Metal insoluble salt anion electrode Ag | AgCl | Cl–(aq) Cl–(aq) | AgCl | Ag
0.0591 1 0.0591
E OP E oOP – log o
ERP ERP – log [Cl – ]
1 [Cl – ] 1
4. Conc. Cell
(i) Electrode gas conc. cell : Pt, H2 (g) | H (C) | H2 (g), Pt
P1 P2
0.0591 P
E cell log 1
2 P2
(ii) Electrolyte conc. cell : Zn(s) | ZnSO4 (C1) || ZnSO4(C2) | Zn(s)
0.0591 C
E cell log 2
2 C1
(C) CONDUCTANCE
1 1
(1) V = iR (2) R · (3) G (4) K
A R
1000K 1000K
(5) K = G (6) (7) N (8) M
A N M
(9) oM (NaCl) oNa oCl – (10) oM (CH3COOH) oM (HCl) oM (CH3COONa) – oM (NaCl)
m 1000K
(11) (12) Solubility S
om om
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
THE ATLAS
Electrochemistry
1. Conductance of solutions
2. Equivalent and molar
conductivity & relationship
between them
relates Electrolytic 3. Variation of molar
Conductance conduvtivity with
concentration
4. Kohlrausch's law &
it's application
Chemical energy Electrical energy
Batteries
used in 1. Set up of cell
interconverted in
2. Types of electrodes
Galvanic cells
(Voltaic cells) Electroytic cells 3. Faraday's laws of
electrolysis
reaction are reaction are
4. Qualitative aspects
used in of electrolysis
Spontaneous Nonspontaneous
1.(a) Set up of cell oxidation-reduction oxidation-reduction
(b) Cell Notations Electrore fining
(c) Cell potential & producing requiring and
Nearest equation electroplating
(d) Relationship between
standard free energy & G = – G = (+)
equlibrium constant E=+ Electric current E = (–)
2. Types of half cells / electrodes
3. Concentration cells
(a) Electrode concentrations cells
(b) Electrolyte concentration cells oxidation half-reaction reducing half-reaction
occurring at the occurring at the
4.Types of batteries
Anode Cathode
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
EXERCISE-I
GALVANIC CELL :
Representation of Cell diagrams, complete and half cell reactions :
1. Make complete cell diagrams of the following cell reactions :
(a) Cd2+ (aq) + Zn (s) Zn2+ (aq) + Cd (s)
(b) 2Ag+ (aq) + H2 (g) 2H+ (aq) + 2Ag (s)
(c) Hg2Cl2 (s) + Cu (s) Cu2+ (aq) + 2Cl– (aq) + 2Hg (l)
(d) Cr2O27 (aq.) + 14H+ (aq) + 6Fe2+ (aq) 6Fe3+ (aq) + 2Cr3+ (aq) + 7H2O (l)
2. Write cell reaction of the following cells :
(a) Ag | Ag+ (aq) || Cu2+ (aq) | Cu
(b) Pt | Fe2+ , Fe3+ || MnO 4 , Mn2+, H+ | Pt
(c) Pt,Cl2 | Cl– (aq) || Ag+ (aq) | Ag
(d) Pt, H2 | H+ (aq) || Cd2+ (aq) | Cd
3. Write half cells of each cell with following cell reactions :
(a) Zn (s) + 2H+ (aq) Zn2+ (aq) + H2 (g)
(b) 2Fe3+ (aq) + Sn2+ (aq) 2Fe2+ (aq) + Sn4+ (aq)
(c) MnO 4 (aq) + 8H+ (aq) + 5Fe2+ (aq) 2Fe3+ (aq) + Mn2+ (aq) + 4H2O (l)
(d) Pb (s) + Br2 (l) Pb2+ (aq) + 2Br– (aq)
Electrode potential and standard electrode potential :
4. For the cell reaction 2Ce4+ + Co 2Ce3+ + Co2+
Eocell is 1.89 V. If E o 2 is – 0.28 V, what is the value of E o ?
Co | Co Ce 4 | Ce3
5. Determine the standard reduction potential for the half reaction :
Cl2 + 2e– 2Cl–
Given Pt2+ + 2Cl– Pt + Cl2, E oCell = – 0.15 V
Pt2+ + 2e– Pt E° = 1.20 V
o
6. What is E Cell if
2Cr + 3H2O + 3OCl– 2Cr3+ + 3Cl– + 6OH–
Cr3+ + 3e– Cr, E° = – 0.74 V
OCl– + H2O + 2e– Cl– + 2OH–, E° = 0.94 V
G°, EoCell and Keq :
7. Is 1.0 M H+ solution under H2SO4 at 1.0 atm capable of oxidising silver metal in the presence of 1.0 M Ag+ ion?
Eo = 0.80 V, E o = 0.0 V
Ag |Ag H |H2 (Pt )
8. If for the half cell reactions Cu2+ + e– Cu+ E° = 0.15 V
Cu2+ + 2e– Cu E° = 0.34 V
Calculate E° of the half cell reaction
Cu+ + e– Cu
also predict whether Cu+ undergoes disproportionation or not.
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
9. If Eo = – 0.44 V, Eo = 0.77 V. Calculate Eo .
Fe2 | Fe Fe3 | Fe2 Fe3 | Fe
10. Calculate the equilibrium constant for the reaction
Fe2+ +Ce4+ Fe3+ + Ce3+ , [given : E 0 Ce4 / Ce3 1.44 V;E0 Fe3 / Fe2 0.68 V ]
11. Calculate the EMF of a Daniel cell when the concentration of ZnSO4 and CuSO4 are 0.001 M and 0.1M
respectively. The standard potential of the cell is 1.1V.
12. Calculate the equilibrium constant for the reaction Fe + CuSO4 FeSO4 + Cu at 25°C.
Given E0 (Fe/Fe2+) = 0.44V, E0 (Cu/Cu2+) = 0.337V.
13. For a cell Mg(s) | Mg2+(aq) || Ag+ (aq) | Ag, Calculate the equilibrium constant at 25°C. Also find the maximum
work that can be obtained by operating the cell.
E0 (Mg2+/Mg) = 2.37V, E0 (Ag+/Ag) = 0.8 V.
14. The standard reduction potential at 25°C for the reduction of water
2H2O + 2e H2 + 2OH is 0.8277 volt. Calculate the equilibrium constant for the reaction
2H2O H3O+ + OH at 25°C.
15. At 250C the value of K for the equilibrium Fe3+ + Ag Fe2+ + Ag+ is 0.531mol/litre. The standard electrode
potential for Ag+ + e– Ag is 0.799V. What is the standard potential for Fe3+ + e– Fe2+ ?
16. The EMF of the cell M | Mn+ (0.02M) || H+ (1M) | H2(g) (1 atm), Pt at 25°C is 0.81V. Calculate the valency of
the metal if the standard oxidation of the metal is 0.76V. (log 2 = 0.3)
17. Equinormal Solutions of two weak acids, HA (pKa = 3) and HB (pKa = 5) are each placed in contact with
equal pressure of hydrogen electrode at 25°C. When a cell is constructed by interconnecting them through
a salt bridge, find the emf of the cell.
18. In two vessels each containing 500ml water, 0.5m mol of aniline (Kb= 109) and 25mmol of HCl are added
separately. Two hydrogen electrodes are constructed using these solutions. Calculate the emf of cell made
by connecting them appropriately.
19. Calculate E 0 and E for the cell Sn | Sn 2+ (1M) || Pb 2+ (10 3M) | Pb, E 0 (Sn 2+| Sn) = 0.14V,
E0 (Pb2+| Pb) = 0.13V. Is cell representation is correct?
20. At what concentration of Cu2+ in a solution of CuSO4 will the electrode potential be zero at 25°C?
Given : E0 (Cu | Cu2+) = 0.34 V.
21. A zinc electrode is placed in a 0.1M solution at 25°C. Assuming that the salt is 20% dissociated at this
dilutions calculate the electrode potential. E0 (Zn2+| Zn) = 0.76V. (log 2 = 0.3, log 5 = 0.7)
22. From the standard potentials shown in the following diagram, calculate the potentials E1º and E 2º .
º
23. For the reaction, 4Al(s) + 3O2(g) + 6H2O () + 4OH– (aq) 4 [Al(OH)4–(aq)] ; Ecell = 2.73 V..
If Gf (OH ) = –157 kJ mol–1 and Gºf (H2 O) = –237.2 kJ mol–1, determine Gºf [Al (OH)4–].
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
Concentration cells :
24. Calculate the EMF of the following cell Zn | Zn2+ (0.01M) || Zn2+ (0.1 M) | Zn at 298 K.
25. Calculate the EMF of the cell, Zn – Hg(c1M) | Zn2+ (aq)| Hg – Zn(c2M) at 25°C, if the concentrations of the zinc
amalgam are: c1 = 10g per 100g of mercury and c2 = 1g per 100 g of mercury.
26. Calculate pH using the following cell :
Pt (H2) | H+ (x M) | | H+ (1 M) | Pt (H2) if Ecell = 0.2364 V.
1 atm 1 atm
27. Calculate the EMF of following cells at 25°C.
Pt, H2 (2atm) | HCl |H2 (10 atm), Pt.
28. EMF of the cell Zn | ZnSO4 (a1= 0.2) || ZnSO4(a2) | Zn is 0.00885 V at 25°C. Calculate the value of a2.
2.303RT
(log 2 = 0.3, 0.059 )
F
29. Consider the cell Ag|AgBr(s)|Br (aq)||Cl– (aq)|AgCl(s)|Ag at 25º C. The solubility product constants of AgBr
& AgCl are respectively 5 × 1013 & 1 × 1010 . For what ratio of the concentrations of Br & Cl ions would
the emf of the cell be zero ?
