IIT-JAM 2005 With Solution PDF

CHEM ACADEMY 1 IIT-JAM 2005
IIT-JAM 2005
Note: Attempt ALL the 44 questions. Question 1-30 (Objective questions) carry three marks each and
question 31-44 (Subjective Questions) carry fifteen marks each.
1. Arrange the following in the decreasing order of acidity of the hydrogen indicated in italic
(i) CH 3COCH3 (ii) CH 3COCH 2COCH 3
(iii) CH3OOCCH 2COOCH 3 (iii) CH 3COCH 2 NO 2

(a) (ii) > (iii) > (i) > (iv) (b) (iv) > (ii) > (iii) > (i)
(c) (iv) > (iii) > (ii) > (i) (d) (ii) > (iv) > (iii) > (i)
2. For the reaction shown below if the concentration of KCN is increased four times, the rate of the
reaction will be :
CHEM ACADEMY
(a) doubled (b) increased four times
(c) unaffected (d) halved
3. Benzyl chloride is reacted with different nucleophiles shown below. Arrange them in the decreasing
order of reactivity.
Nucleophiles : HO, CH3COO, PhO, CH3O
(a) CH3O > HO > PhO > CH3COO (b) HO > CH3O > PhO > CH3COO
(c) HO > PhO > CH3O > CH3COO (d) CH3COO > CH3O > HO > PhO
4. The rate of nitration of the following aromatic compounds decreases in the order
(i) benzene (ii) pyridine (iii) thiophene (iv) toluene
(a) (iv) > (i) > (iii) > (ii) (b) (iii) > (iv) > (i) > (ii)
(c) (iii) > (ii) > (i) > (iv) (d) (ii) > (i) > (iv) > (iii)
5. The major product formd in the reaction on 1, 3-butadiene wtih bromine is
(a) BrCH2CH(Br)CH = CH2 (b) CH2 = CH—CH2CH2Br
(c) CH2 = C(Br)—C(Br) = CH2 (d) BrCH2CH = CHCH2Br
6. The reaction of (+)2-iodobutane and NaI* (I* is radioactive isotope of iodine) in acetate was studied
by measuring the rate of racemization (kr) and the rate of incorporation of I* (ki).
(+)CH3CH(I)CH2CH3 + NaI*  CH3CH(I*)CH2CH3 + NaI
For the reaction, the relationship between kr and ki is:
(a) ki = 2 × kr (b) ki = (1/2) × kr (c) ki = kr (d) ki = (1/3) × kr
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7.
In the scheme shown above (P), (Q), (R) and (S) are
(a) (P) = purine bases, (Q) = pyrimidine bases, (R) = nucleotides, (S) = nucleosides
(b) (P) = nucleosides, (Q) = nucleotides, (R) = pyrimidine bases, (S) = purine bases
(c) (P) = nucleosides, (Q) = nucleotides, (R) = (S) = purine bases
(d) (P) = nucleotides, (Q) = nucleosides, (R) = pyrimidine base, (S) = purine base
8. The products obtained from the following reaction are:
(a) (b)
(c) (d)
9. CHEM ACADEMY
The product(s) obtained in the following reaction is (are)
(a) (b)
(c) (d)
10. Match the isoelectric point with the amino acids.
Amino acids Isoelectric point
(X) H2NCH2COOH (I) 9.5
(Y) HOOCCH2CH2CH(NH2)COOH (II) 6.0
(Z) H2N(CH2)4CH(NH2)COOH (III) 3.1
(a) (X)-(II), (Y)-(III), (Z)-(I) (b) (X)-(III), (Y)-(I), (Z)-(II)
(c) (X)-(I), (Y)-(II), (Z)-(III) (d) (X)-(II), (Y)-(I), (Z)-(III)
11. The compound having the highest melting point is:
(a) LiCl (b) LiF (c) LiI (d) LiBr
12. The shape of SF4 is
(a) tetrahedral (b) trigonal bipyramidal
(c) square planer (d) octahedral
13. The degree of hydration is expected to be maximum for
(a) Mg2+ (b) Na+ (c) Ba2+ (d) K+
14. The decreasing order of the first ionization energy of the following elements is:
(a) Xe > Be > As > Al (b) Xe > As > Al > Be
(c) Xe > As > Be > Al (d) Xe > Be > Al > As
