PHYSICAL CHEMISTRY

TARGET : JEE (ADVANCED) 2014

TEST SYLLABUS
Course : VIJETA (JPAD)
Date : 13.04.2014
Syllabus :

TEST : CUMULATIVE TEST-1 (CT-1)

Mole & Equivalent Concept, Ionic equilibrium &

&

VIJAY (JRAD)

Date : 10-04-2014

Electrochemistry.

DPP No. : 01
This DPP is to be discussed in the week (10-04-2014 to 12-04-2014)

DPP No. # 01 (JEE-ADVANCED)

Total Marks : 169

Max. Time : 118 min.

Single correct Objective ('1' negative marking) Q.1 to Q.15

(3 marks, 2 min.)

[45, 30]

One or more correct objective ( no negative marking) Q.16 to Q.20

Single digit integer type ('1' negative marking) Q.21 to Q.25
Double digit integer type (no negative marking) Q.26 to Q.29
Assertion and Reason ('1' negative marking) Q.30 to Q.32
Comprehension ('1' negative marking) Q.33 to Q.41
Match the Following (no negative marking) Q.42 to Q.45

(4
(4
(4
(3
(3
(8

[20,
[20,
[16,
[09,
[27,
[32,

marks,
marks,
marks,
marks,
marks,
marks,

2
3
3
3
2
6

min.)
min.)
min.)
min.)
min.)
min.)

10]
15]
12]
09]
18]
24]

1.

Three oxides of a certain hypothetical element contain 50%, 33.33% and 25% element by mass respectively.
The simplest ratio of the valencies of element in the three oxides is :
(A) 2 : 3 : 4
(B) 3 : 4 : 6
(C) 1 : 2 : 3
(D) None of these

2.

3 g of carbon and 5 g of oxygen react with each other completely. Which of the following options is true
regarding composition of final mixture :
(A) nCO2 = 0.15625 ; nC = 0.09375

(B) n CO = 0.0625 ; nCO2 = 0.1875

(C) n CO = 0.25 ; nO2 = 0.03125

(D) n CO = 0.1875 ; nCO2 = 0.0625

3.

If the density of methanol is 0.792 kg L1, what is its volume needed for making 0.0027 m 3 of its 0.22 M
solution ?
(A) 0.24 dm3
(B) 24 cm3
(C) 24 dm3
(D) 2.4 cm3

4.

In the permaganate titration, the solution of reductant is made acidic by adding dil. H2SO4, rather than HCl
or HNO3 because :
(A) HCl is a reducing agent and it gets oxidised resulting into decrease in the volume of KMnO4 equivalent to
the reducing agent under estimation.
(B) HNO3 is an oxidising agent and it gets reduced resulting into increase in the volume of KMnO4 equivalent
to the reducing agent under estimation.
(C) H2SO4 (dil) is neither an oxidizing agent nor a reducing agent.
(D) All of these

5.

2 litres of an acidified solution of KMnO4, containing 1.58 g of KMnO4 per litre, is decolourised by passing
sufficient amount of SO2 gas. If whole of the of the sulphur from x g of FeS2 is converted into SO2 to be used
in above reaction, calculate the value of x :
(A) x = 1.5
(B) x = 3
(C) x = 4.5
(D) x = 6
Page No # 1

6.

A certain volume of hydroxyl amine (NH2OH) solution was boiled with an excess of FeCl3 solution to cause
the reduction of Fe3+ ions according to the reaction :
Fe3+ + NH2OH Fe2+ + N2O + H+ + H2O
The resulting solution was estimated for Fe2+ ions with 0.5 M K2Cr2O7 solution in acidic medium. If the volume
of K2Cr2O7 solution and NH2OH solution used are found to be equal, what is the molarity of NH2OH solution:
(A) 1.5 M
(B) 3 M
(C) 0.75 M
(D) 1 M

7.

An unknown sample was dissolved in water and made to titrate with 0.1 M HCl solution initially using
phenolphthalein indicator. The volume of HCl consumed was found to be VP ml. Then to the resulting solution,
methyl orange indicator was added and again titrated with same HCl solution. The volume of HCl consumed
now was found to be VM ml. If VP = VM, then the unknown sample might not contain :
(A) only Na2CO3
(B) equimolar mixture of NaOH, Na2CO3 and NaHCO3
(C) equimolar mixture of NaOH and NaHCO3
(D) equimolar mixture of NaOH and Na2CO3

8.