30. For the galvanic cell : Ag|AgCl(s)| KCl (0.2M) || KBr (0.001 M)| AgBr(s) | Ag,
Calculate the EMF generated and assign correct polarity to each electrode for a spontaneous process after
taking into account the cell reaction at 250C.
2.303RT
[K sp( AgCl) 2.4 10 10 ; K sp( AgBr ) 3.2 1013 ] Given 0.06,log2 0.3, log3 0.48, log5 0.7
f
ELECTROLYTIC CELL :
31. Calculate the no. of electrons lost or gained during electrolysis of
(a) 3.55 gm of Cl– ions (b) 1 gm Cu2+ ions (c) 2.7 gm of Al3+ ions
32. How many faradays of electricity are involved in each of the case
(a) 0.25 mole Al3+ is converted to Al.
(b) 27.6 gm of SO3 is convered to SO 23
(c) The Cu2+ in 1100 ml of 0.5 M Cu2+ is converted to Cu.
33. 0.5 mole of electron is passed through two electrolytic cells in series. One contains silver ions, and the other
zinc ions. Assume that only cathode reaction in each cell is the reduction of the ion to the metal. How many
gm of each metals will be deposited.
34. The electrosynthesis of MnO2 is carried out from a solution of MnSO4 in H2SO4 (aq). If a current of
25 ampere is used with a current efficiency of 80%, how long would it take to produce 0.87 kg of MnO2?
35. A constant current of 30 A is passed through an aqueous solution of NaCl for a time of 1.93 hrs. How many
grams of NaOH are produced? What is volume of Cl2 gas at S.T.P. produced?
36. If 0.224 litre of H2 gas is formed at the cathode, how much O2 gas is formed at the anode under identical
conditions?
37. If 0.224 litre of H2 gas is formed at the cathode of one cell at S.T.P., how much of Mg is formed at the cathode
of the other electrolytic cell.
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
38. Assume 96500 C as one unit of electricity. If cost of electricity of producing x gm Al is Rs x, what is the cost
of electricity of producing x gm Mg?
39. Chromium metal can be plated out from an acidic solution containing CrO3 according to following equation:
CrO3(aq) + 6H+ (aq) + 6e– Cr(s) + 3H2O
Calculate :
(i) How many grams of chromium will be plated out by 28950 coulombs and
(ii) How long will it take to plate out 1.56 gm of chromium by using 12.5 ampere current
40. Calculate the quantity of electricity that would be required to reduce 12.3 g of nitrobenzene to aniline, if the
current efficiency for the process is 50 percent. If the potential drop across the cell is 3.0 volts, how much
energy will be consumed?
41. How long a current of 2A has to be passed through a solution of AgNO3 to coat a metal surface of 80 cm2 with
5m thick layer? Density of silver = 10.8g/cm3.
42. 3A current was passed through an aqueous solution of an unknown salt of Pd for 1Hr. 2.9 g of Pd+n was
deposited at cathode. Find n.
43. 50mL of 0.1M CuSO4 solution is electrolyzed with a current of 0.965 A for a period of 200 sec. The reactions
at electrodes are :
Cathode : Cu2+ + 2e Cu(s) Anode : 2H2O O2 + 4H+ + 4e.
Assuming no change in volume during electrolysis, calculate the molar concentration of Cu2+, H+ and SO42
at the end of electrolysis.
44. 10g fairly concentrated solution of CuSO4 is electrolyzed using 0.01F of electricity. Calculate:
(a) The weight of resulting solution (b) Equivalents of acid or alkali in the solution.
45. An electric current is passed through electrolytic cells in series one containing Ag(NO3)(aq.) and other
H2SO4(aq). What volume of O2 measured at 27°C and 608mm Hg pressure would be liberated from H2SO4 if
(a) one mole of Ag+ is deposited from AgNO3 solution
(b) 8 × 1022 ions of Ag+ are deposited from AgNO3 solution.
46. Cadmium amalgam is prepared by electrolysis of a solution of CdCl2 using a mercury cathode. How long
should a current of 5A be passed in order to prepare 12% CdHg amalgam on a cathode of 2gm Hg
(Cd = 112.4)
47. After electrolysis of NaCl solution with inert electrodes for a certain period of time. 600 mL of the solution was
left. Which was found to be 1N in NaOH. During the same time, 31.75 g of Cu was deposited in the copper
voltameter in series with the electrolytic cell. Calculate the percentage yield of NaOH obtained.
48. Copper sulphate solution (250 mL) was electrolysed using a platinum anode and a copper cathode. A constant
current of 2 mA was passed for 16 minutes. It was found that after electrolysis the concentration of the
solution was reduced to 50% of its original value. Calculate the concentration of copper sulphate in the
original solution.
49. A solution of Ni(NO3)2 is electrolysed between platinum electrodes using a current of 5 ampere for
20 mintue. What mass of Ni is deposited at the cathode?
50. A current of 3.7A is passed for 6 hrs. between Ni electrodes in 0.5L of 2M solution of Ni(NO 3)2. What
will be the molarity of solution at the end of electrolysis?
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
CONDUCTANCE
Conductivities and cell constant :
51. The resistance of a conductivity cell filled with 0.01N solution of NaCl is 220 ohm at18oC.Calculate the
equivalent conductivity of the solution. The cell constant of the conductivity cell is 0.88 cm 1.
52. The molar conductivity of 0.1 M CH3COOH solution is 4.6 S cm2 mole1 . What is the specific conductivity
and resistivity of the solution ?
53. The conductivity of pure water in a conductivity cell with electrodes of cross sectional area 4 cm 2 and
2 cm apart is 8 × 107 S cm 1.
(i) What is resistance of conductivity cell ?
(ii) What current would flow through the cell under an applied potential difference of 1 volt?
54. Resistivity of 0.1M KCl solution is 220 ohm cm in a conductivity cell. Calculate the cell constant if its
resistance is 330 ohm.
55. Resistance of a 0.1M KCl solution in a conductance cell is 300 ohm and specific conductance of 0.1M
KCl is 1.9 × 10-2 ohm -1 cm -1. The resistance of 0.1M NaCl solution in the same cell is 380 ohm.
Calculate the equivalent conductance of the 0.1M NaCl solution.
56. For 0.01N KCl, the resistivity 800 mho cm. Calculate the conductivity and equivalent conductance.
57. A solution containing 2.08 g of anhydrous barium chloride is 400 CC of water has a specific conductivity
0.0058 ohm –1cm –1. What are molar and equivalent conductivities of this solution.
Application of Kohlrausch's law :
58. Equivalent conductance of 0.01 N Na2SO4 solution is 112.5 ohm–1 cm2 eq–1. The equivalent conductance
at infinite dilution is 150 ohm –1 cm 2 eq–1. What is the degree of dissociation in 0.01 N Na2SO 4 solution?
59. Specific conductance of a saturated solution of AgBr is 8.5 × 10 –7 ohm –1cm –1 at 250C. Specific
conductance of pure water at 25°C is 0.75 ×10–6 ohm –1 cm –1. m for KBr , AgNO 3 and KNO 3 are 152,
133, 125 (S cm 2 mol –1) respectively. Calculate the solubility of AgBr in gm/litre.
60. Saturated solution of AgCl at 25°C has specif ic conductance of 1.2 × 10 –6 ohm –1 cm –1 .
The Ag+ and Cl – are 54.5 and 65.5 ohm –1 cm 2 / equi. respectively. Calculate the solubility product
of AgCl at 25°C.
61. Hydrofluoric acid is weak acid. At 25°C, the molar conductivity of 0.002M HF is 180 ohm –1 cm2 mole–1.
If its m = 450 ohm –1 cm 2 mole–1, calculate its degree of dissociation and equilibrium constant at the
given concentration.
62. The value of m for HCl, NaCl and CH3CO2Na are 426, 126 and 90 S cm2 mol–1 respectively. Calculate the
value of m for acetic acid. If the equivalent conductivity of the given acetic acid is 47.97 at 25° C, calculate
its degree of dissociation.
63. Calculate the specific conductance of a 0.1 M aqueous solution of NaCl at room temperature, given
that the mobilities of Na+ and Cl – ions at this temperature are 4.26 × 10–8 and 6.80 × 10–8 m 2 v –1 s–1,
respectively.
64. For the strong electroytes NaOH, NaCl and BaCl 2 the molar ionic conductivities at infinite dilution are
248.1×10–4, 126.5 ×10–4 and 280.0 ×10-4 mho cm2 mol –1 respectively. Calculate the molar conductivity
of Ba(OH)2 at infinite dilution.
65. At 25°C, (H+) = 3.4982 ×10 –2 S m 2 mol –1 and (OH–) = 1.98 ×10–2 S m 2mol –1.
Given: Sp. conductnace = 5.7 ×10–6 S m –1 for H2O, determine pH and Kw.
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
EXERCISE-II
1. The emf of the cells obtained by combining Zn and Cu electrode of a Daniel cell with N calomel electrode in
two different arrangements are 1.082V and 0.018V respectively at 25°C. If the standard reduction potential of
N calomel electrode is 0.28V and that of Zn is 0.76 V, find the emf of Daniell cell.
2. Given the standard reduction potentials Tl+ + e TI, E0 = 0.34 V and TI3+ + 2e TI+, E0 = 1.25 V.
Examine the spontaneity of the reaction, 3TI+ 2TI + TI3+. Also find E 0 for this disproportionation.
3. The emf of the cell Ag|AgI|KI(0.05M) || AgNO3(0.05M) |Ag is 0.8V. Calculate the solubility product of AgI.
4. The cell Pt, H2(1 atm) | H+(pH = x) || Normal calomel Electrode has an EMF of 0.67V at 25°C. Calculate the
pH of the solution. The oxidation potential of the calomel electrode on hydrogen scale is 0.28 V.
2.303RT
Given f
0.06
5. Estimate the cell potential of a Daniel cell having 1 M Zn++ & originally having 1 M Cu++ after sufficient NH3
has been added to the cathode compartment to make NH3 concentration 2 M.
