AIEEE 2007 Chemistry

General Instructions
(a) (b) (c) (d) (e) There are objective type questions with four options having single correct answer. For each incorrect response, one fourth (1/4) of the total marks allotted to the question would be deducted. No deduction from the total score will, however, be made if no response is indicated for an item in the answer sheet. The candidates are advised not to attempt such item in the answer sheet if they are not sure of the correct response. More than one answer indicated against a question will be deemed as incorrect response and will be negatively marked.

1.The equivalent conductances of two strong electrolytes at infinite dilution in H2O (where ions move freely through a solution) at 25 C are given below 0CH3 COONa = 91.0 Scm2 equiv 1 0HCl = 426.2 S cm2 equiv 1 What additional information/quantity one needs to calculate 0 of an aqueous solution of acetic acid? (a) 0 of chloroacetic acid (ClCH2COOH) (b) 0 of NaCl (c) 0 of CH3COOK (d) The limiting equivalent conductance of H+ ( 0H+ ) Solution (b) From Kohlrauschs law, 0CH3 COOH = 0CH3 COONa + 0HCl 0NaCl 2.Which one of the following is the strongest base in aqueous solution? (a) Methylamine (b) Trimethylamine (c) Aniline (d) Diemethylamine Solution (d)  In aqueous solution, the basicity order of 1 > 2 > 3 amines and with methyl group, the basicity order is 2 > 1 > 3. In case of aniline, lone pair of nitrogen is involved in resonance, so it is weaker base than aliphatic amines. 3.The compound formed as a result of oxidation of ethyl benzene by KMnO4 is (a) benzyl alcohol. (b) benzophenone. (c) acetophenone. (d) benzoic acid.

Solution (d) The reaction is CH2CH3

KMNO4 H+

COOH

Ethyl benzene

Benzoic acid

4.The IUPAC name of the following compound is

(a) 3-ethyl-4,4-dimethylheptane. (b) 1,1-diethyl-2,2-dimethylpentane. (c) 4,4-dimethyl-5,5-diethylpentane. (d) 5,5-diethyl-4,4-dimethylpentane. Solution (a) The IUPAC name is
7 6 5 4

CH3 C

H3C

CH2

CH2

CH

CH2

CH3

CH3 CH2CH3
3-Ethyl-4,4-dimethylheptane

5.Which of the following species exhibits diamagnetic behavior? + (a) NO (b) O2 O2 (d)O2 2 (c) Solution (b) The electronic configurations are as follows:
2 2 2 2 2 O2 2 = s 1s s 1s s 2 s s 2 s s 2 pz 2 2 2 p 2 p2 x = p 2 py p 2 px = p 2 py

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No unpaired electron, so it is diamagnetic. + 2 O2 = s 1s2 s 1s2 s 2 s2 s 2 s2 s 2 pz
2 2 0 p 2 p2 x = p 2 py p 2 px = p * 2 py

100/r mL solution contains 29 g H2SO4 1000 mL solution contains 3.6 98 g H2SO4 Therefore, 3.6 98 = 29 r 1000 100

One unpaired electron, so it is paramagnetic. 2 O2 = s 1s2 s 1s2 s 2 s2 s 2 s2 s 2 pz

2 1 1 p 2 p2 x = p 2 py p 2 px = p 2 py

Two unpaired electrons, so it is paramagnetic. 2 NO = s 1s2 s 1s2 s 2 s2 s 2 s2 s 2 pz

2 1 0 p 2 p2 x = p 2 py p 2 px = p 2 py

Solving, we get r = 1.22g mL-1. 10.  The first and second dissociation constants of an acid H2A are 1.0 10-5 and 5.0 1010, respectively. The overall dissociation constant of the acid will be (a) 0.2 105 (b)5.0 105 (c)5.0 1015 (d)5.0 1015 Solution (d) From the expression K = K1 K2, we have K = 10 5 5 10 10 = 5 10 15 11.  A mixture of ethyl alcohol and propyl alcohol has a vapor pressure of 290 mm Hg at 300 K. The vapor pressure of propyl alcohol is 200 mm Hg. If the mole fraction of ethyl alcohol is 0.6, its vapor pressure (in mm Hg) at the same temperature will be (a) 360 (b)350 (c)300 (d)700 Solution (b) Let p be the vapor pressure of pure ethyl alcohol, then according to Raoults law 290 = 200 0.4 + p 0.6 290 80 = 350 mm Hg 0.6 12.  In the conversion of limestone to lime, CaCO3 (s) CaO(s) + CO2 (g), the values of Ho and So are + 179.1 kJ mol1 and 160.2 J K1, respectively, at 298 K and 1 bar. Assuming that Ho and So do not change with temperature, the temperature above which conversion of limestone to lime will be spontaneous is (a) 1118 K (b) 1008 K (c) 1200 K (d) 845 K p=
Solution (a) We will find out the equilibrium temperature at which G = 0. We know that