15. The radioactive isotope used to locate brain tumors is
16.
CHEM ACADEMY
(a) 12 D (b) 15
7 N (c) 131
53 I (d) 13
6 C
The crystal field stabilization energy of high spin d7 octahedral complex is:
4 4 9 9
(a)   0  2P (b)   0  3P (c)   0  2P (d)   0  3P
5 5 5 5
17. The complex with the most colour among the following is:
(a) [FeF6]3– (b) [MnCl4]2– (c) [CoCl4]2– (d) [CoF6]3–
18. On addition of a solution of AgNO3 to a solution of Na2S2O3, it turns black on standing due to the
formation of:
(a) Ag (b) Ag2S (d) Ag2S2O2 (d) Ag2SO4
19. Among the following complexes,
(i) [Ru(bipyridyl)3]+ (ii) [Cr(EDTA)]–
(iii) trans-[CrCl2(oxalate)2]3– (iv) cis-[CrCl2(oxalate)2]3–
the ones that show chirality are
(a) (i), (ii), (iv) (b) (i), (ii), (iii) (c) (ii), (iii), (iv) (d) (i), (iii), (iv)
20. The electronic configurations that have orbital angular momentum contribution in octahedral
environment are
(a) d1 and high spin d4 (b) d1 and d2
(c) d2 and high spin d6 (d) high spin d4 and high spin d6
21. For an ideal solution formed by mixing of pure liquids A and B.
(a) Hmixing = 0 (b) Hmixing < 0 (c) Hmixing > 0 (d) Smixing = 0
22. The relationship between the equilibrium constant K1 for the reaction :
1
CO(g) + O2(g)  CO2 (g)
2
and the equilibrium constant K2 for the reaction:
2CO(g) + O2(g)  2CO2(g) is:
(a) 2K1 = K2 (b) K1 = K22 (c) K1 = K2 (d) K12 = K2
23. For H-like atoms, the ground state energy is proportional to
 Z2 1
(a) (b) (c) µZ2 (d)
Z2  Z2
24. The value of integral  e  x x 2dx is
1 2 x x x
(a) x 2e x  2xe  x  2e  x (b)  (x e  2xe  2e )
2
1 2 x x x
(c) (x e  2xe  2e ) (d)  x 2e  x  2xe  x  2e  x
2
1
25. From the reaction aA  products, the plot of versus time (t) gives a straight line. Order of the
[A]
reaction is
26.
(a) 0
CHEM ACADEMY (b) 1 (c) 2 (d) 3
The pH of a solution prepared from 0.005 mole of Ba(OH) 2 in 100 cc water is
(a) 10 (b) 12 (c) 11 (d) 13
27. For an electron whose x-positional uncertainity is 1 × 1010 m, the uncertainity in x-component of
the velocity in ms–1 will be of the order of (Data: me = 9 × 10–31 kg, h = 6.6 × 1034 Js)
(a) 106 (b) 109 (c) 1012 (d) 1015
28. For the following system in equilibrium, CaCO3 (s)  CaO(s)  CO 2 (g)
the number of components, (C), phases (P) and degrees of freedom (F), respectively, are
(a) 2, 2, 2 (b) 1, 3, 0 (c) 3, 3, 2 (d) 2, 3, 1
29. For the distribution of molecular velocities of gases, identify the correct order from following
(where vmp, vav, vrms are the most probable velocity, average velocity, root mean square velocity,
respectively):
(a) vrms, vav, vmp (b) vmp, vrms, vav (c) vav, vrms, vmp (d) vmp, vav, vrms
o o o
30. Given that E Fe2 / Fe   0.44V and E Fe3 / Fe2   0.77 V, the E Fe3 / Fe is :
(a) 1.21 V (b) 0.33 V (c) –0.036 V (d) 0.036 V
31. Identify the major product(s) formed in the following reactions. Intermediates and reaction
mechanisms need not be discussed.
(a) (b)
(c)
32. How may the following transformations be effected? Indicate the reagents/reaction conditions clearly
in each step.
(a) (Not involving any functional group transformation of the COOH group in the starting material)
(b) (Using diethyl malonate as the only source of carbon)