Kf for [Cu(NH3)4]2+ = 1 × 1012, E0 for the reaction,
2.303RT
Zn + Cu2+ Zn2+ + Cu is 1.1 V. Given 0.06
f
6. The pKsp of Agl is 16. If the Eº value for Ag+ Ag is 0.8 V . Find the Eº for the half cell reaction
2.303RT
AgI (s) + e Ag + I. Given 0.06
f
7. Calculate the potential of an indicator electrode versus the standard hydrogen electrode, which originally
contained 0.1M MnO4 and 0.8M H+ and which was treated with 90% of the Fe2+ necessary to reduce all the
MnO4 to Mn+2.
2.303RT
MnO4 + 8H+ + 5e Mn2+ + 4H2O, E0 = 1.5V Given 0.06,log2 0.3, log3 0.48, log5 0.7
f
8. Kd for complete dissociation of [Ag(NH3)2]+ into Ag+ and 2NH3 is 6 × 108. Calculate E0 for the following half
reaction; Ag(NH3)2+ + e Ag + 2NH3
2.303RT
Ag+ + e Ag, E0 = 0.8 V Given f
0.06,log2 0.3, log3 0.48
9. Determine the degree of hydrolysis and hydrolysis constant of aniline hydrochloride in M/32 solution of salt
at 298 K from the following cell data at 298 K.
2.303RT
Pt | H2 (1 atm) | H+(1M) || M/32 C6H5NH3Cl | H2 (1 atm) | Pt ; Ecell= – 0.18 V. Given 0.06
f
10. Given, E° = –0.268 V for the Cl– | PbCl2 | Pb couple and – 0.127 V for the Pb2+ | Pb couple, determine Ksp for
2.303RT
PbCl2 at 25°C? Given 0.06, log2 0.3
f
11. Calculate the equilibrium constant for the reaction:
3Sn(s) + 2Cr2O72– + 28H+ 3Sn4+ + 4Cr3+ + 14H2O
E0 for Sn/Sn2+ =0.136 V E0 for Sn2+/Sn4+ = – 0.154 V
2.303RT
E0 for Cr2O72–/Cr3+ = 1.331 V Given f
0.06
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
12. Calculate the voltage of the cell at 25° C
Mn(s) | Mn(OH)2(s) | Mn2+(x M), OH –(1.00 × 10–4M) || Cu2+(0.5M) | Cu(s)
given that Ksp = 1.9 × 10–13 for Mn(OH)2(s) E0 (Mn2+/Mn) = –1.18 V , E0 (Cu2+/Cu) = 0.34 V
2.303RT
Given f
0.06, log2 0.3
13. Calculate the voltage, E, of the cell
Ag(s) | AgIO3(s) | Ag+(x M), HIO3 (0.04M) || Zn2+ (0.2M) | Zn(s)
2.303RT
if Ksp = 3.312 × 10–8 for AgIO3(s) and Ka = 0.16 for HIO3. Given 0.06,log5 0.7
f
14. The voltage of the cell
Pb(s) | PbSO4(s) | NaHSO4(0.8 M) || Pb2+(2.50 x 10–5M) | Pb(s)
is E = +0.06 V. Calculate K 2 = [H +] [SO 4 2–] / [HSO 4 –], the dissociation constant for HSO 4 .
2.303RT
Given : Pb (s) + SO42–(aq) PbSO4 (s) + 2e– (E0 = 0.366), E0(Pb2+/Pb) = –0.126 V Given 0.06
f
15. Same quantity of electricity is being used to liberate iodine (at anode) and a metal x (at cathode). The mass
of x deposited is 0.6g and the iodine is completely reduced by 50 cc of 0.125M sodium thiosulphate. Find the
equivalent mass of x.
16. The standard reduction potential values, E0(Bi3+|Bi) and E0(Cu2+|Cu) are 0.224V and 0.344V respectively. A
mixture of salts of bismuth and copper at unit concentration each is electrolysed at 25°C. to what value can
2.303RT
[Cu2+] be brought down before bismuth starts to deposit, in electrolysis. Given 0.06
f
17. In a fuel cell, H2 & O2 react to produce electricity. In the process, H2 gas is oxidized at the anode & O2 at
the cathode. If 67.2 litre of H2 at STP react in 16 minutes, what is the average current produced ? If the entire
current is used for electrode deposition of Cu from Cu (II) solution, how many grams of Cu will be deposited?
Anode : H2 + 2OH 2H2O + 2 e–
Cathode : O2 + 2 H2O + 4e 4 OH– (Molar mass of Cu = 63.5 g/mol )
18. One of the methods of preparation of per disulphuric acid, H2S2O8, involve electrolytic oxidation of H2SO4 at
anode (2H2SO4 H2S2O8 + 2H+ + 2e) with oxygen and hydrogen as byproducts. In such an electrolysis,
11.2 L of H2 and 3.36 L of O2 were generated at STP. What is the weight of H2S2O8 formed?
19. During the discharge of a lead storage battery the density of sulphuric acid fell from 1.5 to
1.2 g.ml1. H2SO4 of density 1.5 g mL1 is 40% and that of density 1.2g mL1 is 20% by weight. The battery
holds 2.94L of acid and the volume practically remains constant during the discharge. Calculate the number
of ampere hours for which the battery must have been used. The discharging reactions are:
Pb + SO42 PbSO4 + 2e (anode)
PbO2 + 4H+ + SO42 + 2e PbSO4 + 2H2O (cathode)
20. A lead storage cell is discharged which causes the H2SO4 electrolyte to change from a concentration of 40%
by weight (density 1.2g ml–1 at 25°C) to 32.5% by weight. The original volume of electrolyte is one litre.
Calculate the total charge released at anode of the battery. Note that the water is produced by the cell
reaction as H2SO4 is used up. Over all reaction is
Pb(s) + PbO2(s) + 2H2SO4(l) 2PbSO4(s) + 2H2O(l)
21. A current of 2 amp was passed for 3.86 hours through a solution of CuSO4 , 4.572g of Cu2+ ions were
deposited as Cu at cathode. Calculate percentage current efficiency of the process.
(Molar mass of Cu = 63.5 g/mol )
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
22. An acidic solution of Cu2+ salt containing 0.4 g of Cu2+ is electrolyzed until all the copper is deposited. The
electrolysis is continued for seven more minutes with the volume of solution kept at 100 ml and the current
at 1.93 amp. Calculate the volume of gases evolved at STP during the entire electrolysis.
23. In the refining of silver by electrolytic method what will be the weight of 100 gm Ag anode if 5 ampere current
is passed for 2.895 hours? Purity of silver is 90% by weight.
24. Assume that impure copper contains only iron, silver and a gold as impurities. After passage of 200 A, for
488.29s of the mass of the anode decreased by 40g and the cathode increased in mass by 31.75 g. Estimate
the % iron and % copper originally present. (Some amount of hydrogen evolved at cathode) (Molar mass of
Cu = 63.5 g/mol)
25. 100ml CuSO4(aq) was electrolyzed using inert electrodes by passing 0.965 A till the pH of the resulting
solution was 1. The solution after electrolysis was neutralized, treated with excess KI and titrated with 0.04M
Na2S2O3. Volume of Na2S2O3 required was 35 ml. Assuming no volume change during electrolysis, calculate:
(a) duration of electrolysis if current efficiency is 80% (b) initial concentration (M) of CuSO4.
26. The equivalent conductance of 0.10 N solution of MgCl 2 is 97.1 mho cm 2 equi –1 at 25°C. a cell with
electrode that are 1.5 cm 2 in surface area and 0.5 cm apart is filled with 0.1 N MgCl 2 solution. How
much current will flow when potential difference between the electrodes is 5 volt.
27. A dilute aqueous solution of KCl was placed between two electrodes 10 cm apart, across which a
potential of 6 volt was applied. How far would the K+ ion move in 2 hours at 25°C? Ionic conductance of
K+ ion at infinite dilution at 25°C is 77.2 ohm –1 cm 2 mole–1?
28. When a solution of specific conductance 1.342 ohm –1 metre–1 was placed in a conductivity cell with
parallel electrodes, the resistance was found to be 170.5 ohm. Area of electrodes is 1.86 × 10 –4 m 2.
Calculate separation of electrodes.
29. The specific conductance at 25°C of a saturated solution of SrSO4 is 1.9 × 10–4 ohm–1 cm–1 while that of
water used is 5 × 10–5 mho cm–1. Determine at 25°C the solubility in gm per litre of SrSO4 in water. Molar
ionic conductance of Sr2+ and SO42– ions at infinite dilution are 60 and 80 ohm–1 cm2 mole–1 respectively.
[ Sr = 87.6 , S = 32 , O = 16 ]
30. Calculate the solubility and solubility product of Co2 [Fe(CN)6] in water at 250C from the following data :
Conductivity of a saturated solution of Co 2[Fe(CN)6] is 2.06 × 10–6 –1 cm –1 and that of water used
5.2 × 10–7–1 cm –1 . The ionic molar conductivities of Co2+ and Fe(CN)64– are 86.0 –1 cm 2 mol –1 and
444.0 –1 cm –1mol –1.
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
QUESTION BANK
1. A standard hydrogen electrons has zero electrode potential because
(A) hydrogen is easier to oxidise
(B) this electrode potential is assumed to be zero
(C) hydrogen atom has only one electron
(D) hydrogen is the lighest element.
