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I

CHEM ISTR Y
Paper -I

Inme Allowed : Three Hours I

. I Maximum Marks : 200 I

QUEST ION PAPER SPECI FIC INSTRUCTIONS

Please read each of the following instructions carefully before attempting questio
ns :
There are EIGHT questions in all, out of which FIVE are to be attempted.
Question nos. 1 and 5 are compulsory. Out of the remaining SIX questions, THREE
are to be al/empted
selecting at least ONE question from each of the two Sections A and B.
Allempts of questions shall be counted in chronological order. Unless struck off,
attempt of a question shall
be counted even if allempted partly. Any page or portion of the page left blank
in the Answer Book must
be clearly struck off.
All questions carry equal marks. The number of marks carried by a question/part
is indicated against it.
Answers must be wrillen in ENGLI SH only.
Unless otherwise mentioned, symbols and notations haVe their usual. standard
meanings.
Assume suitable data, if necessary and indicate.the same clearly.
Neat sketches may be drawn, wherever required.

SECT ION-A
(h = 6.626 X w-34 JS; ko = 1.38 X 23 J K- 1; R
RH = 10973731.6 m-1; c = 3 x JoB ms,-1)

w-

· Q. I. Answer briefly all tbe parts :
Q. !(a)

=

8.314 JK- 1 mol- 1;

7t

= 3.14;

}0X4=40

A Phase Rule can be written as F = C - P + 2, where F is the number of degrees
Qf
freedom, P is the number of phases and C is the number of components.
(i) Define the terms degree · offreedom , phase and compon ent.

(ii) Use the Phase Rule to show why, when plotting a phase diagram of a 2-comp
onent
system, it is necessary to fix a variable (usually volume).
6,4
Q. !(b) What is meant by the lattice energy of an ionic compound ? What
quantities need to be
determined and how are they used to calculate the lattice energy of an ionic compou
nd ?
10

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2Aplh. 2(a) Heisenberg's Uncertainty Principle (HUP). A. (ii) Calculate the wavelength. (ii) Give an alternative non-mathematical statement of HUP. I (c) AxAp (i) ~ hl4n Define the symbols Ax and Ap .m. show that implies that &'A = Mp/p 2 = 'A. rature whereas hydrogen gas (ii)· "Nitrogen gas gets cooled on expansion at room-tempe 5.com . (i) 2 ••': www. Indicate whether the H atom emits energy or absorbs energy Justify your answer. I 0.4. of the radiation associated associated with the same (iii) Account for the observation that the amount of energy r than that associated electronic transition (n = 6 to n = 2) in the He+ ion is greate 5." Explain. d to the position. 2(b) A certain line in the spectrum of atomic hydrogen is associ d energy level (n = 2). I (d) Explain the following observations on the basis HCl gas is introduced (i) When NH3 gas is introduced at one e~d of a long tube while de is observed to simultaneously at the other end.. on in (iv) assuming and hence calculate the uncertainty in the wavelength of the electr 4. as applie p.examrace. Calculate the minimum value of Ap for an electron 9 molecule of length L = 3 x I o. the propagation of errors (iv) Starting from the de Broglie relation. in nm. .6 that the wavelength 'A = 2L. This ring is closer to the than the NH 3 end. the maximum value of (iii) For a particle trapped in a one-dimensional box of length trapped in a linear Ax is L. '! The BF molecule is isoelectronic with carbon monoxide.5 on your diagrams ? of the kinetic theory of gases : Q. = hlp. Comment on your answer. and clearly state the units. . ated with the electronic transition Q. x.5 gets warmer. a ring of white ammonium chlori HCI end of the tube form in the tube after a few minutes.. and momentum. of a particle can be given mathematically as : Q. of the H atom from the sixth energy level· (n = 6) to the secon during the transition.6. Q. What assum straightforward than which makes the MO construction for this molecule much more for CO? ures of BF and CO in (ii) Discuss the similarities and differences in the electronic struct le Lewis structures can terms of cr and 1t bonds and nonbonding orbitals. What possib for each species based be drawn for BF and CO and which is the most reasonable 5. with the spectral line.5 with the corresponding transition in the H atom. L.• . ption can be made in BF (i) Construct an MO diagram· for the BF molecule.

