IIT-JEE-Chemistry–1998

Time : 2 hrs. Max. Marks :100

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Instructions

1. This question paper is in two sections and contains eight pages. Section I has 40
objective type questions. Section II has 15 question. There are no negative marks for wrong
answers.
2. Answer section I only on the printed form on the third page of the answer book.
3. Answer questions-problems of section II starting from page 4 of the answer book. All
parts of a question must be answered sequentially at one place only.
4. Attempt all questions.
5. Answers must be written only in the language of your choice as shown in your admit
card.
6. Use of logarithmic tables is permitted.
7. Use of slide rule/Calculator is not permitted.

Useful data :
Gas constant, R = 0.082 litre atm K–1 mol–1
= 1.987 cal K–1 mol–1
= 8.314 J K–1 mol–1
1 Faraday constant = 96.500 Coulombs mol–1
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SECTION I

Instructions :
1. You must first transfer the Question Paper Code given on top of this section to your
answer book in the appropriate box marked Question Paper Code.
2. Answer Section I only on the printed form on the third page of your answer book by
writing the appropriate letters (A), (B), (C), (D) against the question number in the table.
Answers for section I written in this space alone will be awarded marks.
3. Section I consists of 40 objective type questions.
4. This section should take about one hour to answer.
5. Each question in this section carries 2 marks.
6. Read questions 1 to 28 carefully and choose from amongst the alternatives given below
each question the correct lettered choice(s). A question may have one or more correct
alternatives. In order to secure any marks for a given question, all correct lettered
alternative(s) must be chosen.

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1. Which of the following statement(s) is(are) correct when a mixture of NaCI and
K2Cr2O7 is gently warmed with conc. H2SO4 :

(A) A deep red vapour is evolved

(B) The vapour when passed into NaOH solution gives a yellow solution of Na2CrO4
(C) Chlorine gas is evolved
(D) Chromyl chloride is formed.

2. Highly pure dilute solution of sodium in liquid ammonia :

(A) Shows blue colour
(B) exhibits electrical conductivity
(C) produces sodium amide
(D) produces hydrogen gas

4. p-Chloroaniline and anilinium hydrochloride can be distinguished by:

(A) Sandmeyer reaction (B) NaHCO3
(C) AgNO3 (D) Carbylamine test

5. The energy of an electron in the first Bohr orbit of H atom is – 13.6 eV. The possible
energy value(s) of the excited state(s) for electrons in Bohr orbits of hydrogen is(are) :
(A) – 3.4 eV (B) – 4.2 eV
(B) – 6.8 eV (D) + 6.8 eV

6. In nitroprusside ion the iron and NO exist as FeII and NO+ rather than FeIII and

NO. These forms can be differentiated by :

(A) estimating the concentration of iron.

(B) measuring the concentration of CN.
(C) measuring the solid state magnetic moment.
(D) thermally decomposing the compound.

7. Which of the following statement(s) is(are) correct :

(A) The coordination number of each type of ion in CsCI crystal is 8.
(B) A metal that crystallizes in bcc structure has a coordination number of 12.
(C) A unit cell of an ionic crystal shares some of its ions with other unit cells.
(D) The length of the unit cell in NaCI is 552 pm. ( rNa+ = 95 pm; rCI- =181 pm)
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8. Sodium nitrate decomposes above –8000C to give :
(A) N2 (B) O2
(C) NO2 (D) Na2O

9. Which of the following statement(s) is(are) correct with reference to the ferrous and
ferric ions :
(A) Fe3+ gives brown colour with potassium ferricyanide.
(B) Fe2+ gives blue precipitate with potassium ferricyanide.
(C) Fe3+ gives red colour with potassium thiocyanate.
(D) Fe2+ gives brown colour with ammonium thiocyanate.

10. Which of the following statement(s) is(are) correct :

(A) The electronic configuration of Cr is [Ar] 3d5 4s1. (Atomic Number of Cr = 24.)
(B) The magnetic quantum number may have a negative value.
(C) In silver atom, 23 electrons have a spin of one type and 24 of the opposite type.
(Atomic Number of Ag = 47).
(D) The oxidation state of nitrogen in HN3 is –3.