2. If the pressure of H2 gas is increased from 1 atm to 100 atm keeping H+ concentration constant at 1 M, the
change in reduction potential of hydrogen half cell at 25°C will be
(A) 0.059 V (B) 0.59 V (C) 0.0295 V (D) 0.118 V
3. The equilibrium constant for the reaction
Sr(s) + Mg+2 (aq) Sr+2 (aq) + Mg(s) is 2.69 × 1012 at 25°C
The E° for a cell made up of the Sr/Sr+2 and Mg+2/Mg half cells
(A) 0.3667 V (B) 0.7346 V (C) 0.1836 V (D) 0.1349 V
4. When G = –100 kJ mol–1 and n = 1, the potential of the cell is
(A) 2 V (B) 1 V (C) 10 V (D) 5 V
5. For a cell reaction involving a two electron change, the standard emf of the cell is found to be 0.295 V at 25ºC.
The equilibrium constant of the reaction at 25ºC will be
(A) 1 × 10–10 (B) 29.5 × 10–2 (C) 10 (D) 1 × 1010
6. Standard electrode potential of three metals A, B and C are + 0.5 V, – 3.0 V and – 1.2 V respectively. The
reducing power of these metals are
(A) B > C > A (B) A > B > C (C) C > B > A (D) A > C > B
7. Consider the following E0 values :
0
EFe 3
| Fe2
= + 0.77 V ; E 0Sn2 | Sn = – 0.14 V
Under standard conditions the potential for the reaction is
Sn(s) + 2Fe3+ (aq) 2Fe2+(aq) + Sn2+(aq)
(A) 1.68 V (B) 1.40 V (C) 0.91 V (D) 0.63 V
8. The standard e.m.f of a cell, involving one electron change is found to be 0.591 V at 25ºC The equilibrium
constant of the reaction is (F = 96, 500 C mol–1 , R = 8.314 JK–1 mol–1)
(A) 1.0 × 101 (B) 1.0 × 105 (C) 1.0 × 1010 (D) 1.0 × 1030
9. In a cell that utilizes the reaction Zn(s) + 2H+(aq) Zn2+(aq) + H2(g)
addition of H2SO4 to cathode compartment, will
(A) lower the E and shift equilibrium to the left
(B) lower the E and shift the equilibrium to the right
(C) increase the E and shift the equilibrium to the right
(D) increase the E and shift the equilibrium to the left
o
10. The EM 3
| M2
values for Cr, Mn Fe and Co are – 0.41, + 1.57, 0.77 and + 1.97 V respectively. For which one
of these metals the change in oxidation state from +2 to +3 is easiest ?
(A) Cr (B) Mn (C) Fe (D) Co
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
11. Reduction potential of silver wire dipped in 0.1 M HCl solution saturated with AgCl is 0.25 V.
If E oAg | Ag = – 0.799 V, the Ksp of AgCl in pure water will be
(A) 2.95 × 10–11 (B) 5.1 × 10–11 (C) 3.95 × 10–11 (D) 1.95 × 10–11
12. Consider the reaction of extraction of gold from its ore
1 1
Au(s) + 2CN– (aq.) + O (g) + H2O () Au (CN)2 (aq) + OH– (aq)
4 2 2
Use the following data to calculate G° for the reaction
Kf (Au (CN)2 ) = X
O2 + 2H2O + 4e– 4OH– ; E° = + 0.41 volt
Au3+ + 3e– Au ; E° = + 1.5 volt
Au3+ + 2e– Au+ ; E° = + 1.4 volt
(A) – RT ln X + 1.29 F (B) – RT ln X – 2.11 F
1
(C) – RT ln + 2.11 F (D) – RT ln X – 1.29 F
X
13. Consider the following Galvanic cell.
By what value the cell voltage change when concentration of ions in anodic and cathodic compartments both
increased by factor of 10 at 298 K
(A) +0.0591 (B) –0.0591 (C) –0.1182 (D) 0
14. For the cell
Pt | H2(0.4 atm) | H+(pH = 1) || H+(pH = 2) | H2 (0.1 atm) | Pt
The measured potential at 25°C is
(A) –0.1 V (B) –0.5 (C) –0.041 (D) none
15. For the fuel cell reaction 2H2(g) + O2(g) 2H2O(l) ; f Ho298 (H2O, ) = –285.5 kJ/mol
What is S o298 for the given fuel cell reaction?
Given: O2(g) + 4H+(aq) + 4e– 2H2O(l) E° = 1.23 V
(A) – 0.322 J/K (B) – 0.635 kJ/K (C) 3.51 kJ/K (D) – 0.322 kJ/K
16. The standard reduction potentials of Cu2+/ Cu and Cu2+ / Cu+ are 0.337 and 0.153 V respectively. The
standard electrode potential of Cu+ / Cu half cell is
(A) 0.184 V (B) 0.827 V (C) 0.521 V (D) 0.490 V
17. A hydrogen electrode X was placed in a buffer solution of sodium acetate and acetic acid in the ratio
a : b and another hydrogen electrode Y was placed in a buffer solution of sodium acetate and acetic acid in
the ratio b : a. If reduction potential values for two cells are found to be E1 and E2 respectively w.r.t. standard
hydrogen electrode, the pKa value of the acid can be given as
E1 E 2 E 2 – E1 E1 E 2 E1 – E 2
(A) (B) (C) – (D)
0.118 0.118 0.118 0.118
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
18. Given the data at 25ºC ,
Ag + I– AgI + e– ; Eo = 0.152 V
RT
Ag Ag+ + e– ; Eo = – 0.800 V 2.309 0.059 V
F
What is the value of log Ksp for Agl ?
(A) – 8.12 (B) + 8.612 (C) – 37.83 (D) –16.13
19. For the electrochemical cell, M | M+ || X– | X, E° (M+/M) = 0.44 V and E° (X/X–) = 0.33V. From this data , one
can deduce that
(A) M + X M+ + X– is the spontaneous reaction
(*B) M+ + X– M + X is the spontaneous reaction
(C) Ecell= 0.77 V
(D) Ecell= –0.77 V
20. How many faradays are required to reduce 1 mol of BrO3 to Br–?
(A) 3 (B) 5 (C) 6 (D) 4
21. One gm metal M+2 was discharged by the passage of 1.81 × 1022 electrons. What is the atomic weight of
metal?
(A) 33.35 (B) 133.4 (C) 66.7 (D) 55
22. Aluminium oxide may be electrolysed at 1000ºC to furnish aluminium metal. The cathode reaction is
Al3+ + 3e– Al. To prepare 5.12 kg of aluminium metal by this method would require
(A) 5.49 × 107 C of electricity (B) 1.83 × 107 C of electricity
(C) 5.49 × 104 C of electricity (D) 5.49 × 1010 C of electricity
23. One mole of electron passes through each of the solution of AgNO3, CuSO4 and AlCl3 when Ag, Cu and Al are
deposited at cathode. The molar ratio of Ag, Cu and Al deposited are
(A) 1 : 1 : 1 (B) 6 : 3 : 2 (C) 6 : 3 : 1 (D) 1 : 3 : 6
24. Salts of A (atomic weight = 7), B (atomic weight =27) and C (atomic weight = 48) were electrolysed under
identical conditions using the same quantity of electricity. It was found that when 2.1 g of A was deposited,
the weights of B and C deposited were 2.7 and 7.2 g. The valencies of A, B and C respectively are
(A) 3, 1 and 2 (B) 1, 3 and 2 (C) 3, 1 and 3 (D) 2, 3 and 2
25. The density of Cu is 8.94 g cm–3. The quantity of electricity needed to plate an area 10 cm × 10 cm to a
thickness of 10–2 cm using CuSO4 solution would be
(A) 13586 C (B) 27172 C (C) 40758 C (D) 20348 C
26. During electrolysis of an aqueous solution of sodium sulphate, 2.4 L of oxygen at STP was liberated at
anode. The volume of hydrogen at STP, liberated at cathode would be
(A) 1.2 L (B) 2.4 L (C) 2.6 L (D) 4.8 L
27. During electrolysis of an aqueous solution of CuSO4 using copper electrodes, if 2.5 g of Cu is deposited at
cathode, then at anode
(A) 890 ml of Cl2 at STP is liberated
(B) 445 ml of O2 at STP is liberated
(C) 2.5 g of copper is deposited
(D) a decrease of 2.5 g of mass takes place
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
28. An aqueous solution containing one mole per litre each of Cu(NO3)2, AgNO3, Hg2(NO3)2, Mg(NO3)2 is being
electrolysed by using inert electrodes. The value of standard potentials are
o
Eo 0.80 V , Eo = 0.79V,, E Cu2 | Cu = 0.34V and E o = – 2.3V
Ag |Ag Hg2 | Hg Mg 2 | Mg
2
With increasing voltage, the sequence of deposition of metals on the cathode will be
(A) Ag, Hg, Cu, Mg (B) Mg, Cu, Hg, Ag
(C) Ag, Hg, Cu (D) Cu, Hg, Ag
2
29. The charge required for the oxidation of one mole Mn3O4 into MnO 4 in presence of alkaline medium is
(A) 5 × 96500 C (B) 96500 C
(C) 10 × 96500 C (D) 2 × 96500 C
30. The cost at 5 paise / KWH of operating an electric motor for 8 hours which takes 15 amp at 110 V is
(A) Rs. 66 (B) 66 paise (C) 37 paise (D) Rs. 6.60
31. A solution of sodium sulphate in water is electrolysed using inert electrodes. The products at the cathode
and anode are respectively.
(A) H2, O2 (B) O2, H2 (C) O2, Na (D) none
32. When an aqueous solution of lithium chloride is electrolysed using graphite electrodes
(A) Cl2 is liberated at the anode.
(B) Li is deposited at the cathode
(C) as the current flows, pH of the solution around the cathode remains constant
(D) as the current flows, pH of the solution around the cathode decreases.