One unpaired electron, so it is paramagnetic. 6. The stability of dihalides of Si, Ge, Sn and Pb increases steadily in the sequence (a) PbX2 << SnX2 << GeX2 << SiX2 (b) GeX2 << SiX2 << SnX2 << PbX2 (c) SiX2 << GeX2 << PbX2 << SnX2 (d) SiX2 << GeX2 << SnX2 << PbX2 Solution (d)  Due to inert pair effect, the stability of +2 oxidation state increases as we move down the group. Therefore, SiX2 << GeX2 << SnX2 << PbX2 . 7.Identify the incorrect statement among the following: (a) Br2 reacts with hot and strong NaOH solution to give NaBr, NaBrO4 and H2O. (b) Ozone reacts with SO2 to give SO3. (c)  Silicon reacts with aq. NaOH in the presence of air to give Na2SiO3 and H2O. (d) Cl2 reacts with excess of NH3 to give N2 and HCl. Solution (a) Br2 reacts with hot and strong NaOH to give NaBr, NaBrO3 and H2O. 8.The charge/size ratio of a cation determines its polarizing power. Which one of the following sequences represents the increasing order of the polarizing power of the cationic species, K+, Ca2+, Mg2+, Be2+? (a) Ca2+ < Mg2+ <Be2+ <K + (b) Mg2+ <Be2+ <K + < Ca2+ (c) Be2+ < K + < Ca2+ < Mg2+ (d) K + < Ca2+ < Mg2+ <Be2+ Solution (d) Higher is the charge/size ratio, higher is the polarizing power. Therefore, K + < Ca2+ < Mg2+ <Be2+ . 9. The density (in g mL ) of a 3.60 M sulphuric acid solution that is 29% H2SO4 (molar mass = 98 g mol1) by mass will be (a) 1.45 (b)1.64 (c)1.88 (d)1.22 Solution (d)  Let the density of solution be r. Molarity of solution given = 3.6 M, that is 1 L of solution contains 3.6 mol of H2SO4 or 1 L of solution contains 3.6 98 g of H2SO4. Since the solution is 29% by mass, 100 g solution contains 29 g H2SO4
1

G = H T S 0 = H T S Therefore, H = T S . Hence, T= 179.1 1000 = 1118 K 160.2

13.  The energies of activation for forward and reverse reactions for A 2 +B2 2AB are 180 kJ mol1 and 200 kJ mol1, respectively. The presence of a catalyst lowers the activation energy of both (forward and reverse) reactions by 100 k J mol1. The enthalpy change of the reaction (A 2 + B2 2AB) in the presence of catalyst will be (in kJ mol1) (a) 20 (b)300 (c)120 (d) 280 Solution (a) From Fig. 1,

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In absence of catalyst In presence of catalyst Potential energy 200 180 80 100 Reaction coordinate

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16.  Consider the reaction, 2A + B Products. When concentration of B alone was doubled, the half life did not change. When the concentration of A alone was doubled, the rate increased by two times. The unit of rate constant for this reaction is (a) s1 (b) L mol1 s1 (c) It has no units. (d) mol1 s1 Solution (b)  For the reaction 2A + B product , when concentration of B is doubled, the half life did not change, hence the reaction is of first order with respect to B because half life is independent of concentration of first-order reaction (t1/2 = 0.693/k). When the concentration of A is doubled, the reaction rate is doubled, hence the reaction is of first order with respect to A. So, the overall order is 1 + 1 = 2 and the units of rate constant for a second order reaction is L mol1 s1. 17. Identify the incorrect statement among the following (a) 4f and 5f orbitals are equally shielded. (b)  d-Block elements show irregular and erratic chemical properties among themselves. (c)  La and Lu have partially filled d orbitals and no other partially filled orbitals. (d) The chemistry of various lanthanoids is very similar. Solution (a) 4f and 5f belongs to different energy levels, hence shielding effect is not the same for both of them. Shielding of 4f is more than 5f. Also, 5f is less deeply buried than 4f. 18. Which one of the following has a square planar geometry? (a) [PtCl4 ]2 (b) [CoCl4 ]2 (c) [FeCl4 ]2 (d) [NiCl4 ]2 (Atomic numbers of Co = 27, Ni = 28, Fe = 26, Pt = 78) Solution (a)  Most of the 4d and 5d series elements show square planar geometry. 19.  Which of the following molecules is expected to rotate the plane of plane-polarized light? (a) (b) CHO HO H SH COOH H2N H H