CHEM ACADEMY
(c)
33. Suggest a suitable mechanism for each of the following reactions.
(a) PhCOCH2CH3 +
(b)
34. Rationalize the following observations using suitable mechanism.

(a) Nitratino of 4t-butyltoluene gives 4-nitrotoluene as one of the products.
(b) cis-1-t-butylcyclohexyltrimethylammonium hydroxide undergoes Hoffmann elimination to yield
4-t-butylcyclohexene whereas the trans isomer does not (use conformations) explain.
1. dry ether
(c) PhMgBr + 2PhCHO 
2. acid workup
 PhCOPh + PhCH OH
2
35. (a) Suggest a chemical method for the separation of a mixture contain p-N, N-dimethylaminophenol
and p-aminobenzoic acid and give a confirmatory test for phenol.
(b) Write the structures of X, Y and Z in the following
(i)
(ii)
(iii)
36. (a) Predict the hybridization and draw the structure of the following molecules based on VSEPR
theory (i) I3– (ii) SO32– (iii) P(CH3)3F2
(b) Explain why PCl5 exists and PH5 does not.
37. (a) Write balanced equations for the formation of
(i) P2O7–4 from PO4–3 (ii) [(H2O)4Fe(OH)2Fe(OH2)4]4+ from [Fe(OH2)6]+3
(b) Which one of the two solutions has lower pH? Justify your answer.
(i) 0.1 M Fe(ClO4)2 or 0.1 M Fe(ClO4)3
(ii) 0.1 M Hg(NO3)2 or 0.1 M Zn(NO3)2
38.
CHEM ACADEMY
(a) Between Co(H2O)62+ and Cu(H2O)62+, which has more distorted structure and why?
(b) Calculate CFSE (in units of 0) and spin only magnetic moment for the following complexes.
(i) [CoF6]3– (ii) [Fe(CN)6]3– (iii) [NiCl4]2–
39. (a) The radioactive element Ra (Z = 86) emits three alpha particles in succession. Deduce in which
group the resulting element will be found?
(b) A radioisotope sample has an initial activity of 23 dis/min. After 1/2 h, the activity is 11.5 dis/
min. How many atoms of the radioactive nuclide were present originally? [t1/2 = 0.69]
40. (a) Write the products of the following reactions:
(i) CH3I + HO–  (ii) CF3I + HO–  (iii) 2CF3I + Na[Mn(CO)5] 
(b) Arrange BF3, BCl3 and BBr3 in the increasing order of Lewis acidity and justice.
41. Justify the following
(a) Considering CO2 as an ideal gas, equipartition theorem products its total energy as 6.5 kT.
(b) S for a process is the same whether the process takes place reversibly or irreversibly.
(c) The quantity G equals the maximum non-expansion work done by a system in a constant
temperaure-pressure process.
(d) At constant temperature and pressure, G = 0 for a reversible phase change.
(e) Transition states cannot be isolated as independent chemical species.
3000
42. The rate constant k for a second order reaction P + Q  Products is expressed log10 k  20  ,
T
where the concentration is in mol lit–1, T is in absolute temperature and time is in minutes. The
initial concentrations of both the reactants are 0.05 M. Calculate the activation energy and half life
of the reaction at 27ºC. (R = 2 cal K–1 mol–1)
43. The equilibrium constant for the reaction
Fe3O4(s) + CO(g)  3FeO(s) + CO2(g)
at 600°C is 1.00. If a mixture initially consisting of 1 mole of Fe3O4, 2 moles of CO, 0.5 mole of
FeO and 0.3 mole of CO2 is heated to 600°C at constnat total pressure of 5 atospheres, how many
moles of each substance would be present at equilibrium ?
44. (a) Use the time-independent Schrodinger equation to calculate the energy of a particle of mass
8 x y z
“m” with V = 0 in the state   3
sin sin sin in a cubical box of length “a”.
a a a a
(b) At 20ºC, the vapour pressure of two pure liquids X and Y which form an ideal solution are 70
torr and 20 torr respectively. If the mole fraction of X in solution is 0.5, find the mole fraction of X
and Y in the vapour phase in equilibrium with the solution.
CHEM ACADEMY
SOLUTION
OBJECTIVE QUESTIONS
1. Conjugate base of strong acid is weak (i.e. stable), so stability of conjugate base of CH3COCH3,
CH3COCH2COCH3, CH3COOCCH2COOCH3 and CH3COCH2NO2 can be arranged as
Here has greater electron withdrawing ability than Therefore, (ii) has
greater acidity than (iii).
Correct option is (b)
2. This reaction follows SN1 – pathway due to living group is present at tertiary carbon atom.
The rate of SN1 reaction  reactant.
So, rate will be independent of nucleophilic concentration.
Correct option is (c)
3. in PhO– and CH3COO– negative charge on oxygen is delocalized via resonance, but CH3COO– has