33. The highest electrical conductivity of the following aqueous solutions is of
(A) 0.1 M acetic acid (B) 0.1 M chloroacetic acid
(C) 0.1 M fluoroacetic acid (D) 0.1 M difluoroacetic acid
34. The value of molar conductance of HCl is greater than that of NaCl at a given temperature and concentration
because
(A) ionic mobility of HCl is greater than that of NaCl
(B) the dipole moment of NaCl is greater than that of HCl
(C) NaCl is more ionic than HCl
(D) HCl is Bronsted acid and NaCl is a salt of a strong acid and strong base
35. Resistance of a conductivity cell filled with a solution of an electrolyte of concentration 0.1 M is 100 . The
conductivity of this solution is 1.29 Sm–1. Resistance of the same cell when filled with 0.2 M of the same
solution is 520 . The molar conductivity of 0.2 M solution of the electrolyte will be
(A) 124 × 10–1 S m2 mol–1 (B) 1240 × 10–4 S m2 mol–1
(C) 1.24 S m2 mol–1 (D) 12.4 × 10–4 S m2 mol–1
o
36. The limiting molar conductivities m for NaCl, KBr and KCl are 126, 152 and 150 S cm2 mol–1 respectively..
o
The m for NaBr is
(A) 128 S cm2 mol–1 (B) 176 S cm2 mol–1 (C) 278 S cm2 mol–1 (D) 302 S cm2 mol–1
37. The resistance of 0.5 M solution of an electrolyte in a cell was found to be 50 . If the electrodes in the cell
are 2.2 cm apart and have an area of 4.4 cm2 then the molar conductivity (in S m2 mol–1) of the solution is
(A) 0.2 (B) 0.02 (C) 0.002 (D) None of these
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
38. 2 –1
Equivalent conductance of 0.1 M HA(weak acid) solution is 10 Scm equivalent and that at infinite dilution
is 200 Scm2equivalent–1 Hence pH of HA solution is
(A) 1.3 (B) 1.7 (C) 2.3 (D) 3.7
39. If x is specific resistance of the electrolyte solution and y is the molarity of the solution, then m is given by
1000 x y 1000 xy
(A) y
(B) 1000 (C) xy
(D)
x 1000
40. The dissociation constant of n-butyric acid is 1.6 × 10–5 and the molar conductivity at infinite dilution is
380 × 10–4 Sm2 mol–1. The specific conductance of the 0.01 M acid solution is
(A) 1.52 × 10–5 Sm–1 (B) 1.52 × 10–2 Sm–1
(C) 1.52 × 10–3 Sm–1 (D) None
41. The molar conductivities ºNaOAc and ºHCl at infnite dilution in water at 25ºC are 91.0 and
426.2 S cm2/mol respectively. To calculate ºHOAc the additional value required is
(A) ºH2O (B) ºKCl (C) ºNaOH (D) ºNaCl
42. The conductivity of a saturated solution of Ag3PO4 is 9 × 10–6 Sm–1 and its eqivalent conductivity is
1.50 × 10–4 S m2 equivalent–1. The Ksp of Ag3PO4 is
(A) 4.32 × 10–18 (B) 1.8 × 10–9 (C) 8.64 × 10–13 (D) None of these
43. A saturated solution in AgA (Ksp = 3 × 10–14) and AgB (Ksp = 1 × 10–14) has conductivity of 375 × 10–10 Scm–1
and limiting molar conductivity of Ag+ and A– are 60 Scm2 mol–1 and 80 Scm2 mol–1 respectively then what will
be the limiting molar conductivity of B– (in Scm2 mol–1)?
(A) 150 (B) 180 (C) 190 (D) 270
44. Equal volumes of 0.015 M CH3COOH & 0.015 M NaOH are mixed together. What would be molar conductivity
of mixture if conductivity of CH3COONa is 6.3 × 10–4 S cm–1 ?
(A) 8.4 S cm2 mol–1 (B) 84 S cm2 mol–1 (C) 4.2 cm2 mol–1 (D) 42 S cm2 mol–1
45. ECell for reduction of NO 3 NO by Cu(s), when [HNO3] = 1M, PNO = 10–3 atm, [Cu2+] = 0.1 M is :
RT
(Given : at 298 K (2.303) = 0.06 volt ; ENO = +0.96 volt ; E 2 = +0.34 volt)
F 3 / NO Cu / Cu
(A) 0.61 (B) 0.71 (C) 0.51 (D) 0.81
Paragraph for Question Nos. 46 to 48
A sample of water from a large swimming pool has a resistance of 10000 at 25ºC when placed in a certain
conductance cell. When filled with 0.02 M KCl solution, the cell has a resistance of 100 at 25ºC. 585 gm
of NaCl were dissolved in the pool, which was throughly stireed. A sample of this solution gave a resistance
of 8000 .
[Given : Molar conductivity of NaCl at that concentration is 125 –1 cm2 mol–1 and molar conductivity of KCl
at 0.02 M is 200 –1 cm2 mol–1]
46. Cell constant (in cm–1) of conductance cell is
(A) 4 (B) 0.4 (C) 4 × 10–2 (D) 4 × 10–5
47. Conductivity (Scm–1) of H2O is
(A) 4 × 10–2 (B) 4 × 10–3 (C) 4 × 10–5 (D) None of these
48. Volume (in Litres) of water in the pool is
(A) 1.25 × 105 (B) 1250 (C) 12500 (D) None of these
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
More than one may be correct
49. During discharging of lead storage battery, which of the following is/are true ?
(A) H2SO4 is produced (B) H2O is consumed
(C) PbSO4 is formed at both electrodes (D) Density of electrolytic solution decreases
50. Which of the following arrangement will produce oxygen at anode during electrolysis ?
(A) Dilute H2SO4 solution with Cu electrodes. (B) Dilute H2SO4 solution with inert electrodes.
(C) Fused NaOH with inert electrodes. (D) Dilute NaCl solution with inert electrodes.
51. If 270.0 g of water is electrolysed during an experiment performed by Miss Rachita with 75% current efficiency
then
(A) 168 L of O2 (g) will be evolved at anode at 1 atm & 273 K
(B) Total 504 L gases will be produced at 1 atm & 273 K.
(C) 336 L of H2 (g) will be evolved at anode at 1 atm & 273 K
(D) 45 F electricity will be consumed
52. In an electrochemical process, a salt bridge is used
(A) to maintain electroneutrality in each solution (B) to complete the circuit so that current can flow
(C) as an oxidizing agent (D) as a colour indicator
53. When galvanic cell started, with passage of time
(A) spontaneity of the cell reaction decreases; Ecell decreases
(B) reaction quotient Q decreases; Ecell increases
(C) reaction quotient Q increases; Ecell decreases
(D) at equilibrium Q = Kc; Ecell = 0
54. Which one is/are correct among the followings?
Given, the half cell emf’s E 0Cu 2 |Cu 0.337, E0Cu |Cu 0.521
(A) Cu+ disproportionates
(B) Cu and Cu2+ comproportionates (reverse of disproportionation into Cu+)
(C) E oCu | Cu 2 E oCu | Cu is positive
(D) All of these
55. Pick out the correct statements among the following from inspection of standard reduction potentials (Assume
standard state conditions).
Cl2 (aq.) + 2e 2Cl– (aq.) E 1.36 volt
Cl2 / Cl
Br2(aq.) + 2e 2Br– (aq.) E 1.09 volt
Br2 / Br
I2(s) + 2e 2I– (aq.) E 0.54 volt
I2 / I
S2O82 (aq.) + 2e 2SO 24 (aq.) E = + 2.00 volt
S 2O28 / SO 24
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
(A) Cl2 can oxidise SO24 from solution
(B) Cl2 can oxidise Br– and I– from aqueous solution
(C) S2O82 can oxidise Cl– , Br– and I– from aqueous solution
(D) S2O82– is added slowly, Br– can be reduce in presence of Cl–
56. The EMF of the following cell is 0.22 volt.
Ag s AgCl s KCl 1M H 1M H2 g 1 atm| Pt(s).
Which of the following will decrease the EMF of cell.
(A) increasing pressure of H2(g) from 1 atm to 2 atm.
(B) increasing Cl– concentration in Anodic compartment
(C) increasing H+ concentration in cathodic compartment
(D) decreasing KCl concentration in Anodic compartment.
57. Which of the following units is correctly matched?
(A) SI units of conductivity () is S m–1
(B) SI units of molar conductivity is S m2 mol–1
(C) SI unit of ionic mobility is m V–1s–1
(D) All of these
Match the column
58. Column I Column II
(Electrolysis product using inert electrode)
(A) Dilute solution of HCl (P) O2 evolved at anode
(B) Dilute solution of NaCl (Q) H2 evolved at cathode
(C) Concentrated solution of NaCl (R) Cl2 evolved at anode
(D) AgNO3 solution (S) Ag deposition at cathode
59. Column-I Column-II
(A) Zn | Zn+2 (c1) || Mg2+ (c1) | Mg (P) E0cell = 0
(B) Zn | Zn+2 (c1) || Ag+ (c1) | Ag (Q) E0cell 0
(C) Ag | Ag+ || Ag+ | Ag (R) E0cell = + ve
(D) Fe | Fe2+ || Ag+ | Ag (S) E0cell = – ve
60. Column-I Column-II
(Factors on which dependency exist)
(A) Molar conductance (P) Temperature
(B) Emf of a concentration cell (Q) Concentration of species involved
(C) Electrode potential (R) Nature of substance involved
(D) Standard redution potential (S) Pressure of gas
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
EXERCISE-III
Paragraph for Question Nos. 1 to 3 (3 questions)
Chemical reactions involve interaction of atoms and molecules. A large number of atoms/molecules
(approximately 6.023 × 1023) are present in a few grams of any chemical compound varying with their atomic/
molecular masses. To handle such large numbers conveniently, the mole concept was introduced. This
concept has implications in diverse areas such as analytical chemistry, biochemistry, electrochemistry and
radiochemistry. The following example illustrates a typical case, involving chemical/ electrochemical reaction,
which requires a clear understanding of the mole concept.