Figure 1 r H = E(forward) E(backward ) = 80 100 = 20 k J mol1

o = 1.10 V), was 14. The cell Zn | Zn2+ (1 M) || Cu2+ (1 M) | Cu; (E cell allowed to be completely discharged at 298 K. The relative concentration of Zn2+ to Cu2+, [Zn2+]/[Cu2+] is (a) 9.65 104 (b) antilog (24.08) (c) 37.3 (d)1037.3

Solution (d) Using Nernst equation, 0.0591 [Zn2+ ] o log E cell = E cell n [Cu2+ ]

For complete discharge, Ecell = 0, so

o E cell

0.0591 [Zn2+ ] log =0 n [Cu2+ ]

The reactions at anode and cathode are Zn Zn2+ + 2e Cu2+ + 2e Cu So, n = 2,

o = E cell

Zn 0.0591 log 2+ 2 Cu
2+

o = 1.10 V , Solving by substituting given value of E cell we get

1.10 2 [Zn2+ ] = log 0.0591 [Cu2+ ] [Zn2+ ] [Zn2+ ] 37.3 = log = 1037.3 [Cu2+ ] [Cu2+ ] 15. The pKa of a weak acid (HA) is 4.5. The pOH of an aqueous buffered solution of HA in which 50% of the acid is ionized is (a) 7.0 (b)4.5 (c)2.5 (d)9.5 Solution (d) For buffer solution (Henderson equation) [Salt] [Salt] pH = pK a + log = 4.5 + log [Acid] [Acid] As the acid is 50% ionized, which means that [salt] = [acid] pH = 4.5 + log 1 = 4.5 Therefore, pOH = 14 pH = 14 4.5 = 9.5

CH2OH (c) (d) H2N H Ph NH2 H Ph

Solution (a) The compound has a chiral carbon atom.

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CHO HO * H
Chiral carbon (A Carbon attached to four different substituents)

(a)

(b)

Plane of symmetry (which divides the molecule into two equal halves)

CH2OH (c) H2N H Ph NH2 H Ph

Chiral (d) H 2N
Plane of symmetry Achiral

SH COOH H Two identical H

groups attached

Achiral

Achiral

20. The secondary structure of protein refers to (a) fixed configuration of the polypeptide backbone. (b) a-helical backbone. (c) hydrophobic interactions. (d) sequence of a -amino acids. Solution (b)  Secondary structure of proteins involves a-helical backbone and b -sheet structures. These are formed as a result of hydrogen bonding between different peptide groups. 21. Which of the following reactions will yield 2,2-dibromopropane? (a) CH3 CH CH2 + HBr (b) CH3 CH3CH (c) (d) CH C CH + 2HBr CHBr + HBr

23.  The reaction of toluene with Cl2 in presence of FeCl3 gives predominantly: (a) m-chlorotoluene. (b) benzoyl chloride. (c) benzyl chloride. (d) o- and p-chlorotoluene.
Solution (d) The reaction involved is electrophilic addition reaction: CH3 CH3 CH3
Cl2 FeCl3

Cl +

Cl
Toluene (o, p-directing in nature) o-Chlorotoluene (Minor) p-Chlorotoluene (Major)

CH + 2HBr

Solution (b) The reaction is as follows: C CH + HBr

Markonikovs rule

CH3

CH3

C Br

CH2
(Markonikovs rule)

24. Presence of a nitro group in a benzene ring (a) deactivates the ring towards electrophilic substitution. (b) activates the ring towards electrophilic substitution. (c) renders the ring basic. (d) deactivates the ring towards nucleophilic substitution. Solution (a)  Nitro group reduces the electron density in the benzene ring due to strong -I effect.
O N O

HBr Br CH3 C Br
2,2-Dibromopropane

CH3

O
+

O O
+

O O

22.  In the chemical reaction, CH3CH2NH2 + CHCI3 + 3KOH A + B + 3H2O , the compounds (A) and (B) are, respectively, (a) C2H5NC and 3KCl (b) C2H5CN and 3KCl (c) CH3CH2CONH2 and 3KCl (d) C2H5NC and K2CO3 Solution (a)  This is an example of carbylamine reaction. So, the products will be C2H5NC and 3KCl.