more delocalization than PhO–, so CH3COO– is less nucleophilic than PhO–, O H and CH3O–.
4. CHEM ACADEMY
The rate of electrophilic substitution reaction is depends on the electron density in ring. Thiophene
has most electron density in the ring and pyridine has least. Hence, the order towards the electrophilic
substitution will be
thiophene > toluene > benzene > pyridine
5.
Correct option is (d)
6.
1 1
When mole of NaI* reacts with (I), then it causes formation of mole of (II) (i.e. inversion
2 2
1 1
product), but mole of (I) and mole of (II) , give 1 mole of racemic mixture (I)
2 2
 1 1 
    mole(I)  () mole(II)  .
 2 2 
So rate of racemisation is twice of inversion.
1
 kr = 2ki  ki  kr
2
7. Correct option is (d)
8.

9. It is an example of claisen rearrangement which includes 3, 3-sigmatropic rearrangement and phenol
tautomerism as shown below.
CHEM ACADEMY
10. As the number of basic (–NH2) units increases, the pI value increases.
As the number of acidic (–COOH) units increases, the pI value decrease.
Correct option is (a)
11. LiF has highest lattice energy and also maximum ionic character, so it has highest melting point.
12.

13. (a) Degree of hydration is proportional to charge/radius; here Mg2+ has highest charge as well as
smallest radius.
14.

15. Correct option is (c)
16. d7 in octahedral field split as shown below
CHEM ACADEMY
2 3 4
CFSE    0  5   0  2    0
5 5 5
4
Two electrons are paired in t2g set of AOs. So correct value of CFSE =   0 + 2P
5
17. Most colour (or maximum intensity) is observed in the order
Charge transfer > dn – tetrahedral (n  5) > dn – octahedral (non-centrosymmetry) >
dn – octahedral (centrosymmetry, n  5) > d5 - tetrahedral > d5 - octahedral (non-centrosymmetry)
> d5 - octahedral (centrosymmetry)
(a) [FeF6]3–  Fe3+  d5 – octahedral (b) [MnCl4]2–  Mn2+  d5 - tetrahedral
(c) [CoCl4]2–  Co2+  d7 - tetrahedral (d) [CoF6]3–  Co3+  d6 - tetrahedral
So, [CoCl4]2– is most intense coloured.
18. (b) Chemical reaction occuring in above reaction can be represented as
2AgNO3 + Na2S2O3  Ag2S2O3 + NaNO3
Ag2S2O3 + H2O  Ag 2S  H 2SO 4

