IIT-JEE-Chemistry–1998

Time : 2 hrs.                                                                           Max. Marks : 100

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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. ( r + = 95 pm; r - =181 pm) Na CI

8. Sodium nitrate decomposes above –800 C to give : 0

(A) N                                       (B) O
2 2

(C) NO                                     (D) Na O
2 2

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] 3d 4s . (Atomic Number of Cr = 24.)
5 1

(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 (P ) has : 4

(A) six P–P single bonds                        (B) four P–P single bonds
(C) four lone pairs of electrons               (D) PPP angle of 60 . 0

13. Which of the following will react with water :

(A) CHCI                                           (B) CI CCHO
3 3

(C) CCI                                                       (D) CICH CH CI

4 2 2
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) C H NH                                     (B) (CH3)3 N
6 5 2

(C) C H NHC H                                    (D) C H NHNH

6 5 6 5 6 5 2

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

(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 (C H CH CI) can be prepared from toluene by chlorination with :
6 5 2

(A) SO CI                                 (B) SOCI

2 2 2

(C) CI                                    (D) NaOCI

2

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) C H
6 6

(C) C H
2 6

(D) CH OH 3

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 t of the reaction. 1/2

(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 r /r of A B

gases A and B is given by:

(A) (P / P ) (M / M )
A B A B
1/2

(B) (M / M ) (P / P )
A B A B
1/2

(C) (P / P ) (M / M )
A B B A
1/2

(D) (M / M ) (P / P )
A B B A
1/2

27. For the reaction CO(g) + H O(g) «CO (g) + H (g) at a given temperature, the equilibrium
2 2 2

amount of CO (g) can be increased by:

2

(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 M solution of HCI is 8. –8

(B) The conjugate base of H PO is HPO . 2 4

–
4
2–

(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 :
_____________________________________________________________________
                  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 reaction of     Cyanide (CN–) is a strong nucleophile.

chlorobenzene with potassium cyanide.

30. F atom has a less negative electron affinity

than CI atom. Additional electrons are repelled more
effectively by 3p electrons in CI atom than by
2p electrons in F atom.

31. Nuclide Ai   is less stable than Ca .

30
13
40
20 Nuclides having odd number of protons and
neutrons are general unstable.

AI — O and O — H bonds can be broken with

32.  AI (OH) is amphoteric in nature
3 equal ease in AI(OH)3.

Hydrogen bonding is present in ammonia.

33. The value of Van der Waals’ constant ‘a’

is larger for ammonia than for nitrogen.
The electrons are lost from 4s orbital to form
34. ZN is diamagnetic.
2+
ZN .
2+

The product contains one asymmetric carbon.

35. Addition of Br to 1–butene gives two

2

optical isomers.

36. The electronic structure of O is

3

  

    
    structure is not allowed because octet around
O cannot be expanded.

Electronegativity difference between Li and

37. LiCI is predominantly a covalent CI is too small.
compound.
In HNO there are two nitrogen-to-oxygen
3

bonds whereas in HNO there is only one. 2

38. HNO is a stronger acid than HNO .

3 2 Ionic radius of Mg is smaller than that   of
2+

Ba .
2+

Acetic acid has no alpha hydrogens.

39. Sulphate is estimated as BaSO and not as
4

MgSO .4

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.

______________________________________________________________________

1. (a) When the ore haematite is burnt in air with coke around 2000 C along with lime, the0

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, (Si O ) with proper labeling.
3 9
6–

(c) During the qualitative of a mixture containing CU and ZN ions, H S gas is passed through
2+ 2+
2

an acidified solution containing these ions in order to test Cu alone. Explain briefly.
2+

2. (a) Thionyl chloride can be synthesized by chlorinating SO using PCI . Thionyl chloride is
2 5

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 Ca (PO ) F yields a fertilizer “triple superphospate”
5 4

Represent the same through balanced chemical equation.

3. (a) Complete and balance the following chemical equations.

(i) PO 4 10 + PC I5 ®
(ii) SnC I4 + C H CI 2 5+ 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 KIO (formula weight = 214.0) was treated with an
3

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, 2Fe + 3I ® 2Fe + I -.
3+ – 2+
3

The standard reduction potentials in acidic conditions are 0.77 V and 0.54 V respectively for
Fe Fe and I -| I - couples.
3+ 2+
3 3

5. (a) Interpret the non-linear shape of H S molecule and non-planar shape of PCI using valence
2 3

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 H O using
2 2

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 (C H O ), on treatment with excess methyl magnesium chloride followed by

4 8 2

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 (C H O), which does not undergo self aldol condensation, gives benzaldehyde
11 8

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.
 

     

(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 and 50.5 g when filled with an ideal gas at 760 mm Hg at 300 K. Determine the
–1

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 CO (g), H O (I) and propene (g) are – 393.5, –285.8 and
2 2

20.42 kJ mol respectively. The enthalpy of isomerisation of cyclopropane to propene is –33.0 kJ

–1

mol . –1

12. (a) The degree of dissociation is 0.4 at 400 K and 1.0 atm for the gaseous reaction PCI  5

PCI + CI . Assuming ideal behaviour of all the gases, calculate the density of equilibrium
3 2

mixture at 400 K and 1.0 atmosphere. (Relative atomic mass of P = 31.0 and CI = 35.5)
(b) Given : Ag(NH ) + Ag+ + 2NH , Kc = 6.2 × 10 and Ksp of AgCI =1.8 × 10
3 2 3
–8 –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
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 . Calculate the vapour pressure
–1

of this solution at 298 K.

14. (a) The rate constant of a reaction is 1.5 × 107 s at 500C and 4.5 × 107 s at 100 C. Evaluate
–1 –1 0

the Arrhenius parameters A and Ea.

(b) For the reaction, N O (g) = 2NO (g) + 0.5 O (g), calculate the mole fraction N O (g)
2 5 2 2 2 5

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 Ag CrO in water at 298K if the emf
2 4

of the cell Ag | Ag+ (satd. Ag CrO soln.) || AG+ (0.1M) | Ag is 0.164 V at 298 K.
2 4

(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)?