Overall electron density on benzene ring decreases making electrophilic substitution difficult. Hence, it deactivates the ring towards electrophilic substitution. 25.  In which of the following ionization processes, the bond order has increased and the magnetic behavior has changed? + (a) N2 N2 + (b) C2 C2

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(c) NO NO + + (d) O2 O2 Solution (c) The electronic configurations are as follows:
2 C2 = s 1s2 s 1s2 s 2 s2s 2 s2 p 2 p2 x = p 2 py + 1 C2 = s 1s2 s 1s2 s 2 s2 s 2 s2 p 2 p2 x = p 2 py

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28.  A 5.25% solution of a substance is isotonic with a 1.5% solution of urea (molar mass = 60 g mol1) in the same solvent. If the densities of both the solutions are assumed to be equal to 1.0 g m3, molar mass of the substance will be (a) 210.0 g mol1 (b) 90.0 g mol1 (c) 115.0 g mol1 (d) 105.0 g mol1 Solution (a) Isotonic solutions have the same osmotic pressure. 1 = C1RT = 2 = C2RT so, C1 = C2. Let M be the molar mass of the substance. Now as the densities are same 5.25 15 60 = M = 5.25 = 210 M 60 1.5 29.  Assuming that water vapor is an ideal gas, the internal energy change (U) when 1 mol of water is vaporized at 1 bar pressure and 100 C (given that molar enthalpy of vaporization of water at 1 bar and 373 K is 41 kJ mol1 K1) will be: (a) 41.00 kJ mol1 (b) 4.100 kJ mol1 1 (c) 3.7904 kJ mol (d) 37.904 kJ mol1 Solution (d) The reaction is H2O(l) Vaporization H2O(g)

The electron has been removed from bonding molecular orbital, so the bond order decreases. In NO NO + ,
2 NO s 1s2 s * 1s2 s 2 s2 s * 2 s2 s 2 pz 2 1 0 p 2 p2 x = p 2 py p * 2 px = p 2 py 2 2 NO + s 1s2 s * 1s2 s 2 s2 s * 2 s2 s 2 pz p 2 p2 x = p 2 py

The electron has been removed from antibonding orbital, so bond order increases and the magnetic nature changes from paramagnetic to diamagnetic. 26.  The actinoids exhibit more number of oxidation states in general than the lanthanoids. This is because (a) the 5f orbitals extend farther from the nucleus than 4f orbitals. (b) the 5f orbitals are more buried than the 4f orbitals. (c)  there is similarity between 4f and 5f orbitals in their angular part of the wave function. (d) the actinoids are more reactive than the lanthanoids.

where ng = 1 0 = 1. Now,
H = U + ngRT U = H ngRT = 41 8.3 10 3 373 = 37.9 kJ mol1 30.  In a saturated solution of the sparingly soluble strong electrolyte AgIO3 (molar mass = 283 g mol1) the equilibrium which sets in is AgIO3 (s)
Ag+ (aq) + IO3 (aq)

Solution (a)  This is because of very small energy gap between 5f, 6d and 7s subshells. Hence, all their electrons can take part in bond formation. 27.  Equal masses of methane and oxygen are mixed in an empty container at 25 C. The fraction of the total pressure exerted by oxygen is 1 2 (a) (b) 2 3 1 273 1 (c) (d) 3 298 3 Solution (d) Let the mass of methane and oxygen be x g. Then Mole fraction of oxygen = Number of moles of oxygen Totalnumber of moles

The number of moles of oxygen = x/32 and the total number of moles of methane = x/16. So, 1 Mole fraction of oxygen = = x x 3 + 32 16 Let the total pressure be p. Then, Partial pressure of (O2) = Mole fraction of oxygen p = 1 p p= 3 3 x 32

If the solubility product constant Ksp of AgIO3 at a given temperature is 1.0 108, what is the mass of AgIO3 contained in 100 mL of its saturated solution? 1.0 10 4 g (a) (b) 28.3 10 2 g (c) 2.83 10 3 g (d) 1.0 10 7 g Solution (c) For the reaction, AgIO3 (s)
Ag+IO3

Let S be the solubility product of AgIO3, then

K sp = [Ag+ ][IO3 ]

1.0 10 8 = S 2 S = 10 4 mol L1 Mass of AgIO3 contained in 100 mL of its saturated solution is 10 4 283 100 = 283 10 5 = 2.83 10 3 g per 100 ml 1000

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(a) propanal. (c) n-butyl alcohol. Solution (d) The reaction is CH3 CH2 OH
P + I2

31.  A radioactive element gets spilled over the floor of a room. Its half-life period is 30 days. If the initial activity is 10 times the permissible value, after how many days will it be safe to enter the room? (a) 100 days (b) 1000 days (c) 300 days (d) 10 days Solution (a) We know that

(b) butanal. (d) n-propyl alcohol.