A 4.0 molar aqueous solution of NaCl is prepared and 500 mL of this solution is electrolysed. This leads to
the evolution of chlorine gas at one of the electrodes (atomic mass : Na = 23, Hg = 200; 1 Faraday = 96500
coulombs) [JEE 2007]
1. The total number of moles of chlorine gas evolved is
(A) 0.5 (B) 1.0 (C) 2.0 (D) 3.0
2. If the cathode is a Hg electrode, the maximum weight (g) of amalgam formed from this solution is
(A) 200 (B) 225 (C) 400 (D) 446
3. The total charge (coulombs) required for complete electrolysis is
(A) 24125 (B) 48250 (C) 96500 (D) 193000
Paragraph for Question Nos. 4 to 5 (2 questions)
Redox reactions play a pivoted role in chemistry and biology. The values of standard redox potential (E°) of
two half-cell reactions decide which way the reaction is expected to proceed. A simple example is a Daniel
cell in which zinc goes into solution and copper gets deposited. Given below are a set of half-cell reactions
(acidic medium) along with their E° (V with respect to normal hydrogen electrode) values. Using this data
obtain the correct explanations to Questions 14-16.
I2 + 2e– 2I– E° = 0.54
Cl2 + 2e– 2Cl– E° = 1.36
3+ –
Mn + e Mn 2+ E° = 1.50
3+ –
Fe + e Fe 2+ E° = 0.77
+ –
O2 + 4H + 4e 2H2O E° = 1.23 [JEE 2007]
4. Among the following, identify the correct statement.
(A) Chloride ion is oxidised by O2 (B) Fe2+ is oxidised by iodine
(C) Iodine ion is oxidised by chlorine (D) Mn2+ is oxidised by chlorine
5. While Fe3+ is stable, Mn3+ is not stable in acid solution because
(A) O2 oxidises Mn2+ to Mn3+ (B) O2 oxidises both Mn2+ to Mn3+ and Fe2+ to Fe3+
3+
(C) Fe oxidises H2O to O2 (D) Mn3+ oxidises H2O to O2
6. Electrolysis of dilute aqueous NaCl solution was carried out by passing 10 milli ampere current. The time
required to liberate 0.01 mol of H2 gas at the cathode is (1 Faraday = 96500 C mol–1) [JEE 2008]
(A) 9.65 × 104 sec (B) 19.3 × 104 sec (C) 28.95 × 104 sec (D) 38.6 × 104 sec
7. For the reaction of NO 3 ion in an aqueous solution, E° is +0.96 V. Values of E° for some metal ions are given below
V2+ (aq) + 2e– V E° = – 1.19 V
Fe3+ (aq) + 3e– Fe E° = – 0.04 V
Au3+ (aq) + 3e– Au E° = + 1.40 V
Hg2+ (aq) + 2e– Hg E° = + 0.086 V
The pair(s) of metal that is(are) oxidised by NO 3 in aqueous solution is(are)
(A) V and Hg (B) Hg and Fe (C) Fe and Au (D) Fe and V [JEE 2009]
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
Paragraph for Questions 8 to 9
The concentration of potassium ions inside a biological cell is at least twenty times higher than the outside.
The resulting potential difference across the cell is important in several processes such as transmission of
nerve impulses and maintaining the ion balance. A simple model for such a concentration cell involving a
metal M is :
M(s) |M+ (aq. 0.05 molar) ||M+ (aq. 1.0 molar)| M(s)
For the above electrolytic cell the magnitude of the cell potential |Ecell| = 70 mV. [JEE 2010]
8. For the above cell :-
(A) Ecell < 0 ; G > 0 (B) Ecell > 0 ; G < 0 (C) Ecell < 0 ; G° > 0 (D) Ecell > 0 ; G° < 0
9. If the 0.05 molar solution of M+ is replaced by a 0.0025 molar M+ solution, then the magnitude of the cell
potential would be :-
(A) 35 mV (B) 70 mV (C) 140 mV (D) 700 mV
10. Consider the following cell reaction L [JEE 2011]
2Fe(s) + O2(g) + 4H+(aq) 2Fe2+(aq) + 2H2O() E° = 1.67 V
At [Fe2+] = 10–3 M, P(O2) = 0.1 atm and pH = 3, the cell potential at 25°C is
(A) 1.47 V (B) 1.77 V (C) 1.87 V (D) 1.57 V
11. AgNO3(aq.) was added to an aqueous KCl solution gradually and the conductivity of the solution was measured.
The plot of conductance ( ) versus the volume of AgNO3 is : [JEE 2011]
volume volume volume volume
(P) (Q) (R) (S)
(A) P (B) Q (C) R (D) S
Paragraph for Questions Nos. 12 to 13
The electrochemical cell shown below is a concentration cell.
M|M2+ (saturated solution of a sparingly soluble salt, MX2)|| M2+ (0.001 mol dm–3) | M
The emf of the cell depends on the difference in concentration of M2+ ions at the two electrodes. The emf of
the cell at 298 is 0.059 V [JEE 2012]
12. The solubility product (Ksp ; mol3dm–9) of MX2 at 298 based on the information available the given concentration
cell is (take 2.303 × R × 298/F = 0.059 V)
(A) 1 × 10–15 (B) 4 × 10–15 (C) 1 × 10–12 (D) 4 × 10–12
13. The value of G(kJ mol–1) for the given cell is (take 1F = 96500 C mol–1)
(A) –5.7 (B) 5.7 (C) 11.4 (D) –11.4
14. Given : E0 –0.74 V ; E 0MnO – / Mn 2 1.51V ; a E 0 1.33 V ; E 0Cl / Cl– 1.36 V
Cr 3 / Cr 4 Cr2O 2 – / Cr 3
7
Based on the data given above, strongest oxidising agent will be : [JEE (Mains) 2013]
(A) MnO4– (B) Cl¯ (C) Cr3+ (D) Mn2+
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
15. An aqueous solution of X is added slowly to an aqueous solution of Y as shown in List I. The variation in
conductivity of these reactions is givne in List II. Match List with List II and select the correct answer using
the code given below the lists : [JEE (Adv.) 2013]
List- I List- II
(P) (C2H5 )3 N CH3 COOH (1) Conductivity decreases and then increases
X Y
(Q) K(0.1 M) AgNO 3 (0 .01M) (2) Conductivity decreases and then does not
X Y
change much
(R) CH3 COOH KOH (3) Conductivity increases and then does not
X Y
change much
(S) NaOH H (4) Conductivity does not change much and
X Y
then increases
Codes :
P Q R S
(A) 3 4 2 1
(B) 4 3 2 1
(C) 2 3 4 1
(D) 1 4 3 2
16. The standard reduction potential data at 25°C is given below.
E°(Fe3+, Fe2+) = + 0.77 V; [JEE (Adv.) 2013]
E°(Fe2+, Fe) = – 0.44 V
E°(Cu2+, Cu) = + 0.34 V;
E°(Cu+, Cu) = + 0.52 V;
E°[O2(g) + 4H+ + re– 2H2O] = + 1.23 V;
E°[O2(g) + 2H2O + 4e– 4OH–] = + 0.40 V
E°(Cr3+, Cr) = – 0.74 V ;
E°(Cr2+, Cr) = – 0.91 V
Match E° of the redox pair in List with the values given in List II and select the correct answer using the code
given below the lists :
List- I List- II
(P) E° (Fe3+, Fe) 1. – 0.18 V
(Q) E°(4H2O 4H+ + 4OH–) 2. – 0.4 V
(R) E°(Cu2+ + Cu 2Cu+) 3. – 0.04 V
(S) E°(Cr3+, Cr2+) 4. – 0.83 V
Codes :
P Q R S
(A) 4 1 2 1
(B) 4 3 4 1
(C) 1 2 3 4
(D) 3 4 1 2
17. Given below are the half-cell reactions :
Mn2+ + 2e– Mn ; Eº = –1.18 V
2(Mn3+ + e– Mn2+) ; Eº = +1.51 V
The Eº for 3Mn2+ Mn + 2Mn3+ will be [JEE- Mains - 2014]
(A) –2.69 V ; the reaction will occur (B) –0.33 V ; the reaction will not occur
(C) –0.33 V ; the reaction will occur (D) –2.69 V ; the reaction will not occur
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
18. The equivalent conductance of NaCl at concentration C and at infinite dilution are C and , respectively. The
correct relationship between C and is given as
(where the constant B is positive) [JEE- Mains - 2014]
(A) C = – (B) C (B) C = – (B) C (C) C = + (B) C (D) C = + (B)C
19. Resistance of 0.2 M solution of an electrolyte is 50. The specific conductance of the solution is 1.4 S m–
1. The resistance of 0.5 M solution of the same electrolyte is 280 . The molar conductivity of 0.5 M solution
of the electrolyte in S m2 mol–1 is [JEE- Mains - 2014]
(A) 5 × 10 –3 (B) 5 × 10 3 (C) 5 × 10 2 (D) 5 × 10–4
20. In a galvanic cell, the salt bridge [JEE (Adv.) 2014]
(A) does not participate chemically in the cell reaction.
(B) stops the diffusion of ions from one electrode to another.
(C) is necessary for the occurrence of the cell reaction.
(D) ensures mixing of the two electrolytic solutions.
21. Two Faraday of electricity is passed through a solution of CuSO4. The mass of copper deposited at the
cathode is : (at. mass of Cu = 63.5 amu) (JEE mains 2015)
(A) 127 g (B) 0 g (C) 63.5 g (D) 2 g
22. Copper is purified by electrolytic refining of blister copper. The correct statement(s) about this process is(are)
(JEE Advanced 2015)
(A) Impure Cu strip is used as cathode (B) Acidified aqueous CuSO4 is used as electrolyte
(C) Pure Cu deposits at cathode (D) Impurities settle as anode-mud
23. Galvanization is applying a coating of : [JEE Main 2016]
(A) Pb (B) Cr (C) Cu (D) Zn
24. For the following electrochemical cell at 298 K, [JEE Advanced 2016]
Pt(x) |H2(g, 1 bar)| H+(aq, 1M)|M 4+(aq), M2+(aq)| Pt(s)
[M2 (aq)]
Ecell = 0.092 V when = 10x.