Calculate (i) [H+] and (ii) [PO43] in a 0.15 M solution of phosphoric acid, H3PO4. Given that for H3PO4 :
Ka = 7.5 103, Ka = 6.2 108, Ka = 3.6 1013.
1
2
3
(A) [H+] = 0.03 M
(B) [PO43] = 7.44 1019 M
(C) Both (A) and (B)
(D) None of these

9.

The pH of a solution containing 0.1 M CH3COONa and 0.1 M (C2H5COO)2Ba will be :

Ka(CH3COOH) = 2 105, Ka(C2H5COOH) = 8 106 :
(A) 8.13
(B) 9.24
(C) 10.18
(D) 11.18

10.

60 mL of 0.2 M Ba(OH)2 solution is added to 50 mL of 0.6 N H3PO4 solution. The pH of the mixture would be
about : (Ka1, Ka2 and Ka3 for H3PO4 are 103, 108 and 1012 respectively).
(A) 11.82
(B) 3.6
(C) 12.18
(D) 7.82

11.

The solubility product of As2O3 is 10.8 109. It is 50% dissociated in saturated solution. The solubility of
salt is :
(A) 102

(B) 2 102

(C) 5 103

(D) 5.4 109

12.

At 298K the standard free energy of formation of H 2O() is 257.20 kJ/mole while that of its
ionisation into H+ ion and hydroxyl ions is 80.35 kJ/mole, then the emf of the following cell at
298 K will be(take F = 96500 C]
H2(g,1 bar) | H+ (1M) || OH (1M) | O 2 (g, 1bar)
(A) 0.40 V
(B) 0.50 V
(C) 1.23 V
(D) 0.40 V

13.

A galvanic cell is composed of two hydrogen electrodes, one of which is a standard one. In which of the
following solutions should the other electrode be immersed to get maximum e.m.f. (Ka = 105 for acetic
acid and Ka = 103 for phosphoric acid)
(A) 0.1 M HCl

(B) 0.1 M CH3COOH

(C) 0.1 M H3PO4

(D) 0.1 M H2SO4

14.

Electrolytic reduction of 6.15 g of nitrobenzene using a current effeciency of 40% will require which of the
following quantity of electricity. [C = 12, H = 1, N = 14, O = 16]
(A) 0.75 F
(B) 0.15 F
(C) 0.75 C
(D) 0.125 C

15.

The conductivity of a solution which is 0.2M in AgNO3 and 0.1M in Ba(NO3)2 is :

[ (Ag+) = 6 103 Sm2mol1 , (Ba2+) = 13 103 Sm2 mol1 and (NO3) = 7 103 Sm2mol1 ]
Page No # 2

(A) 5.3 Sm1

(B) 4.3 Sm1

(C) 3.3 Sm1

(D) 2.3 Sm1

16.

Which of the following statements is/are correct :

(A) Valency factor of Wustite (Fe0.93O) in it's oxidation to Fe3+ is 0.79.
(B) Both the chlorine present in bleaching powder have same individual oxidation number, zero.
(C) In case of iodimetric titration, KI is made to react with an oxidising agent and the liberated I2 gas is made
to titrate with hypo solution.
(D) Equivalent mass of Cu3P in the given reaction is M/11 (where M = mol. mass)
Cu3P + KMnO4 + H+ Cu2+ + H2PO4 + K+ + Mn2+

17.

The pH of 0.1 M solution of a weak base is 11. On diluting the solution, select the INCORRECT statement(s):
(A) pH increases
(B) [OH] increases
(C) decreases
(D) Number of H+ ions in solution increases

18.

Identify the correct statement(s) :

(A) A solution prepared by dissolving 0.1 mole of H3PO4 in 250 mL solution will have [H3PO4] + [H2PO4] +
[HPO42] + [PO43] = 0.4 M.
(B) Titration curves for the titration of 0.1 M oxalic acid with 0.1 M NaOH and 0.2 M oxalic acid with 0.2 M
NaOH both pass through the same pH at the 1st equivalence point.
(C) Solubility of Fe(OH)3 (Ksp = 4 1038) in water is less than

K sp / 27 .

(D) The solubility of SrF2 in water exceeds 3 K sp / 4 .

19.

On electrolysis, in which of the following , O2 would be liberated at the anode :

(A) dilute H2SO4 with Pt electrodes
(B) aqueous AgNO3 solution with Pt electrodes
(C) dilute H2SO4 with Cu electrodes
(D) aqueous NaOH solution with Fe cathode & Pt anode

20.

Mark out the correct statement(s) regarding electrolytic molar conductivity :

(A) It increases as temperature increases.
(B) It experiences resistance due to vibration of ions about mean position.
(C) Increase in concentration decreases the electrolytic molar conductivity of both strong as well as weak
electrolyte.
(D) Greater the polarity of solvent, greater is the electrolytic molar conduction.

