MAHESH JANMANCHI

AIEEE 2010

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MAHESH JANMANCHI

AIEEE 2010

Maximum Marks: 144

Question paper format and Marking scheme: 1. 2. 3. This question paper has 30 questions. Q. No 4 to 9 and 13 to 30 consist of 4 marks each and Q. No 1 to 3 and 10 to 12 consist of 8 marks. each (one fourth) of total marks allotted to each question will be deducted for indicating incorrect response. No deduction from the total score will be made if no response is indicated for an item in the answer sheet.

4.

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MAHESH JANMANCHI
1.

AIEEE 2010

The standard enthalpy of formation of NH3 is 46.0 kJ mol1. If the enthalpy of formation of H2 from its atoms is 436 kJ mol1 and that of N2 is 712 kJ mol1, the average bond enthalpy of NH bond in NH3 is (1) 964 kJmol-1 (2) +352 kJmol-1 (3) +1056 kJmol-1 (4) 1102 kJmol-1 (2) Enthalpy of formation of NH3 = - 46 kJ/mole N 2 + 3H 2 2 NH 3 H f = 2 46 kJ mol 1
Bond dissociation is endothermic (+ve) and bond formation is exothermic( - ve) Assuming x is the bond energy of N-H bond ((kJ mol-1), then

Sol.

712 + ( 3 436 ) 6 x = 46 2 x = 352 kJ/mol

2. The time for half life period of a certain reaction A products is 1 hour. When the initial concentration of the reactant A, is 2.0 mol L1, how much time does it take for its concentration to come from 0.50 to 0.25 mol L1 if it is a zero order reaction ? (1) 4 h (2) 0.5 h (3) 0.25 h (4) 1 h (3)

Sol.

For a zero order reaction k =

[ A0 ] [ At ] t

(1)

Since [A0] = 2M, t1/2 = 1 hr;

k= 2 =1 2x1

when t = t1/2 , [At] = [A0]/2 [ A ]0 k= 2t 1

2

(2)

sub in equation (1) 0.5 0.25 t= = 0.25 hr 1

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MAHESH JANMANCHI
3.

AIEEE 2010

A solution containing 2.675 g of COCl3. 6 NH3 (molar mass = 267.5 g mol1) is passed through a cation exchanger. The chloride ions obtained in solution were treated with excess of AgNO3 to give 4.78 g of AgCl (molar mass = 143.5 g mol1). The formula of the complex is (At. Mass of Ag = 108 u) (1) Co ( NH 3 )6 Cl3 (2) CoCl 2 ( NH 3 )4 Cl
(3) CoCl3 ( NH 3 )3 (4) CoCl ( NH 3 )5 Cl 2

Sol.

(1)

AgNO 3 CoCl .6NH x Cl x AgCl 3 3 n ( AgCl ) = X x n ( CoCl3 .6NH3 ) 4.78 2.675 =X X= 3 143.5 267.5 The complex is Co ( NH3 )6 Cl3
4. Consider the reaction: Cl2 ( aq ) + H 2 S ( aq ) S ( s ) + 2 H + ( aq ) + 2Cl ( aq )

The rate equation for this reaction is rate = k [ Cl2 ][ H 2S] Which of these mechanisms is/are consistent with this rate equation? (A) Cl2 + H 2 S H + + Cl + Cl + + HS ( slow )
Cl + + HS H + + Cl + S

(B) H 2 S H + + HS

Cl2 + HS 2Cl (1) B only (B) Both A and B

( fast equilibrium ) + H + + S ( fast equilibrium )

(C) Neither A nor b (D) A only

( fast )

Sol.

(4) Rate equation is to be derived from slow or rate determining step. (* Since both the reactants are involved in RDS) from mechanism (A), Rate = k[Cl2] [H2S] If 104 dm3 of water is introduced into a 1.0 dm3 flask to 300 K, how many moles of water are in the vapour phase when equilibrium is established? (Given : Vapour pressure of H2O at 300 K is 3170 pa; R = 8.314 J K-1 mol-1) (1) 5.56 103 mol (B) 1.53 102 mol (C) 4.46 102 mol (D) 1.27 103 mol (4) Volume occupied by water molecules in vapour phase is ( 1- 10-4)dm3. i.e., approximately 1dm3(1L) PV 3170 10-5atm 1L n= = = 1.27 103 mol -1 -1 RT 0.0821Latm k mol 300K

5.

Sol.

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MAHESH JANMANCHI
6.