[M4 (aq)]
0 RT
Given : EM4 /M2 = 0.151 V, 2.303 = 0.059 V
F
The value of x is :
(A) –2 (B) –1 (C) 1 (D) 2
25. Given [JEE- Mains - 2017]
EoCl / Cl –
1.36 V, EoCr 3 / Cr –0.74 V ;
2
E oCr O2 – / Cl3 1.33 V, EMnO
o
–
/ Mn 2
1.51 V
2 7 4
Among the following, the strongest reducing agent is
(A) Cl– (B) Cr (C) Mn2+ (D) Cr3+
26. For the following cell, [JEE Advanced 2017]
Zn(s) | ZnSO4(aq) || CuSO4(aq) | Cu(s)
when the concentration of Zn2+ is 10 times the concentration of Cu2+, the expression for G (in J mol–1) is :
[F is Faraday constant ; R is gas constant ; T is temperature : Eº (cell) = 1.1 V]
(A) 2.303 RT + 1.1 F (B) 2.303 RT – 2.2 F
(C) 1.1 F (D) – 2.2 F
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
27. How long (approximate) should water be electrolysed by passing through 100 amperes current so that the
oxygen released can completely burn 27.66 g of diborane? (Atomic weight of B = 10.8 u)
[JEE Main 2018]
(A) 1.6 hours (B) 6.4 hours (C) 0.8 hours (D) 3.2 hours
28. When an electric current is passed through acidified water, 112 mL of hydrogen gas at N.T.P. was collected
at the cathode in 965 seconds. The current passed, in ampere, is : [Online JEE Main 2018]
(A) 1.0 (B) 0.5 (C) 0.1 (D) 2.0
29. When 9.65 ampere current was passed for 1.0 hour into nitrobenzene in acidic medium, the amount of
p-aminophenol produced is [Online JEE Main 2018]
(A) 9.81 g (B) 109.0 g (C) 98.1 g (D) 10.9 g
30. If the standard electrode potential for a cell is 2 V at 300 K, the equilibrium constant (K) for the reaction
Zn(s) + Cu2+ (aq) Zn2+(aq) + Cu (s)
at 300 K is approximately (R = 8 JK–1 mol–1, F = 96000 C mol–1) [Online JEE Main 2019]
(A) e320 (B) e–160 (C) e–80 (D) e160
31. The anodic half-cell of lead-acid battery is recharged using electricity of 0.05 Faraday. The amount of PbSO4
electrolyzed in g during the process is : (Molar mass of PbSO4 = 303 g mol–1) [Online JEE Main 2019]
(A) 22.8 (B) 11.4 (C) 7.6 (D) 15.2
32. Consider the following reduction processes : [Online JEE Main 2019]
Zn2+ + 2e– Zn(s) ; E° = –0.76 V
Ca2+ + 2e– Ca(s) ; E° = –2.87 V
Mg2+ + 2e– Mg(s) ; E° = –2.36 V
Ni2+ + 2e– Ni(s) ; E° = –0.25 V
The reducing power of the metals increases in the order :
(A) Ni < Zn < Mg < Ca (B) Zn < Mg < Ni < Ca (C) Ca < Mg < Zn < Ni (D) Ca < Zn < Mg < Ni
33. In the cell [Online JEE Main 2019]
Pt(s) | H2(g, 1bar) | HCl(aq) | AgCl(s) | Ag(s) | Pt(s) the cell potential is 0.92 V when a 10–6 molal HCl solution
is used. The standard electrode potential of (AgCl / Ag,Cl–) electrode is :
2.303 RT
Given , 0.06 V at 298 K
F
(A) 0.40 V (B) 0.76 V (C) 0.20 V (D) 0.94
34. For the cell Zn(s)|Zn2+ (aq)||Mx + (aq)|M(s), different half cells and their standard electrode potentials are given
below : [Online JEE Main 2019]
x+ 3+ + 3+ 2– 2+
M (aq)/M(s) Au (aq)/Au(s) Ag (aq)/Ag(s) Fe (aq)/Fe (aq) Fe (aq)/Fe(s)
x+
Eº M /M/(V) 1.40 0.80 0.77 –0.44
If Eº Eº Zn2 /Zn 0.76V, which cathode will give a maximum value of Eºcell per electron transferred?
(A) Fe3+/Fe2+ (B) Ag+/Ag (C) Au3+ / Au (D) Fe2+/Fe
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
35. Given the equilibrium constant : [Online JEE Main 2019]
KC of the reaction :
Cu(s) + 2Ag+(aq) Cu2+ (aq) + 2Ag(s) is 10 × 1015, calculate the E0cell of this reaction at 298 K
RT
2.303 F at 298K 0.059 V
(A) 0.04736 V (B) 0.4736 V (C) 0.4736 mV (D) 0.04736 mV
dEº
36. The standard electrode potential Eº and its temperature coefficient for a cell are 2V and –5 × 10–4
dT
VK–1 at 300 K respectively. The cell reaction is Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s). The standard reaction
enthalpy (rHº) at 300 K in kJ mol–1 is, [Online JEE Main 2019]
–1 –1
[UseR = 8 JK mol and F = 96,000 Cmol ] –1
(A) 192.0 (B) –384.0 (C) –412.8 (D) 206.4
37. mo for NaCl, HCl and NaA are 126.4, 425.9 and 100.5 S cm2 mol–1, respectively. If the conductivity of 0.001
M HA is 5 × 10–5 S cm–1, degree of dissociation of HA is : [Online JEE Main 2019]
(A) 0.125 (B) 0.75 (C) 0.50 (D) 0.25
38. Given : [Online JEE Main 2019]
Co3+ + e– Co2+ ; E° = + 1.81 V
Pb4+ + 2e– Pb2+ ; E° = + 1.67 V
Ce4+ + e– Ce3+ ; E° = + 1.61 V
Bi3+ + 3e– Bi ; E° = + 0.20 V
Oxidizing power of the species will increase in the order :
(A) Bi3+ + < Ce4+ < Pb4+ < Co3+ (B) Co3+ < Ce4+ < Bi3+ < Pb4+
(C) Ce4+ < Pb4+ < Bi3+ < Co3+ (D) Co3+ < Pb4+ < Ce4+ < Bi3+
39. Which one of the following graphs between molar conductivity (m) versus C is corrrect ?
[Online JEE Main 2019]
Na KC
KC
Cl l
l
m m N m
Na KCl Na KC aCl
(A) m C (B) Cl (C) l (D)
l
C C C C
40. Consider the statements S1 and S2 : [Online JEE Main 2019]
S1 : Conductivity always increases with decrease in the concentration of electrolyte.
S2 : Molar conductivity always increases with decrease in the concentration of electrolyte.
The correct option among the following is :
(A) S1 is correct and S2 is wrong (B) Both S1 and S2 are wrong
(C) Both S1 and S2 are correct (D) S1 is wrong and S2 is correct
41. A solution of Ni(NO3)2 is electrolysed between platinum electrodes using 0.1 Faraday electricity. How many
mole of Ni will be deposited at the cathode ? [Online JEE Main 2019]
(A) 0.15 (B) 0.20 (C) 0.05 (D) 0.10
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
42. The standard Gibbs energy for the given cell reaction in kJ mol–1 at 298 K is : [Online JEE Main 2019]
Zn(s) + Cu2+ (aq) Zn2+(aq) + Cu(s), E° = 2 V at 298 K
(Faraday's constant, F = 96000 C mol–1)
(A) –192 (B) –384 (C) 384 (D) 192
43. Given that E O /H O = +1.23 V ; E S O 2–/SO 2– = 2.05 V ; E Br /Br = 1.09 V ; E Au3+/Au = 1.4 V
–
2 2 2 8 4 2
The strongest oxidizing agent is : [Online JEE Main 2019]
(A) Au3+ (B) O2 (C) Br2 (D) S2O82–
44. Calculate the standard cell potential (in V) of the cell in which following reaction takes place:
Fe2+(aq) + Ag+(aq) Fe3+(aq) + Ag(s)
0 0
Given that E Ag / Ag x V , EFe2 /Fe y V , E0Fe3 /Fe z V [Online JEE Main 2019]
(A) x – z (B) x + y = 0 (C) x + 2y – 3z (D) x – y
Subjective
45. Two students use same stock solution of ZnSO4 and a solution of CuSO4. The e.m.f of one cell is
0.03 V higher than the other. The conc. of CuSO4 in the cell with higher e.m.f value is 0.5 M. Find out the
2.303 RT
conc. of CuSO4 in the other cell 0.06 . [JEE 2003]
F
46. Find the equilibrium constant at 298 K for the reaction,
Cu2+(aq) + In2+(aq) Cu+(aq) + In3+(aq)
o
Given that E oCu2 |Cu 0.15 V , EIn
o
3 |In 0 .42 V , E 2 0.40 V [JEE 2004]
In |In
47. (a)Calculate G0f of the following reaction
Ag (aq ) + Cl (aq ) AgCl(s)
Given : G0f (AgCl) = –109 kJ/mole, G0f (Cl–) = –129 kJ/mole, G0f (Ag+) = 77 kJ/mole
Represent the above reaction in form of a cell
Calculate E0 of the cell. Find log10KSP of AgCl
(b) 6.539 × 10–2 g of metallic Zn (amu = 65.39) was added to 100 ml of saturated solution of AgCl.
[ Zn2 ] , given that
Calculate log10
[ Ag ] 2
Ag+ + e– Ag E0 = 0.80 V ; Zn2+ + 2e– Zn E0 = –0.76V
Also find how many moles of Ag will be formed? [JEE 2005]
48. –14 –7
We have taken a saturated solution of AgBr.Ksp of AgBr is 12 × 10 . If 10 mole of AgNO3 are added to
1 litre of this solution find conductivity (specific conductance) of this solution in terms of 10–7 S m–1 mol–1.