21.

(a) 'a' moles of K2Cr2O7 are needed in acidic medium for the oxidation of 9 moles of ethanol to acetic acid.
(b) An unknown metal chloride undergoes reduction reaction with Mg producing metal and MgCl2. Experiments
show that 52.4 g of metal chloride reacts with 9.6 g of Mg according to above reaction. The equivalent weight
of metal in the given metal chloride is 'b'.
b
Report your answer as .
a

22.

Determine the concentration of H3O+ ion (in mol/L) in a solution containing 2 103 M HOCl & 2 104 M
NaOCl. Given : Dissociation constant of HOCl = 1.5 104.
Report your answer after multiplying by 10,000.

23.

Determine the number of moles of AgI which may be dissolved in 1 L of 1 M CN solution. Ksp for AgI and
Kf for [Ag (CN)2] are 4 10 17 M2 & 6.25 1017 respectively .
Report your answer after multiplying by 11.
Page No # 3

24.

How many of the following statements is/are correct?

(i) The discharging of lead storage battery constitutes a galvanic cell.
(ii) During charging of lead stroage battery, anode is negatively charge.
(iii) The mass lost at anode is equal to mass gained at cathode in any galnanic cell
(iv) Ecell is intensive quantity and is independent of temperature
(v) The overall reaction in an electrolytic cell need not always look like a redox reaction.
(vi) If E0cell of a cell reaction is negative, then the reaction is non-spontaneous under all conditions.

25.

Pure water is saturated with pure solid AgCl. A silver rod is placed in the solution and the potential is
measured against normal calomel electrode at 25C. This experiment is then repeated with a saturated
solution of AgI. If the difference in potential in the two cases is 0.177V, the ratio of solubility product (Ksp) of
AgCl and AgI at the temperature of the experiment is 10x . Determine the value of x.

26.

89.6 litres of a mixture of nitrogen and hydrogen measured at S.T.P. were passed over a catalyst. After the
reaction, the volume of the mixture reduced to 67.2 litres. Ammonia thus formed was dissolved in 100 mL
of an aqueous ammonia solution of density 0.83 g/mL containing 11 % by mass of NH4OH. Determine the
percent weight strength of the final solution.
Report your answer rounding it off to the nearest whole number.

27.

A certain amount of Dichloroacetic acid (CHCl2COOH) is oxidised to CO2, H2O and Cl2 by 300 gram-equivalents
of KMnO4 in acidic medium. How many moles of Barium hydroxide are required to completely neutralize the
same amount of acid ?

28.

Calculate the volume (in mL) of 0.1 M Na2SO4 solution, which must be added to 10 mL of HCl solution
(pH = 1), so that pH of the resulting solution becomes 2. (Given : Ka for H2SO4 = 102 and Ka = )
2

29.

During the preparation of H2S2O8 (peroxydisulphuric acid) using H2SO4 electrolytically, O2 gas also releases
at anode as by product. When 10.08 L of H2 releases at cathode and 2.24 L O2 at anode at STP, the weight
of H2S2O8 produced in gram is : (Round it off to nearest whole number)

30.

STATEMENT-1 : If KIO3 reacts with excess KI in acidic medium, and the produced I2 is titrated with hypo
solution, then milliequivalents of KIO3 used and hypo used are equal.
STATEMENT-2 : According to law of equivalence, in a chemical reaction, milliequivalents of all the reactants
are equal and also equal to milliequivalents of each product.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True

31.

STATEMENT-1 : The pH of a 0.003 M aqueous solution of NH4CN can be approximately calculated using the
formula : pH =

1
( pK w + pK a pK b ) Given : Ka(HCN) = 4 1010 & Kb(NH3) = 2 105
2

STATEMENT-2 : The degree of hydrolysis (h) of NH4CN in its 0.003 M aqueous solution comes out to be
greater than 0.1 and so, its value cannot be neglected with respect to 1 .
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True
Page No # 4

32.

Statement-1 : Ecell = 0 for a chloride ion concentration cell.

Statement-2 : For this concentration cell, Ecell =

[Cl ]LHS
RT
ln
.
nF
[Cl ]RHS

(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True
Comprehension # 1
For a reaction : aA + bB cC + dD
Three students stated different ways of determining limiting reagent.
Student 1 : Calculate the minimum moles of 'A' needed to completely consume 'B', and if available amount
of 'A' exceeds what is needed, then 'B' is limiting reagent otherwise 'A' will be limiting reagent.
Student 2 : Calculate the ratio of the moles of the reactants initially taken, then compare it to theoretical
mole ratio(according to stochiometry of the reaction). If the theoretical ratio exceeds ratio of moles actually
taken, then reactant in numerator will be limiting reagent.
Student 3 : Calculate the amount of product (any one of the product) that can be obtained if each reactant
is completely consumed and that reactant is limiting reagent which has produced least mass of product.
Assume that atleast one of A or B is the limiting reagent.
Now answer the following two questions :
33.