·' Q.5.0154 K to the four molecules ICI. (iii) Determine the value of the equilibrium constant. . HI. He. 0. 5(a) Account for each of the following observations : (i) The complex [NiC14 ] 2. · (i) Which balloon contains the greatest mass of gas ? Explain.5. Keq• for the reaction at 25°C. E 0 . --J Why is it usually a poor approximation to equate activities and concentrations for ionic solutions ? (ii) Outline the Debye-Hiickel theory of dilute ionic solutions. for the half reaction below : 5.. 1 . Assign the. 1'10°.0 atmosphere pressure with the pure gases C02.examrace. 0.164 K. for the half reaction Oz(g) + 4W(aq)+ 4e. (iv) The standard reduction potential.5. (ii) Compare the average kinetic energies of the gas molecules in the balloons. for the reaction at 25°C.5 which balloon will be the smallest.'.is attracted towards a magnetic field.55 V What is meant by the standard electrode potential and how is it measured ? (ii) Determine the value of the standard Gibbs energy change.: . order of increasing rotational partition function for the four molecules at I 00 K.. Using this information in addition to the information given above.23 V.~ 2 H20(I) has a value of 1. 3(a) Match the following rotational temperatures 8. 12 and IBr.5 (ii) [PtC1 2(NH3) 2] has two isomers. N2 and CH4 . 5. Explain.01 = 0. H20 2 decomposes according to the following equation : E0 (i) = 0. 9. determine the value of the standard reduction potential. 4(b) (i) . Why is the central result of this theory described as a limiting Jaw ? (iii) When and why can Debye-Hiickel theory fail to describe the behaviour of ionic · solutions accurately ? 5. Explain your reasoning. 0 2. E0 .12 K.082 K. 4(a) At 25°C. (iii) Which balloon contains the gas that would be expected to deviate most from the behaviour of an ideal gas ? Explain. Explain your reasoning.com .1 0. 3 www.5 Q..5. 3(b) Five identical balloons are each filied to the same volume at 25°C and 1. Predict 5. I '' ' ~ Q. (iv) Twelve hours after being filled. all the balloons have decreased in size.5 SECTION-·B Q. 20 Q.

Initial [N.e. I0 Q.OLA ! · I 0.O.5.~. 10 Q. [Cr(en)(OH 2)iC1) 2]+ + Hp k =3. 6(b) The reaction catalyzed by an enzyme recently purified from E. S(c) Based on the rate constants given. . www. . k. Assume initial rate conditions (i.5 Q. Is the initial complex cis or trans ? Explain your answer. describe how the value of the rate constant. E+S (i) k_. k.1 [Cr(en)(OH 2)4]3+ + Cl- 5. k_. k. indicate if the stepwise substitution reaction shown below proceeds via an associative or dissociative· mechanism.e : (I) First-order in substrate concentration (2) Zero-order i~ substrate concentration ? C-RRHr-H-lk. rate equation for the above reaction in the forward direction. what would be the effect on the rate constant.com .1 [Cr(en)(OH2) 3(Cl)] 2+ + ct- [Cr(en)(OH2)3(Cl)]2+ + H20 k =3. Explain your answer. (ii) Describe how the graph in part (i) could be used to find the reaction rate at a given time. only one isomer of the complex product is obtained. (iv) If more N 20 5 were added to the reaction mixture at constant temperature.5 . k ? Explain. Show all of your work and the necessary assumptions and equations. coli is shown below : . (iii) Considering the rate law and the graph in part {i). Q.0xl0-7s. Q. 6(a) The reaction 2Np 5 {i) ~ 4N0 2 + 0 2 is first order with respect to N 20 5• Using the axes below.examrace. ' (ii) Under what circumstances the kinetics ar.. could be determined. complete the graph that represents the change in [N 0 ] over 2 5 time as the reaction proceeds.1xl0-ss. I 0 . S(b) In the reaction [CoCliNH3)4]+ + Cl- ~ [CoC1 3(NH 3) 3] + NH3. ES . t. S(d) Explain why f-f transitions in the electronic spectra of lanthanide complexes are weaker than d-d transitions in the corresponding spectra of transition metal complexes. [P] 1= 0 = 0).] Time 5.5. E+P Derive the Steady State.

and the equilibrium 10. indicating appropriate symmetry labels for the orbitals. 7(b) (i) 15.10 (ii) Super-acids. and the crystal field splitting parameter. 8(a) Write brief notes on the following : (i) Ferredoxins 10. Q.examrace. (ii) Explain the ways in which increased ligand-field splitting for second and third row transition metals affects the geometry of four-coordinate Pt(II) complexes compared with the geometry of four-coordinate Ni(II) complexes. 7(a) For the complex [CoCI 4] 2- (i) : Draw a diagram to show the energy splitting of the 3d orbitals. 8(b) (i) Compare the solvent behaviour of water. the occupancy of the orbi~ls with electrons. I 0. show a larger ligand field splitting than complexes of first row transition metals.com . and liquid ammonia.10 Q.10 ·5 www.5 Give reasons why complexes of second and third row transition metals typically . How does ammonium hydroxide behave in liquid ammonia ? (ii) The relaxation-time for a reversible first-order reaction is I x constant is 1 x 103• Find K 1 and K_ 1• w-s s.Q. (ii) Calculate the crystal-field stabilization energy in multiples of the crystal-field splitting parameter. Q.