AIEEE 2010

One mole of a symmetrical alkene on ozonolysis gives two moles of an aldehyde having a molecular mass of 44 u. The alkene is (1) propene (2) 1butene (3) 2butene (4) ethene (3) But-2-ene is a symmetrical alkene. So, it gives two moles of the same aldehyde. O 3 CH CH=CH CH 2.CH CHO 3 3Zn/H O 3 2 Molar mass of CH CHO is 44 u. 3

Sol.

7.

If sodium sulphate is considered to be completely dissociated into cations and anions in aqueous solution, the change in freezing point of water ( ( T f ) , when 0.01 mol of sodium sulphate is dissolved in 1 kg of water, is (kf = 1.86 K kg mol1) (1) 0.0372 K (2) 0.0558 K (3) 0.0744 K (4) 0.0186 K

Sol.

(2) Vant Hoff factor (i) for Na2SO4 = 3 (assuming complete ionization) Na2 SO4 2 Na + + SO4 2
T f = i.k f . m
= 3 1.86 0.01 = 0.0558 K 1

8.

From amongst the following alcohols the one that would react fastest with conc. HCl and anhydrous ZnCl2, is (1) 2-Butanol (2) 2Methylpropan2ol (3) 2Methylpropanol (4) 1Butanol (2) 3 alcohols react fastest with Lucas reagent i.e., an. ZnCl2/conc.HCl due to formation of 3 carbocation 2methyl propan2ol is the only 3 alcohol. In the chemical reactions, NH 2

Sol.

9.

2 HCl 278K

NaNO

HBF 4

the compounds A and B respectively are (1) nitrobenzene and fluorobenzene (3) benzene diazonium chloride and fluorobenzene Sol. (3)

(2) phenol and benzene (4) nitrobenzene and chlorobenzene

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MAHESH JANMANCHI

AIEEE 2010

This is Schiemann reaction (also called the Balz-Schiemann reaction). It is a chemical reaction in which anilines are transformed to arylfluorides through diazonium fluoroborates . 10. 29.5 mg of an organic compound containing nitrogen was digested according to Kjeldahls method and the evolved ammonia was absorbed in 20 mL of 0.1 M HCl solution. The excess of the acid required 15 mL of 0.1 M NaOH solution for complete neutralization. The percentage of nitrogen in the compound is (1) 59.0 (2) 47.4 (3) 23.7 (4) 29.5 (3) Moles of HCl reacting with Ammonia = (moles of HCl absorbed ) (moles of NaOH solution required) = ( 20 0.1103 ) (15 0.1103 )
= moles of NH3 evolved = moles of nitrogen in organic compound wt. of nitrogen in org. compound = 0.5 103 14 = 7 103 g 7 103 % wt = x100 = 23.7% 29.5 103

Sol.

11.

The energy required to break one mole of ClCl bonds in Cl2 is 242 kJ mol1. The longest wavelength of light capable of breaking a single Cl Cl bond is ( c = 3108 ms-1 and NA = 6.021023 mol-1 ) (1) 594 mm (2) 640 mm (3)700 mm (4) 494 mm

Sol.

(4)

242 103 Joule. 6.02 x1023 The energy is contained in photon of wavelength ' ' . hc 6.625 1034 3 108 =E Energy required for 1 Cl2 molecule =

242 10 6.02 1023 = 0.494 x 10-6 m = 494 nm

3

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MAHESH JANMANCHI
12.

AIEEE 2010

Ionisation energy of He+ is 19.6 x 1018 J atom1. The energy of the first stationary state (n = 1) of Li2+ is (1) 4.411016 J atom 1 (2) -4.411017 J atom 1 (3) -2.21015 J atom 1 (4) 8.821017 J atom 1

Sol.

(2)

IE 2
IEHe+ IELi2+ 22 = 2 3

19.6 x1018 22 = 2 IELi2+ 3

IELi 2+ = 19.6 x10 18 x 9 4
18

Therefore ELi 2+ = 19.6 x10 = -4.4110 13.

17

9 x (IE ans E are same in magnitude but opposite in sign) 4

J atom 1

Consider the following bromides:

The correct order of S N 1 reactivity is

(1) B > C > A

Sol Sol.

(2) B > A > C

(3) C > B > A

(4) A > B > C

(1) SN1 reaction proceeds via carbocation intermediate. As the formation of carbocation is rate determining step,the most stable one forms the product faster. Hence reactivity order for A, B, C depends on stability of carbocation formed.

B forms 20 allyl carbocation ,which is the most stable among given. The next stable carbocation is formed by C. It forms a 20 carbocation. The least stable carbocation is formed by A. It forms a 10 carbocation.
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MAHESH JANMANCHI
14. Which one of the following has an optical isomer? 2+ (1) Zn ( en ) NH (2) 3 2 3+ (3) Co H O ( en ) (4) 2 4

AIEEE 2010

Co ( en ) 3

3+

Zn ( en ) 2

2+

Sol.