(black)

19. Out of (i), (ii), (iii), (iv) only (iii) has got plane of symmetry, so it is not chiral
20. To have an orbital contribution, t2g orbitals must not be symmetrically occupied (i.e. it should not
have t 32g or t 62g configuration).
21. For an ideal solution, Hmixing = 0
1
22. For reaction, CO(g) + O 2 (g)  CO 2 (g)
2
Equilibrium constant K1 can be calculated as
[CO2 ]
K1  ... (i)
[CO][O 2 ]1/ 2
For reaction, 2CO(g)  O2 (g)  2CO 2 (g)
2
[CO2 ]2
 [CO 2 ] 
K2    ... (ii)
[CO] [O2 ] [CO][O 2 ]1/ 2 
2
Using equation (i) and equation (ii), we get
K 2  K12
23.
CHEM ACADEMY
Energy of H-like atoms (En) = 

µe 4  Z2 
 
8 20 h 2  n 2 
For ground state, n = 1  E  µz 2

x
 (e ) (x 2 ) dx
24. 
2nd 1st
On integrating by parts,
  
x 2e x  2 xe x dx   x 2e  x  2  xe  x  e x   x 2 e x  2xe x  2e x

25. For nth order reaction, aA 
k
 products
1  1 1 
We have, (n  1)  n 1    k eff .t;
 [A] [A]0n 1 
1
here, vs t graph is straight line, so from question, n = 2
[A]n 1
26. Ba(OH)2  Ba+2 + 2OH–
0.005 mole 0.005 mole 2 × 0.005 mole
2  0.005  1000
 [OH  ]  M  0.1M  10 1 M
100
1014
[H  ]  14
 1013 M
 10  pH   log[H  ]   log[1013 ]  13
[OH  ] 
101
h h
27. We have, x Px   x m Vx 
4 4
h 6.625 1034
 Vx   Vx   Vx  5.8  105  Vx ~ 106
4 11010  4 9 10 31
28. CaCO3 (s)  CaO(s)  CO 2 (g)
Phase = 3
Component (C) = N – E
N = 3 (No. of species)
CHEM ACADEMY
F=C–P+2
E = 1 Equilibrium
C=2
=2–3+2=1
29. Expression representing value of most probable, average velocity and root mean square velocity
are as shown below.
3RT 8RT 2RT
Vrms  , Vav  , Vmp 
M M M
Fe 3  e 
 Fe 2 , G1  (1)(F)(E0 ) ...(i)
Fe 3 / Fe2
30. Fe 2  2e 
 Fe, G 2  (2)(F)(E0 2 ) ...(ii)
Fe / Fe
(i) + (ii) Net reaction: Fe+3 + 3e–  Fe, G3 = G1 + G2
0 0 0
 –(3)(F) (E Fe3 / Fe )   F[E Fe3 / Fe2  2E Fe2 / Fe ]
1
 E0  [0.77V  2( 0.44V)]  0.036V
Fe3 / Fe 3
 E0  0.036V
Fe 3 / Fe
DESCRIPTIVE QUESTIONS
31. (a)
(c)
32. (a)
CHEM ACADEMY
33. (a) Chemical reaction occuring in above transformation can be illustrated as
CHEM ACADEMY
34. (a) Chemial reaction occuring in above transformation can be illustrated as
As shown in the above mechanism, electrophilic substitution of t-butyl carbocation by H+, takes
place, because tertiary - butyl carbocation is quite stable, so it is completetively replaced by H+.
cis-4t-butylcyclohexyltrimethylammonium hydroxide undergoes Hoffmann elimination, because

‘H’ anti to trimethylammonium is present.
Here ‘H’ anti to leaving group is not present, so elimination is not possible.
(c) Chemical reaction occuring in statement given above can be illustrated as
35. (a) CHEM ACADEMY
36. (a) (i)
Central ‘I’ has 3 l.p. and 2 b.p., So, it is sp3d hybridized.