11. A new carbon-carbon bond formation is possible in

(A) Cannizzaro reaction (B) Friedel-Crafts alkylation
(C) Clemmensen reduction (D) Reimer-Tiemann reaction

12. White phosphorus (P4) has :

(A) six P–P single bonds (B) four P–P single bonds
(C) four lone pairs of electrons (D) PPP angle of 600.

13. Which of the following will react with water :

(A) CHCI3 (B) CI3CCHO
(C) CCI4 (D) CICH2CH2CI

14. The standard reduction potential values of three metallic cations, X, Y, Z are 0.52, –
3.03 and –1.18V respectively. The order of reducing power of the corresponding metals
is:
(A) Y > Z > X (B) X > Y > Z
(C) Z > Y > X (D) Z > X > Y

15. Among the following compounds, which will react with acetone to give a
product containing >C = N – :
(A) C6H5NH2 (B) (CH3)3 N
(C) C6H5NHC6H5 (D) C6H5NHNH2

16. Which of the following compounds will show geometrical isomerism:

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(A) 2-butene (B) propone
(C) 1-phenylpropene (D) 2-methyl-2-butene

17. The geometry and the type of hybrid orbital present about the central atom in BF3 is:
(A) linear, sp (B) trigona planar, sp2
(C) tetrahedral, sp3 (D) pyramidal, sp3

18. Benzyl chloride (C6H5CH2CI) can be prepared from toluene by chlorination with :
(A) SO2CI2 (B) SOCI2
(C) CI2 (D) NaOCI

19. Which of the following will undergo aldol condensation :

(A) acetaldehyde (B) propanaldehyde
(C) benzaldehyde (D) trideuteroactaldehyde

20. Addition of high proportions of manganese makes steel useful in making rails
(A) gives hardness to steel.
(B) helps the formation of oxides of iron.
(C) can remove oxygen and sulphur
(D) can show highest oxidation state of +7.

21. Decrease in atomic number is observed during :

(A) alpha emission
(B) beta emission
(C) positron emission
(D) electron capture.

22. Benzenediazonium chloride on reaction with phenol in weakly basic medium gives :
(A) diphenyl ether
(B) p-hydroxyazobenzene
(C) chlorobenzene
(D) benzene

23. Among the following compounds, the strongest acid is:

(A) HC º CH
(B) C6H6
(C) C2H6
(D) CH3OH

24. For a first order reaction :

(A) the degree of dissociation is equal to (1 – e–kt).
(B) a plot of reciprocal concentration of the reactant vs. time gives a straight line.
(C) the time taken for the completion of 75% reaction is thrice the t1/2 of the reaction.

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(D) the pre-exponential factor in the Arrhenius equation has the dimension of time, T–1.

26. According to Graham’s law, at a given temperature the ratio of the rates of diffusion
rA/rB of gases A and B is given by:
(A) (PA / PB) (MA / MB)1/2
(B) (MA / MB) (PA / PB)1/2
(C) (PA/ PB ) (MB / MA)1/2
(D) (MA / MB) (PB/ PA)1/2

27. For the reaction CO(g) + H2O(g) «CO2 (g) + H2(g) at a given temperature, the
equilibrium amount of CO2(g) can be increased by:
(A) adding a suitable catalyst
(B) adding an inert gas
(C) decreasing the volume of the container.
(D) increasing the amount of CO (g).

28. Which of the following statement(s) is(are) correct :

(A) The pH of 1.0 × 10–8 M solution of HCI is 8.
(B) The conjugate base of H2PO4– is HPO42–.
(C) Autoprotolysis constant of water increases with temperature.
(D) When a solution of a weak monoprotic acid is titrated against a strong base, at half-
neutralisation point pH = (1/2) pKa.

ASSERTION-REASON TYPE QUESTIONS

Directions : The questions below (29 to 40) consist of an assertion in column 1 and the
reason in column 2. Against the specific question number, write in the appropriate space.
(A) If both assertion and reason are correct, and reason is the correct explanation of the
assertion.
(B) If both assertion and reason are correct, but reason is not the correct explanation of the
assertion.
(C) If assertion is correct but reason is incorrect.
(D) If assertion is incorrect but reason is correct.