34.

Which student(s) has/have defined limiting reagent correctly :

(A) Student-1
(B) Student-2
(C) Student-3

(D) All of these

If Student 1 in first experiment finds that when 1 mole of 'A' reacted with excess of reagent 'B' and in second
experiment when 1 mole of 'B' reacted with excess of reagent 'A', then in the later experiment mass of the
product produced was greater. Then which should be the limiting reagent :
(A) A
(B) B
(C) None
(D) Cannot be predicted

Comprehension # 2
Zelina, a student of class XI is working in the chemistry lab of her school. She is provided with 4 containers
of large capacity by the lab assistant.
Container 1 contains 2L of '2.8 V' H2O2.
Container 2 contains 2L of '16.8 V' H2O2.
Container 3 contains sufficient amount of water.
Container 4 is empty.
She has been asked by her teacher to prepare H2O2 solution using the components of container 1, 2 or 3
(partially or completely) and store it in container 4.
Now answer the following two questions :
35.

The volume of water required by Zelina to prepare maximum volume of 2.55% (w/v) H2O2 solution is :
(A) 0.33 L
(B) 1 L
(C) 0.67 L
(D) 2 L

36.

Zelina prepared a 12.6 V H2O2 solution and mixed it with excess of KI solution and titrated the liberated I2 with
9
M hypo solution. Find the maximum volume (in L) of hypo solution that could have been consumed in
7

above process :
(A) 5.44 L

(B) 5 L

(C) 4.67 L

(D) 2.5 L
Page No # 5

Comprehension # 3

Zwitter ions
The chemistry of amino acids is complicated by the fact that the -NH2 group is a base and the -CO2H group is an
acid. In aqueous solution, an H+ ion is therefore transferred from one end of the molecule to the other to form a
zwitter ion (from a German word meaning mongrel ion or hybrid ion).

Zwitter ions are simultaneously electrically charged and electrically neutral. They contain positive and negative
charges, but the net charge on the molecule is zero.
Imagine what would happen if we add a strong acid to a neutral solution of an amino acid in water. In the presence
of strong acid, the -CO2 end of this molecule picks up an H+ ion to form a species with a net positive charge.

In the presence of a strong base, the -NH3+ end of the molecule loses an H+ ion to form a species with a net
negative charge.

The figure below shows what happens to the pH of an acidic solution of glycine when amino acid is titrated with
a strong base, such as NaOH.

In order to understand this titration curve, let's start with the equation that describes the acid-dissociation equilibrium
constant expression for an acid, HA.
Ka

[H3O ][ A ]
[HA ]

The following occurs as we go from left to right across this titration curve.
The pH initially increases as we add base to the solution because the base deprotonates some of the
positively charged H3N+CH2CO2H ions that were present in the strongly acidic solution.
The pH then levels off because we form a buffer solution in which we have resonable concentrations of both
an acid, H3N+CH2CO2H, and its conjugate base, H3N+CH2CO2.
When virtually all of the H3N+CH2CO2H molecules have been deprotonated, we no longer have a buffer
solution and the pH rises rapidly when more NaOH is added to the solution.
The pH then levels off as some of the neutral H3N+CH2CO2 molecules lose protons to form negatively
charged H2NCH2CO2 ions. When these ions are formed, we once again get a buffer solution in which the pH
remains relatively constant until essentially all of the H3N+CH2CO2H molecules have been converted
into H2NCH2CO2 ions.
At this point, the pH rises rapidly until it reaches the value observed for a strong base.
Somewhere between these extremes, we have to find a situation in which the vast majority of the amino
acids are present as the zwitter ion - with no net electric charge. This point is called the isoelectric point (pI)
of the amino acid.
Now answer the following three questions :
Page No # 6

37.

38.

The isoelectric point of an amino acid is :

(A) The pH at which it exists in the acidic form.
(B) The pH at which exists in the basic form.
(C) The pH at which it exists in the Zwitter ion form
(D) The pH which is equal to its pKa value.

+
pKa = 2.35 and pKa = 9.78 for acidic form of glycine. Calculate pH at isoelectric point of NH 3 CH 2 COO :
1

(A) 6.06
39.