Geometry  Trigonal bipyramidal
Shape  Linear
(ii) SO32–
‘S’ has ‘4’ electron clusters surrounding it, so it is sp3 hybridized.
CHEM ACADEMY Geometry  tetrahedral, Shape  Pyramidal
(iii) P(CH3)3F2
‘P’ has 5 b.p. of electron-cluster surrounding it.

So, it is sp3d hybridized.
Geometry  Trigonal bipyramidal
Shape  Trigonal bipyramidal
(b) As phosphorous contains vacant ‘3d’ orbital, So, it can expand its valency from 3 to 5 via
utilization of 3d orbital.
In case of PCl5, overlapping of sp3d orbital of phosphorous with 3p orbital of chlorine is strong
enough to make a stable compound, but sp3d(p) and 1s(H) overlap is not so effective, So, PH5 does
not exist.
37. (a) Balanced equation for the formation of P2O7–4 from P2O4–3 can we written as
(i) 2PO43+ + 2H+  P2O74– + 4H2O
(ii) formation of [(H2O)4Fe(OH)2Fe(OH2)4]4+ from [Fe(OH2)6]+3 can be written as
2[Fe(H 2O)6 ]3  2H 2O 

[(H 2O) 4 Fe(OH) 2 Fe(OH 2 ) 4 ]4  2H3O 
(b) [Fe(H 2O) 6 ]2  2ClO 4

(i) Fe(ClO4 )2  6H 2O 
[Fe(H 2O)6 ]2  H 2O 

[Fe(H 2O)5 (OH)]  H3O 
and [Fe(H 2O)6 ]3  3ClO 4

Fe(ClO 4 )3  6H 2O 
[Fe(H 2O)6 ]3  H 2O 

[Fe(H 2O) 5 (OH)]2  H3O 
As Fe+3 is harder acid then Fe+2, So [Fe(H2O)6]+3 prefers over [Fe(H2O)6]+2 to get deprotonated.
So, that it can bind with OH– (because OH– is harder base than H2O).
So, Fe(ClO4)3 is stronger acid in water and shows lower pH than Fe(ClO4)2.
(ii) Hg(NO3 )2 in aq. medium exist as [Hg(H2 O)6 ]+ and 2NO3 – and Zn(NO3)(aq) exists as
[Zn(H2O)6]+2 and 2NO3–.
As Zn+2 is a harder lewis acid than Hg+2.
So, [Zn(H2O)6]+2 prefers to donate H+. So that Zn+2 can get bind to OH– (because OH– is harder
lewis base than H2O).
So, Zn(NO3)(aq) has lower pH.
38.
CHEM ACADEMY
(a) Crystal field splitting diagram of [Co(H2O)6]+2 can be drawn as
C.F.S.E. of Cu+2 complex = 

As   2 '  [Cu(H2O)6]2+ undergoes more distortion.
(b) (i) [CoF6]3– = Co+3(3d6)
 2   3 
C.F.S.E  4    0   2    0 
 5   5 
2
   0  0.4 0
5
(ii) [Fe(CN)6]–3
C.F.S.E. = –0.40 × 5 + 2P0 = –20 + 2P0
CHEM ACADEMY
s  1(1  2) B.M.  3 B.M. (where P0 = Pairing energy)
(iii) [NiCl4 ]–2
6
C.F.S.E.    t ;  s  2(2  2) B.M.  8 B.M.
5
A 3 particle in succession
A 12
39. (a) 88 Ra  82 X
Atomic number 82 is for Pb and it belongs to group 14.
(b) t = 0, activity (A0) = N0 = 23 dis/min
1
t hr , activity (At) = Nt = 11.5 dis/min
2
1 A0 1
As after t  hr , activity A t   t  t1/ 2  hr = 30 min
2 2 2
0.690 0.690
 N0 = 23 dis/min  t N 0  23  N0  23
1/ 2 30
23  30
 N0   1000 atoms
0.690
40. (a) (i) CH3 – OH + I– (ii) I – O– + HCF3 (iii) Mn(CO)5I + C2F6 + NaI
(b) Increasing lewis acidity order:
BF3 < BCl3 < BBr3
In BF3  2p –2p back bonding most effective due to similar size and energy of ‘p’ orbitals.
BCl3  2p – 3p back bonding less effective because difference in p-orbital energy and also bond
length is large.
In BBr3  2p – 4p least back bonding, due to larger difference in size and energy of p orbital and
also bond length is large.
41. (a) From Equipartition theorem,