CH3 CH2I A

Mg dry ether

CH3CH2MgI B (Grignards reagent)

+H C H
n

dN Activity N dt
n

N 1 1 N = N0 = 2 N0 2 1 1 = 10 = 2n 10 2 Taking log on both the sides, log 10 = n log 2 n=

n

CH3CH2 CH2OH Propanol + Mg(OH)I D

CH3CH2 CH2O MgI C H2O/H+

35.  Which of the following sets of quantum numbers represents the highest energy of an atom? (a) n = 3, l = 0, m = 0, s = + 1/2 (b) n = 3, l = 1, m = 1, s = + 1/2 (c) n = 3, l = 2, m = 1, s = + 1/2 (d) n = 4, l = 0, m = 0, s = + 1/2 Solution (c)  According to (n + l) rule, more is the value of (n + l) more is the energy. Hence, (c) is the correct option as it has maximum value for (n + l). 36. Which of the following hydrogen bonds is the strongest? (a) O-H--F (b)O-H--N (c)FH--F (d)OH--O Solution (c)  The hydrogen bond in HF is the strongest because fluorine is the most electronegative element. 37. In the reaction, 2Al( s) + 6 HCl(aq) 2Al3+ ( aq) + 6Cl (aq) + 3H2 (g) (a)  11.2 L H2(g) at STP is produced for every mole HCl(aq) consumed. (b) 6.0 L HCl(aq) is consumed for every 3 L H2(g) produced. (c)  33.6 L H2(g) produced regardless of temperature and pressure for every mole Al that reacts (d)  67.2 L H2(g) at STP is produced for every mole Al that reacts Solution (a) The reaction is 2Al(s) + 6 HCl(aq) 2Al3+ (aq) + 6Cl (aq) + 3H2 (g) For each mole of HCl reacted, 0.5 mol of H2 gas is formed at STP. 1 mol of an ideal gas occupies 22.4 L at STP. Volume of H2 gas formed at STP per mole of HCI reacted is 22.4 0.5 L. 38.  Regular use of which of the following fertilizers increases the acidity of soil?

1 = 3.32 (as log 2 = 0.3010 ) 0.301

Therefore, t = n t1/2 = 3.32 30 = 99.6 days. 32. Which one of the following conformations of cyclohexane is chiral? (a) Boat (b) Twist boat (c) Rigid (d) Chair Solution (b) Twisted boat form of cyclohexane.
1 6 5 2 4 3

It is chiral because it does not have plane of symmetry. 33. Which of the following is the correct order of decreasing SN2 reactivity? (a) R2CHX > R3CX > RCH2X (b) RCH2X > R3 CX > R2CHX (c) RCH2X > R2 CHX > R3CX (d) R3CX > R3CHX > RCH2X (where X = a halogen). Solution (c)  SN2 reactivity depends on the steric hindrance because it involves the attack of nucleophile from the back side. So, more is the steric hindrance, lesser is the SN2 reactivity. 34.  In the following sequence of reactions,
P + I2 H2 O Mg HCHO CH3CH2OH A B C D the compound D is

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(a) Ammonium sulphate (b) Potassium nitrate (c) Urea (d) Superphosphate of lime Solution (a)  Ammonium sulphate is a salt of strong acid and weak base. On hydrolysis, it produces H+ ions which increase the acidity of soil.
2 (NH4 )2 SO 4 2NH+ 4 + SO 4

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(c) Endothermic processes are never spontaneous. (d) Exothermic processes are always spontaneous. Solution (b)  From the relation G = H - TS, G should be negative for a spontaneous process and for that S has to be positive. 40. Which of the following nuclear reactions will generate an isotope? (a) b-particle emission (b) Neutron particle emission (c) positron emission (d) a-particle emission Solution (b)  Isotopes have same atomic number but different mass number
A

NH+ 4 + H2 O

NH4 OH + H+

39.  Identify the correct statement regarding a spontaneous process: (a)  Lowering of energy in the reaction process is the only criterion for spontaneity. (b)  For a spontaneous process in an isolated system, the change in entropy is positive.

X Z A1 X Z + 1n0

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