(B) 9.78

(C) 2.35

(D) 12.13

Which is the INCORRECT statement regarding titration curve of titration of acidic solution of glycine with
NaOH solution :

+
(A) NH
give dibasic acid titration with NaOH.
3CH 2COOH
+

+
(B) NH 3CH 2COOH and NH 3CH 2COO mixture form during titration can behave as buffer..
(C) pH at Ist equivalence point is equal to pH of isoelectric point.
(D) At pH = pKa , 25% titration has been completed.
2

Comprehension # 4
The cell potential for the unbalanced chemical reaction :
Hg22+ + NO3 + H3O+ Hg2+ + HNO2 + H2O
under standard state conditions is Ecell = 0.02 V
Given : NO3 + 3H3O+ + 2e HNO2 + 4H2O, E = 0.94 V

and

2.303RT
= 0.06.
F

Now answer the following two questions :

Hg22+ + NO3 + H3O+ Hg2+ + HNO2 + H2O
40.

At what pH will the cell potential be zero if the concentration of other components are equal to one ?
(A)

1
6

(B)

1
3

(C)

2
3

(D)

2
9

41.

How many moles of electrons pass through the circuit when 0.6 mole of Hg2+ and 0.30 mole of HNO2 are
produced in the cell that contains 0.5 mole of Hg22+ and 0.40 mole of NO3 at the beginning of the reaction
(A) 0.6 mole
(B) 0.8 mole
(C) 0.3 mole
(D) 1 mole

42.

Match the following :

Column ()
(A) 50 mL of 3M HCl solution + 150 mL of 1M FeCl3 solution
(B) An aqueous solution of NaCl with mole fraction of NaCl as 0.1
(C) 20% (w/w) propanol (C3H7OH) solution

Column ()
(p) 4.17 m
(q) [Cl] = 3 M
(r) [H+] = 0.75 M

(D) 10.95% (w/v) HCl solution

(s) 6.1 m

Page No # 7

43.

Column I
(Reactions)

Column II
(Information conveyed by the reactions)

(A) Complete reaction of Cupric sulphide

with acidified Potassium permanganate

(p) The element in oxidant, which undergoes change in

oxidation number, is in its maximum possible state.

solution producing a bent-shaped gas.

(B) Reaction of HI and HNO3 producing a
halogen gas and nitric oxide gas.

(q) Greater than one mole of oxidising agent is

consumed for every mole of reducing agent.

(C) Reaction of I2 with Hypo producing Sodium

(r) Valency factor of at least one reactant (oxidising

iodide and Sodium tetrathionate.

agent or reducing agent) is unity (1).

(D) Complete reaction of Ferrous oxalate with

acidified Potassium dichromate solution

(s) Moles of reductant consumed is greater than or equal

to twice the moles of oxidant consumed.

producing a gas isoelectronic and

isostructural with nitrous oxide.
(t) Gases evolved do not have their constituent
element (other than oxygen) in their maximum possible
oxidation states.
44.

Column I
(A) AgBr

Column II
(p) Solubility in water is more than expectation.

(B) AgCN

(q) Solubility in acidic solution is more than that

in pure water.
(r) Solubility in strongly basic solution is more
than that in pure water.
(s) Solubility decreases in presence of common
anion.

(C) Fe(OH)3
(D) Zn(OH)2

45.

Match the following electrochemical cells at 25C in Column-I with their characteristics in Column-II :
0
0
0
Given : E Zn 2 / Zn = 0.76 V, E Ag / Ag = 0.81 V,, ED / D = 0.01 V
2

Ksp (AgCl) = 1010, Ksp (AgBr) = 5 1013

Column-I
(A)

Pt(s)| H2 (g)| KOH (aq) || HCl (aq)| H2 (g)| Pt (s)

(1atm)

(B)

Column-II

(0.01M)

(0.01M)

Concentration cell

(q)

Ecell > 0

(r)

Cell reaction is at equilibrium

(1atm)

Zn(s)| Zn2+ (aq)|| Ag+ (aq) | Ag (s)

(0.1M)

(p)

(0.1M)

(C)

Pt(s)| D2 (g)| D+ (aq) || H+ (aq)| H2 (g)| Pt (s)

(D)

Ag(s)| AgBr (s)| Br (aq) || Cl (aq)| AgCl (s)| Ag (s) (s)

(0.1atm)

(0.1M)

(0.01M) (0.001atm)

(5104M)

Cell will have the same emf as the one

made up of standard electrodes.

(0.1M)

(t)

Diluting each electrode solution to double

volume would not affect the emf of cell
(for gases involved, assume no change
in partial pressures).
Page No # 8