(2)

15.

On mixing, heptane and octane form an ideal solution. At 373 K, the vapour pressures of the two liquid components (heptane and octane) are 105 kPa and 45 kPa respectively. Vapour pressure of the solution obtained by mixing 25.0g of heptane and 35 g of octane will be (molar mass of heptane = 100 g mol1 an dof octane = 114 g mol1). (1) 72.0 kPa (2) 36.1 kPa (3) 96.2 kPa (4) 144.5 kPa (1) Mole fraction of Heptane =
25 / 100 25 35 + 100 114 0.25 = 0.557 = 0.45 X Heptane = 0.45 Mole fraction of octane = 1 - 0.45 = 0.55 Total pressure = Xi Pi 0

Sol.

= (105 0.45 ) + ( 45 0.55 ) kPa = 72.0 kPa

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MAHESH JANMANCHI
16.

AIEEE 2010

conc.H SO 2 4 The main product of the following reaction is C H CH CH ( OH ) CH CH ? 6 5 2 3 2

H C 5 6

H C C
CH CH

C H CH 6 5 2

CH 3
C C
CH 3

(1)

3 2

(2)

C H 6 5
C C

CH CH

3 2

H C CH CH 5 6 2 2
C

CH

(3) Sol. (1)

(4)

H C 3

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MAHESH JANMANCHI
Three reactions involving H PO are given below : 2 4 + + H PO (i) H PO + H O H O 3 4 2 3 2 4 + H O H PO 2 + H O + (ii) H PO 2 4 2 2 4 3 (iii) H PO + OH H PO + O 2 2 4 3 4 In which of the above does H PO act as an acid? 2 4 (1) (ii) only (2) (i) and (ii) (3) (iii) only (1) Proton donor is an acid acc to Bronsted Lowry theory. ( i ) H3PO4 + H 2O H3O+ + H 2 PO4 conjugate base acid ( ii ) H 2 PO4 + H 2O H 2 PO4 2 + H3O+ acid conjugate base ( iii ) H 2 PO4 + OH H3PO4 + O2 base conjugate acid So, only in reaction (ii) H PO is acting as acid. 2 4

AIEEE 2010

17.

(4) (i) only

Sol

18.

In aqueous solution the ionization constants for carbonic acid are K1 = 4.2 10-7 and K 2 = 4.8 10-11 Select the correct statement for a saturated 0.034 M solution of the carbonic acid. 2 (1) The concentration of CO3 is 0.034 M
2 (2) The concentration of CO3 is greater than that of HCO3
(3) The concentration of H+ and HCO3 are approximately equal

2 (4) The concentration of H+ is double that of CO3

Sol.

(3) A H 2CO3

H + +HCO3

K1 = 4.2 107 K 2 = 4.8 1011

B HCO3 H + +CO3 2 As K2 << K1 All major H + H +

total

And from I equilibrium, H + HCO3 H + A total CO3 2 is negligible compared to HCO3 or H +

total

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MAHESH JANMANCHI
19.

AIEEE 2010

The edge length of a face centered cubic cell of an ionic substance is 508 pm. If the radius of the cation is 110 pm, the radius of the anion is (1) 288 pm (2) 398 pm (3) 618 pm (4) 144 pm (4) In an FCC lattice, 2 ( r + + r ) = edge length
2 (110 + r ) = 508

Sol.

r = 144 pm 20. The correct order of increasing basicity of the given conjugate bases (R = CH3) is (1) RCOO < HC = C < R < NH (2) R < HC C < RCOO < NH 2 2 (4) RCOO < HC C < NH < R (3) R COO < NH < HC C < R 2 2 (4) Correct order of increasing basic strength is RCOO( ) < CH C( ) < NH ( ) < R ( ) 2 Order of basicity can be explained on the basis of acidity of the acids of the given conjugate base. Stronger the acid, weaker is the conjugate base and vice versa. As RCOOH is the strongest acid among given, RCOO is the weakest base. Acetylene is also acidic due to sp carbon. It is a weak base but stronger than RCOO-. sp3 carbon is less electronegative than sp3 nitrogen, R- is less acidic or more basic than NH2The correct sequence which shows decreasing order of the ionic radii of the elements is (1) Al3+ > Mg 2+ > Na + > F > O2 (2) Na + > Mg 2+ > Al3+ > O 2 > F

Sol.

21.