1
Energy per translational or rotational degree of freedom = kT
2
Energy per vibration degree of freedom = kT
CO2 has 3 translational degree of freedom, 2 rotational degree of freedom and vibrational degree of
freedom = (3 × 3 – 5) = 4.
 Energy per molecule of CO2 from euipartition theorem.
CHEM ACADEMY 1 1
 3  kT  2   4  kT  6.5kT
2 2
(b) If initial and final states achieved by any reversible and irreversible process are same, then S
will be same, because entropy is a state function. So, it is independent of path.
(c) Phase I  Phase II, (Let Hsystem be the enthalpy change from phase I to phase II).
Total entropy change for any process is given by,
Stotal = Ssystem + Ssurrounding ... (1)
If surrounding is at temperature ‘T’ (same as system temperature) and heat absorbed by the
surrounding is qrev.
 qrev = –DHsystem (at constant pressure) ... (2)
Hsystem
 Ssurrounding =
T
Therefore, from equation (1) and (2),
Hsystem
Stotal  Ssystem  (at constant T and P)
T
 –T Stotal = –TSsystem + Ssystem
– T Stotal = G ... (3)
As Stotal = Sphase I  Phase II + SPhase  Phase I
 Stotal = 0 (because entropy is a state function)
(d) dG = VdP – SdT
At constant P, dP = 0 and at constant T, dT = 0
From equation (3)
 G  0 (substitute value of Stotal)
So, at constant T and P, G = 0, for reversible phase change.
(e) In transition state theory, a reaction is assumed to involve the attainment of an activated complex
that goes on to product at an extremely rapid rate. The rate of decomposition of the activated
complex about 6 × 1012 s–1 at room temperature.
42. For the second order reaction

P + Q k Products


t = 0, 0.05 m 0.05 m 0
t=t
Given,
CHEM ACADEMY (0.05 – x) (0.05 – x) x
3000
log10 k  20  ... (1)
T
At T = 300 K, k = 1010.
We have,
Ea
 log10 k  log A  ... (2)
2.303RT
From (1) and (2)
Ea = 3000 × 2.303 × 2 cal/mol = 13818 cal/mol = 13.818 kcal/mol
3000
LogK  20 
T
When T = 27ºC = 300 K
and, For a second order reaction
1
t1/ 2 
A 0 .k
1
 K
A 0 .t1/ 2
1 3000
Log  20 
A 0 .t1/ 2 T
Substituting
T = 300 K
A0 = 0.05
half-life can be calculated
t1/ 2  3.3  1011 min

