Birla Institute of Technology & Science, Pilani, Rajasthan - 333 031

I Semester 2016-2017
CHEM F111 GENERAL CHEMISTRY
Mid-Semester Examination (Closed Book)
Max. Marks: 90 Duration: 90 minutes Date: 07th October 2016
NOTE: There are FIVE questions in all. Attempt all the questions. Start answering each question on a fresh page
and answer all parts of the question together. Pencil should not be used. Symbols have usual meanings. Do not
scribble on the question paper.

USEFUL DATA: σ = 5.6697  10-8 Wm-2K-4; b = 2.9 mmK; c = 3  108 m/s; Mass of electron = 9.109  10-31 kg
1 amu = 1.66  10-27 kg; a0  0.529 Å; h = 6.626  10-34 Js; R = 8.314 JK-1mol-1; 1 bar = 101.3 kPa
x 1
Standard integral:  sin 2bx dx   sin 2bx ; 1Å = 10-10 m; 1 nm = 10-9 m
2 4b

Q. 01. (a) An average human body has a surface area of 0.1 m2. Assuming human body behaves like a black body,
calculate power emitted by this body at 37 °C ? [3]
(b) A linear conjugated molecule of length, L, can be approximated using the particle in a one-dimensional box. The
2 3x
wavefunction corresponding to one of the energy levels is given by  sin ; 0 x L
L L
(i) Write the number of node(s), if any, present in the energy level corresponding to the given wavefunction.
(ii) Evaluate probability of finding the electron described by the above wavefunction within 0.4L to 0.5L.
(iii) If the length, L, of the molecule is 12Å, calculate the wavelength (in nm) of the electromagnetic radiation
required to excite the electron from n = 5 to n = 6 level. [1+4+4]
(c) A particle of mass, M, moving in a two-dimensional ring of radius, r, is associated with zero potential energy
imɸ
and is represented by a wavefunction ψm(ɸ) = e ; where m is rotational quantum number:
(i) Write down the expression of Hamiltonian operator (in polar coordinates).
(ii) Determine the magnitude of kinetic energy associated with this particle when it is present in the ground energy
level; given that the moment of inertia, I, is 4 × 10-42 kg m2.
(iii) Normalize the wavefunction, ψm(ɸ), and determine the value of normalization constant. [1+2+3]
x+
Q. 02. (a) The expression of a particular orbital of a hydrogenic atom (B ) is,
3
1  3  2
 3r  3r 2 a0
 1
   e cos 
4(2 ) 2  a0   0
a
(i) Fill up the following table on the basis of the above information (Answer the question in the tabular format by
drawing table in your answersheet as given below): [5]

Atomic Symbol (B) Atomic charge (x) n l |ml|

(ii) Write the expressions for Coulomb potential energy and total energy corresponding to this orbital. [2]
(iii) Determine the numbers of radial and angular node(s), if any, present in this orbital. [2]
(b) Determine the electronic configuration for an atom belonging to 2nd period of the periodic table with the ground
4
state term symbol S3/2. [4]

(c) Calculate the most probable radius at which an electron will be found when it occupies 1s orbital with radial
4Z 3 2 2 Zr a0
distribution function, P(r )  3 r e
7+
of a hydrogenic atom, O in Angstrom unit (Å). [5]
a0

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Q. 03. (a) Calculate the spacing between the 3rd and 6th spectral lines (in cm-1) in the rotational spectrum of 1H35Cl
molecule having bond length of 0.127 nm. [6]
(b) IR spectra of two pairs of compounds: (i) [CH3C≡N and CH3C≡CCH3], and (ii) [C6H5CH2NH2 and
C6H5CH2CONH2] are given to you. Write the distinguishable IR band(s) for each given pair of compounds. [4]
(c) The force constant for HF molecule is 9.7  102 N m-1. Calculate the wavenumber (in cm-1) of IR radiation to
excite the molecule from n = 0 to n = 1, where n is the vibrational quantum number. [4]
(d) Arrange the following compounds (I, II and III), in order of decreasing ῡC=O stretching frequency. Give reasons
for the order chosen. Explanation for each compound is required. [4]

Q. 04. (a) A compound C8H18O2 with a strong broad IR absorption band at 3293 cm-1 exhibits peaks at  1.22 (12H,
singlet), 1.57 (4H, singlet) and 1.96 (2H, broad singlet) in 1H-NMR spectrum. The proton decoupled 13C NMR of this
compound consists of three lines resonating at  29.4, 37.8 and 70.5. Identify the structure of compound and
assign given chemical shift values of 1H-NMR for different group of protons. [8]
(b) A NMR signal is appearing 120 Hz downfield from TMS in an instrument operating at 300 MHz. (i) What is
signal’s chemical shift (δ)? (ii) What would be its chemical shift if the spectra is recorded in an instrument operating
at 100 MHz? [4]
(c) Complete the following table by writing all the information for compound [A] in given format at one place.
(Answer the question in the tabular format by drawing table in your answersheet as given below) [1+2+1+2]

Compound [A] Number of peaks Label the most Multiplicity of Number of peaks in
1
in H NMR de-shielded protons each peak in H proton decoupled 13C
1

NMR NMR

Q. 05. (a) Reduction of Fe(III) oxide by carbon is presented as, 2Fe2O3 (s)  3C (s) 
 4Fe(s)  3CO2 ( g ) ; Using
the data provided in the table given below, determine: (i) ΔrH298 , (ii) ΔrS298 , (iii) ΔrG298, and (iv) estimate the
minimum temperature at which the reaction becomes spontaneous at 1 bar pressure. [2+2+2+2]
Fe2O3 (s) C (s) Fe (s) CO2 (g)
ΔfH298 (kJmol-1) -824.2 0 0 -393.5

S298 (JK-1mol-1) 87.4 5.7 27.3 213.7

(b) The normal boiling point of a solvent is 80 °C and its ΔvapH = 30.8 kJmol-1. Assuming that ΔvapH is independent of
temperature in the temperature range and that the vapor behaves ideally, calculate its boiling point at 5 kPa. [3]

Br 
(c) The mechanism of Br -catalyzed aqueous reaction, H   HNO2  C6 H 5 NH 2   C6 H 5 N 2  2H 2O , is
described below,
k k
Step 1 : H   HNO2 1 HNO
2 Step 3 : HNO2  Br   2  ONBr  H O
2
k k
Step 2 : HNO2  
1 H   HNO Step 4 : ONBr  C6 H 5 NH 2 
 3 C H N   H O  Br 
2 6 5 2 2

d
(i) Identify the reaction intermediates, I1 and I2; (ii) Determine the rate of the reaction, r  [C6 H 5 N 2 ]
dt
d d
(iii) Determine: [ I1 ] and [ I 2 ] ; (iv) Determine the expression of r using Steady State Approx. [1+1+2+3]
dt dt

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