(3) Na + > F > Mg 2+ > O 2 > Al3+

Sol. (4)

(4) O 2 > F > Na + > Mg 2+ > Al3+

For isoelectronic species ( all have 10 e-), higher the

Z 8 for O 2 = = 0.8 e 10 9 F = = 0.9 10 11 Na + = = 1.1 10 12 Mg 2+ = = 1.2 10 13 Al3+ = = 1.3 10

Z ratio, smaller the ionic radius e

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MAHESH JANMANCHI
(Or)

AIEEE 2010

In case of isoelectronic species, as the magnitude of negative charge increases, size increases and as the magnitude of positive charge increases, size decreases 22. Solubility product of silver bromide is 5.0 1013. The quantity of potassium bromide (molar mass taken as 120 g of mol1) to be added to 1 litre of 0.05 M solution of silver nitrate to start the precipitation of AgBr is (1) 1.2 1010 g (2) 1.2 109 g (3) 6.2 105 g (4) 5.0 108 g (2) Ag + + Br AgBr Precipitation just starts when ionic product just exceeds solubility product ( Q >Ksp) K sp = Ag + Br
K SP 5 1013 Br = = = 1011 Ag + 0.05 i.e., precipitation just starts when 1011 moles of KBr is added to 1L of AgNO3 solution. No. of moles of KBr to be added = 1011 = 1011 120

Sol.

1.2 10 9 g
23. The Gibbs energy for the decomposition of Al2O3 at 500C is as follows : 2 4 Al2O3 Al + O2 , r G = +966 kJ mol 1 3 3 The potential difference needed for electrolytic reduction of Al2O3 at 5000 C is at least (1) 4.5 V (2) 3.0 V (3) 2.5 V (4) 5.0 V (3) The ionic reactions are 2 3+ 4 Cathode : Al2 + 4e Al 3 3 2 2 Anode : O3 O2 + 4e 3 So, the no of electrons transferred = 4
G = nFE G E= nF 966 103 E= 4 96500 = - 2.5 V The potential difference needed for the reduction = 2.5 V

Sol.

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MAHESH JANMANCHI
24.

AIEEE 2010

At 25C, the solubility product of Mg(OH)2 is 1.0 1011. At which pH, will Mg2+ ions start precipitating in the form of Mg(OH)2 from a solution of 0.001 M Mg2+ ions? (1) 9 (2) 10 (3) 11 (4) 8 (2) Mg 2 + + 2OH
Mg ( OH ) 2
2

Sol.

K sp = Mg 2+ OH K sp OH = = 104 2+ Mg OH P = 4 and pH = 10 At pH = 10, Mg2+ starts precipitating.

25. Percentage of free space in cubic close packed structure and in body centred packed structure are respectively (1) 30% and 26% (2) 26% and 32% (3) 32% and 48% (4) 48% and 26% (2) Packing efficiency of cubic close packing = 74% Therefore % free space = 26% Packing efficiency of body centred packing = 68%. Therefore % free space = 32% Out of the following, the alkene that exhibits optical isomerism is (1) 3methyl2pentene (2) 4methyl1pentene (3) 3methyl1pentene (4) 2methyl2pentene (3)

Sol.

26.

Sol.

H H 2C = HC C2 H5

CH3 Only 3-methyl pent-1-ene has a chiral carbon

27.

Biuret test is not given by (1) carbohydrates (2) polypeptides

(3) urea

(4) proteins

Sol.

(1) It is a test characteristic of amide linkage ( - CONH) . Urea also has amide linkage like proteins.

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MAHESH JANMANCHI

AIEEE 2010

28.

The correct order of E 0 with negative sign for the four successive elements M2+ / M Cr, Mn, Fe and Co is (1) Mn > Cr > Fe > Co (2) Cr > Fe > Mn > Co (3) Fe > Mn > Cr > Co (4) Cr > Mn > Fe > Co (1) E0 values for Mn ,Cr , Fe and Co are -1.18V, -0.91V , -0.44 V and -0.28V respectively The polymer containing strong intermolecular forces e.g. hydrogen bonding, is (1) Teflon (2) nylon 6,6 (3) polystyrene (4) natural rubber (2) Nylon 6, 6 is a polymer of adipic acid and hexamethylene diamine. It contains amide linkages. So, it will have very strong intermolecular hydrogen bonding between NH and - C=O groups of two polyamide chains O O
C

Sol.

29.

Sol.

( CH2 )4

C NH CH

2 6

NH
n

30.

For a particular reversible reaction at temperature T, H and S were found to be both +ve. If Te is the temperature at equilibrium, the reaction would be spontaneous when (1) T > T (2) T > T (3) T is 5 times T (4) T = T e e e e (2) G = H T S At equilibrium G = 0 for a reaction to be spontaneous G should be negative. As both H and S are +ve , for ve G T > T e

Sol.

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