Example :
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 Assertion Reason
F–F bond in F2 molecule is strong. F atom is small in size.
Answer : (D)
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29. Benzonitrile is prepared by the Cyanide (CN–) is a strong nucleophile.

reaction of chlorobenzene with
potassium cyanide.

30. F atom has a less negative electron Additional electrons are repelled more effectively
affinity than CI atom. by 3p electrons in CI atom than by 2p electrons in
F atom.

Nuclides having odd number of protons and

31. Nuclide 30 Ai13 is less stable neutrons are general unstable.
than 40Ca20.
AI — O and O — H bonds can be broken with
equal ease in AI(OH)3.

32. AI (OH)3 is amphoteric in nature Hydrogen bonding is present in ammonia.

33. The value of Van der Waals’ The electrons are lost from 4s orbital to form
constant ‘a’ is larger for ammonia than ZN2+.
for nitrogen.
The product contains one asymmetric carbon.
34. ZN2+ is diamagnetic.

35. Addition of Br2 to 1–butene gives

two optical isomers.

36. The electronic structure of O3 is

structure is not allowed because octet around O

cannot be expanded.

Electronegativity difference between Li and CI is

too small.

In HNO3 there are two nitrogen-to-oxygen bonds

whereas in HNO2 there is only one.
37. LiCI is predominantly a covalent

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compound. Ionic radius of Mg2+ is smaller than that of
Ba2+.

Acetic acid has no alpha hydrogens.

38. HNO3 is a stronger acid than HNO2.

39. Sulphate is estimated as BaSO4 and

not as MgSO4.

40. Acetic acid does not undergo

haloform reaction.

SECTION II

Instructions :

1. There are 15 questions in this section.

2. At the end of the answer to a question, leave 3 cm blank space, draw a horizontal line
and start the answer to the next question. The corresponding question number must be
written in the left margin. Answer all parts of a question at one place only.
3. The use of Arabic numerals (0, 1, 2, ……9) only is allowed in answering the questions
irrespective of the language in which you answer.

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1. (a) When the ore haematite is burnt in air with coke around 20000C along with lime, the
process not only produces steel but also produces a silicate slag that is useful in making
building materials such as cement. Discuss the same and show through balanced chemical
equations.
(b) Draw the structure of a cyclic silicate, (Si3O9)6– with proper labeling.
(c) During the qualitative of a mixture containing CU2+ and ZN2+ ions, H2S gas is passed
through an acidified solution containing these ions in order to test Cu2+alone. Explain
briefly.

2. (a) Thionyl chloride can be synthesized by chlorinating SO2 using PCI5. Thionyl chloride
is used to prepare anhydrous ferric chloride starting from its hexahydrated salt.
Alternatively, the anyhydrous ferric chloride can also be prepared from its hexahydrated salt
by treating with 2, 2-dimethoxypropane. Discuss all this using balanced chemical
equations.
(b) Reaction of phosphoric acid with Ca5(PO4) F yields a fertilizer “triple superphospate”
Represent the same through balanced chemical equation.
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3. (a) Complete and balance the following chemical equations.
(i) P4O10 + PCI5 ®
(ii) SnCI4 + C2H5CI + Na ®
(b) Work out the following using chemical equations.
(i) In moist air, copper corrodes to produce a green layer on the surface.
(ii) Chlorination of calcium hydroxide produces bleaching powder.

4. (a) An aqueous solution containing 0.10g KIO3 (formula weight = 214.0) was treated
with an excess of KI solution. The solution was acidified with HCI. The liberated I2
consumed 45.0 mL of thiosulphate solution decolourise the blue starch-iodine complex.
Calculate the molarity of the sodium thiosulphate solution.
(b) Calculate the equilibrium constant for the reaction, 2Fe3+ + 3I– ® 2Fe2+ + I3-.

The standard reduction potentials in acidic conditions are 0.77 V and 0.54 V respectively for
Fe3+|Fe2+ and I3-| I3- couples.