Given : 0 = 6 ×10–3 S m2 mol–1 ; 0 = 8 ×10–3 S m2 mol–1 ; 0 ) = 7×10–3 S m2 mol–1
( Ag ) (Br ) (NO3
[JEE 2006]
49. All the energy from the reaction X Y, rG° = – 193 kJ mol–1 is used for oxidizing M+ as M+ M3+ + 2e–,
E° = – 0.25 V.
Under standard conditions, the number of moles of M+ oxidized when one mole of X is converted to Y is
[F = 96500 C mol–1] [JEE Advanced 2015]
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
50. The molar conductivity of a solution of a weak acid HX(0.01 M) is 10 times smaller than the molar conductivity
0 0
of a solution of a weak acid HY (0.10 M). If X y , the difference in their pKa values, pKa(HX) – pKa(HY),
is (Consider degree of ionization of both acids to be <<1) [JEE Advanced 2015]
51. The conductance of a 0.0015 M aqueous solution of a weak monobasic acid was determined by using a
conductivity cell consisting of platinized Pt electrodes. The distance between the electrodes is 120 cm with
an area of cross section of 1 cm2. The conductance of this solution was found to be 5 × 10–7 S. The pH of
the solution is 4. The value of limiting molar conductivity (om ) of this weak monobasic acid in aqueous
solution is Z × 102 S cm–1 mol–1. The value of Z is [JEE Advanced 2017]
52. For the electrochemical cell. [JEE Advanced 2018]
Mg(s) | Mg2+(aq, 1 M) || Cu2+(aq, 1 M) | Cu(s)
the standard emf of the cell is 2.70 V at 300. When the concentration of Mg2+ is changed to xM, the cell
potential changes to 2.67 V at 300 K. The value of x is ___________.
F
(Given, 11500 KV 1, where F is the Faraday constant and R is the gas constant, ln(10) = 2.30)
R
53. Consider an electrochemical cell : A(s) | An+ (aq, 2M) || B2n+ (aq, 1 M) | B(s). The value of H for the cell
reaction is twice that of G at 300 K. If the emf of the cell is zero, the S (in J K–1 mol–1) of the cell
reaction per mole of B formed at 300 K is ______.
(Given : ln(2) = 0.7, R (universal gas constant) = 8.3 J K–1 mol–1. H, S and G are enthalpy, entropy and Gibbs
energy, respectively) [JEE Advanced 2018]
54. Consider a 70% efficient hydrogen-oxygen fuel cell working under standard conditions at 1 bar and 298 K.
Its cell reaction is
H2(g) + ½O2(g) H2O (l).
The work derived from the cell on the consumption of 1.0 × 10–3 mol of H2(g) is used to compress 1.00 mol
of a monoatomic ideal gas in a thermally insulated container. What is the change in the temperature (in K)
of the ideal gas?
The standard reduction potentials for the two half-cells are given below :
O2(g) + 4H+ (aq) + 4e¯ 2H2O (l), Eº = 1.23 V,
2H+(aq) + 2e¯ H2(g), Eº = 0.00 V.
Use F = 96500 C mol–1, R = 8.314 J mol–1 K–1. [JEE Advanced 2020]
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
ANSWER KEY
EXERCISE-I
1. (a) Zn | Zn2+ | | Cd2+ | Cd, (b) Pt | H2 | H+ | | Ag+ | Ag , (c) Cu | Cu2+ | | Cl– | Hg2Cl2 | Hg
(d) Pt | Fe2+, Fe3+ | | Cr2O27 , Cr3+ | Pt
2. (a) 2Ag + Cu2+ 2Ag+ + Cu, (b) MnO 4 + 5Fe2+ + 8H+ Mn2+ + 5Fe3+ + 4H2O
(c) 2Cl– + 2Ag+ 2Ag + Cl2, (d) H2 + Cd2+ Cd + 2H+
3. Anode Cathode
(a) Zn | Zn2+ H+ | H2 | Pt
(b) Pt | Sn2+, Sn4+ Fe3+ , Fe2+ | Pt
(c) Pt | Fe2+, Fe3+ MnO 4 , Mn2+ | Pt
(d) Pb | Pb2+ Br2, Br– | Pt
4. 1.61 V 5. 1.35 V 6. 1.68 V
7. – 0.80 V, NO 8. 0.53 V, disproportionation 9. – 0.0367 V
10. Kc = 7.6 × 1012 11. E =1.159V 12. Kc = 1.96 × 1026
13. Kc = 1.864 × 10107, G0 = – 611.8 kJ 14. Kw 1014
15. E0 = 0.7826 V 16. n=2 17. E = 0.059
18. E = 0.395 V
19. E0cell = +0.01V, Ecell = 0.0785V, correct representation is Pb|Pb2+ (103M)||Sn2+(1M)|Sn
20. [Cu2+] = 2.97 × 1012M for E = 0 21. E = 0.81 V 22. 0.52 V, 0.61 V
23. –1.30 ×103 kJ mol–1 24. 0.0295 V 25. 0.0295 V
26. pH = 4 27. E = 0.0206V 28. a2 = 0.1 M
29. [Br ] : [Cl] = 1 : 200 30. – 0.0348 V
31. (a) 6.02 × 1022 electrons lost, (b) 1.89 × 1022 electrons gained, (c) (b) 1.80 × 1023 electrons gained
32. (a) 0.75 F, (b) 0.69 F, (c)1.1 F 33. (i) 54 gm, (ii) 16.35 gm 34. 96500 sec
35. 86.4 gm, 24.53 litre 36. 0.112 litre 37. 0.24 gms
38. Rs. 0.75 x 39. (i) 2.6 gm ; (ii) 1389.6 sec 40. 115800C, 347.4 kJ
41. t = 193 sec 42. n=4
43. Cu2+ = 0.08M, H+ = 0.04M, SO2 4 = 0.1M 44. Final weight = 9.6g, 0.01 Eq of acid
45. (a) V(O2) = 7.7L, (b)V(O2) = 1.03L 46. t = 93.65 sec. 47. 60 %
48. 7.958 ×10–5M 49. 1.825 g 50. 2M
51. 400 S cm 2 equivalent –1 52. 0.00046 S cm 1 ; 2174 ohm cm
53. (i) 6.25 × 105 ohm, (ii) 1.6 × 106 amp 54. 1.5 cm –1
55. 150 ohm –1 cm 2 / gm equivalent56. 0.0125 mho g equiv –1 m 2, 0.125 mho m –1
57. (i) 232 Mho cm 2 mol –1 , (ii) 116 Mho cm 2 equivalent –1 58. 0.75
59. 1.175 × 10–4 gm/litre 60. 1 × 10–10 mole2 /litre2 61. = 0.4, k = 5.33 × 10–4
62. (i) 390 S cm2mol–1 (ii) 12.3% 63. 1.067 S m –1
64. 523.2 × 10–4 mho cm 2 mol –1 65. (i) 6.98 (ii) 1.08 × 10–14
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PHYSICAL CHEMISTRY NA (SODIUM SIR)
EXERCISE-II
1. E = 1.1 V 2. E° = 1.59V, non-spontaneous 3. Ksp = 1.16 × 1016
4. pH = 6.5 5. E0 = 0.731V
6. E0 = 0.16V 7. 1.38V 8. 0.3668 V
9. = 3.2 × 10–2, Kh= 3.2 × 10–5 M 10. 2 × 10–5 M3
11. K = 10268 12. 1.652V 13. –1.221V
14. 2 × 10–3
15. Eq. wt. = 96 16. [Cu2+] = 104M 17. 603.125 amp,190.5g
18. 38.8g 19. 289.5 Amp. hr. 20. 120625 coulomb
21. 50 % 22. V(O2) = 117.04 mL, V(H2) = 94.08 mL, Total vol. = 211.12 mL
23. 35.2 gm 24. Cu = 79.38%, Fe = 0.84%
25. 1250 s, 0.064 M 26. 0.1456 ampere 27. 3.46 cm
28. 4.25 × 10–2 metre 29. 0.1836 gm/litre 30. KSP = 6.25 × 10–17
QUESTION BANK
1. B 2. A 3. A 4. B 5. D 6. A 7. C
8. C 9. C 10. A 11. B 12. A 13. C 14. C
15. D 16. C 17. C 18. D 19. B 20. C 21. C
22. A 23. B 24. B 25. B 26. D 27. D 28. C
29. C 30. B 31. A 32. A 33. D 34. A 35. D
36. A 37. C 38. C 39. C 40. B 41. D 42. A
43. D 44. B 45. B 46. B 47. C 48. A 49. C,D
50. B,C,D 51. A,B 52. A,B 53. A,C,D 54. A,C 55. B,C 56. A,D
57. A,B 58. A P,Q ; B P,Q ; C Q,R ; D P,S
59. A Q,S ; B Q,R ; C P ; D Q,R 60. A P,Q,R ; B P,Q,S ; C P,Q,R,S ; D P, R
EXERCISE-III
1. B 2. D 3. D 4. C 5. D 6. B 7. A,B,D
8. B 9. C 10. D 11. D 12. B 13. D 14. A
15. A 16. D 17. D 18. B 19. D 20. ONLY A OR A AND C
21. C 22. B,C,D 23. D 24. D 25. B 26. B
27. D 28. A 29. A 30. D 31. C 32. A 33. C
34. B 35. B 36. C 37. A 38. A 39. A 40. D
41. C 42. B 43. D 44. C
45. 0.05 M 46. KC = 1010
47. (a) E0 = 0.59 V, log10KSP = –10 (b) 52.8, 10–6 moles 48. 55 S m–1
49. 4 50. 3 51. 6 52. 10 53. –11.62 JK–1 mol–1
54. 13.00 to 13.60
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