43. Fe3O4(s) + CO(g)  3FeO(s) + CO2(g)
t = 0, 1 mol 2 mol 0.5 mol 0.3 mole
at equim (1 – x) (2 – x) (0.5 + 3x) (0.3 + x)
(0.3  x)
 5 atm
PCO 2 (0.3  x)  (1  x)
K  Kp  ; 1
eq m PCO 2x
 5 atm
(0.3  x)  (2  x)
0.3  x
 1 ; 2 – x = 0.3 + x; x = 0.85 mole
 CHEM ACADEMY
2x
At equilibrium, Fe3O4 (s) = 1 – x = 0.15 mole
CO(g) = 2 – x = 1.15 mole
FeO(s) = 0.5 + 3x = 3.05 mole
CO2(g) = 0.3 + x = 1.15 mole
8 x y z
44. (a)   sin sin sin ... (1)
a3 a a a
Schrodinger equation is, Ĥ  E
2 2 2 2 
ˆ           V
H ˆ
Time independent t, 
2m  x 2 2 2 
y z 
 2   2 2 2  
   2  2  2   V̂    E
 2m  x y z  
As V = 0,
 2   2   2  2 
       E ... (2)
2m  x 2 y2 z 2 
Substituting  from equation (1), in L.H.S. of equation (2),
  x   y   z  

2 d 2  sin  d 2  sin  d 2  sin  
 8 y z  a  8 x sin z a 8 x z  a 
  sin .sin  3 sin . .  2   3 sin .sin 
2m  a 3 a a dx 2
a a a dy a a a dz 2

 
= E
2
2 8   x y z 
  3
    3sin .sin .sin   E
2m a a  a a a 
3 2 2  8 x y z 
 2  3
sin .sin .sin   E
2ma  a a a a 
3 2 2
   E
2ma 2
32 2 3h 2  h 
 E     2 
2ma 2 8ma 2  
(b) P T = PA + PB  PA  x A PA* , PB  x B PB*
CHEM ACADEMY
Where, PT = Total pressure
xA = Mole fraction of A in solution
xB = mole fraction of B in solution
PA* , PB* = vapour pressure of pure liquids.
PT  x A PA*  x BPB*
= 0.5 × 70 + 0.5 × 20 = 35 + 10 = 45 torr
PA 35 P 10
yA    0.78; y B  B   0.22
PT 45 PT 45
yA(x), yB(y) = mole fraction of vapour.

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CHEM ACADEMY 1 IIT-JAM 2005

(iii) CH3OOCCH 2COOCH 3 (iii) CH 3COCH 2 NO 2

24. The value of integral  e  x x 2dx is

(a) 1.21 V (b) 0.33 V (c) –0.036 V (d) 0.036 V

(b) (Using diethyl malonate as the only source of carbon)

33. Suggest a suitable mechanism for each of the following reactions.

34. Rationalize the following observations using suitable mechanism.

Correct option is (d)

Correct option is (b)

Correct option is (b)

Correct option is (c)

Ag2S2O3 + H2O  Ag 2S  H 2SO 4

Correct option is (b)

Using equation (i) and equation (ii), we get

Energy of H-like atoms (En) = 

For ground state, n = 1  E  µz 2

Correct option is (d)

34. (a) Chemial reaction occuring in above transformation can be illustrated as

cis-4t-butylcyclohexyltrimethylammonium hydroxide undergoes Hoffmann elimination, because

35. (a) CHEM ACADEMY

36. (a) (i)

Central ‘I’ has 3 l.p. and 2 b.p., So, it is sp3d hybridized.

CHEM ACADEMY Geometry  tetrahedral, Shape  Pyramidal

‘P’ has 5 b.p. of electron-cluster surrounding it.

2[Fe(H 2O)6 ]3  2H 2O 

(b) [Fe(H 2O) 6 ]2  2ClO 4

[Fe(H 2O)6 ]2  H 2O 

and [Fe(H 2O)6 ]3  3ClO 4

[Fe(H 2O)6 ]3  H 2O 

C.F.S.E. of Cu+2 complex = 

C.F.S.E. = –0.40 × 5 + 2P0 = –20 + 2P0

(iii) [NiCl4 ]–2

41. (a) From Equipartition theorem,

42. For the second order reaction

t1/ 2  3.3  1011 min

Schrodinger equation is, Ĥ  E

Substituting  from equation (1), in L.H.S. of equation (2),

(b) P T = PA + PB  PA  x A PA* , PB  x B PB*

PA* , PB* = vapour pressure of pure liquids.

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