5. (a) Interpret the non-linear shape of H2S molecule and non-planar shape of PCI3using
valence shell electron pair repulsion (VSEPR) theory. (Atomic numbers : H = 1; P = 15, S =
16; CI = 17)
(b) Hydrogen peroxide acts both as an oxidizing and as a reducting agent in alkaline
solution towards certain first row transition metal ions. Illustrate both these properties of
H2O2 using chemical equations.

6. Give reasons for the following in one or two sentences.

(a) Acid catalysed dehydration of t-butanol is faster than that of n-butanol.
(b) The central carbon-carbon bond in 1, 3–butadiene is shorter than that of n-butane.
(c) Dimethylamine is a stronger base than trimethylamine.
(d) Nitrobenzene does not undergo Friedel-Crafts alkylation.

7. (a) An ester A (C4H8O2), on treatment with excess methyl magnesium chloride followed
by acidification, gives an alcohol B as the sole organic product. Alcohol B, on oxidation with
NaOCI followed by acidification, gives acetic acid. Deduce the structures of A and B. Show
the reactions involved.
(b) An aldehyde A (C11H8O), which does not undergo self aldol condensation, gives
benzaldehyde and two moles of B on ozonolysis. Compound B, on oxidation with silver ion
gives oxalic acid. Identify the compounds A and B.

8. Each of the following reactions gives two products. Write the structures of the products.

9. (a) Write the intermediate steps for each of the following reactions.
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(b) Show the steps to carry out the following transformations.
(i) Ethylbenzene --> benzene
(ii) Ethylbenzene --> 2-phenylpropionic acid

10. Complete the following reactions with appropriate structures of products/reagents.

11. (a) A evacuated glass vessel weighs 50.0 g when empt, 148.0 g when filled with a liquid
of density 0.98 mL–1 and 50.5 g when filled with an ideal gas at 760 mm Hg at 300 K.
Determine the molar mass of the gas.
(b) From the following data, calculate the enthalpy change for the combustion of
cyclopropane at 298 K. The enthalpy of formation of CO2 (g), H2O (I) and propene (g) are
– 393.5, –285.8 and 20.42 kJ mol–1 respectively. The enthalpy of isomerisation of
cyclopropane to propene is –33.0 kJ mol–1.

12. (a) The degree of dissociation is 0.4 at 400 K and 1.0 atm for the gaseous reaction
PCI5 « PCI3 + CI2. Assuming ideal behaviour of all the gases, calculate the density of
equilibrium mixture at 400 K and 1.0 atmosphere. (Relative atomic mass of P = 31.0 and CI
= 35.5)
(b) Given : Ag(NH3)2+« Ag+ + 2NH3, Kc = 6.2 × 10–8 and Ksp of AgCI =1.8 × 10–10
at 298 K.If ammonia is added to a water solution containing excess of AgCI(s)
only,.Calculate the concentration of the complex in 1.0 M aqueous ammonia..

13. (a) Using Van der Waal’s equation, calculate the constant, ‘a’ when two moles of a gas
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confined in a four litre flask exert a pressure of 11.0 atmospheres at a temperature of 300
K. The value of ‘b’ is 0.05 L mol–1.
(b) A solution of a non-volatile solute in water freezes at –0.300C. The vapour pressure of
pure water at 298K is 23.51 mm Hg and Kf for water is 1.86 Kg mol–1. Calculate the vapour
pressure of this solution at 298 K.

14. (a) The rate constant of a reaction is 1.5 × 107 s–1 at 500C and 4.5 × 107 s–1at
1000C. Evaluate the Arrhenius parameters A and Ea.
(b) For the reaction, N2O5 (g) = 2NO2 (g) + 0.5 O2 (g), calculate the mole fraction
N2O5 (g) decomposed at a constant volume and temperature, if the initial pressure is 600
mm Hg and the pressure at any time is 960 mm Hg. Assume ideal gas behaviour.

15. (a) Find the solubility product of a saturated solution of Ag2CrO4 in water at 298K if the
emf of the cell Ag | Ag+ (satd. Ag2CrO4 soln.) || AG+ (0.1M) | Ag is 0.164 V at 298 K.
(b) What will be the resultant pH when 200 mL of an aqueous solution of HCI (pH = 2.0) is
mixed with 300 mL of an aqueous solution of NaOH (pH = 12.0)?

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