Birla Institute of Technology & Science Pilani

Pilani Campus
Second Semester 2021-2022
CHEM F111 General Chemistry
Marks: 20 Mid Sem. Test
---------------------------------------------------------------------------------------------------------------------------------------------
Q. 1
Q. 2 (a) Consider the excited electronic configuration of He, 2p13d1. (i) Write down all the possible terms for this
configuration. (ii) From the above answer identify the term with highest number of microstates and for this term,
write the symbol for each one of the possible levels along with their degeneracy.
[3+5]

s1 = ½; s2 = ½ ; S = 1, 0 ; 2S+1 = 3, 1.
l1 = 1; l2 = 2; L = 3, 2, 1.
The Terms are 3F, 3D, 3P, 1F, 1D, 1P. [3]
3F  (2S+1)(2L+1) = 3 x 7 = 21 microstates [2]
J = 3+1, …, |3-1|= 4, 3, 2
The Levels (degeneracy): 3F (9), 3F (7) and 3F (5) [3]
4 3 2
 (b) Determine the value of the normalization constant for anti-bonding molecular orbital of H2+
molecular ion. Given that the value of overlap integral (S) between the atomic orbitals ɸ1sa and
ɸ1sb is 0.59.
[6]

Ψ- = N (ɸ1Sa - ɸ1Sb)

Where, Ψ- = wave function for anti-bonding molecular orbital, N = normalization constant,

ɸ1Sa and ɸ1Sb are the atomic orbital of two hydrogen atom

In the following, the integrations are done in entire space; (r = 0 to ∞; θ = 0 to π and φ = 0 to 2π)

Therefore, ʃ Ψ-2 dτ = N2ʃ(ɸ1Sa - ɸ1Sb)2 dτ = 1 [1]

or, N2 [ʃ ɸ1Sa2 dτ + ʃ ɸ1Sb2 dτ - 2 ʃ ɸ1Sa ɸ1Sb dτ] = 1

or, N2 [2 - 2S] = 1 [1]

here, ʃ ɸ1Sa ɸ1Sb dτ = S, overlap integral

or, N = 1/√(2 - 2S) [1/2]

Therefore, N = 1/√(2 - 2 x 0.59)

or, N = 1.10 [1/2]

(c) Write down the bond order and the spin only magnetic moment of B2, B2 and B2[3]

Species Configuration Bond order Spin only Magnetic

(B el – AB el)/2 moment in BM
√n(n+2)
B2 1σg21σu21πu1 0.5 1.732
B2 1σg21σu21πu3 1.5 1.732
B2 1σg21σu21πu0 0 0
(see the note below)
(6 x ½ = 3)
Note: B2will not exist; The moment the second electron is removed from B2 it will break into two
B+ species.
 (d) The atomic masses of iodine and hydrogen atoms are 126.9045 g/mol and 1.007825 g/mol, respectively.
Calculate (i) the moment of inertia of HI and (ii) the separation (in cm-1) between the first Stokes and first
anti-Stokes line in the rotational Raman spectrum of HI (The internuclear separation in HI is 160.4 pm). (1 pm
= 10-12 m) [2+4]

126.9045 x 10−3
𝑚𝐼 = = 2.108 x 10−25 𝑘𝑔
6.02 x 1023

1.007825 x 10−3
𝑚𝐻 = = 1.674 x 10−27 𝑘𝑔
6.02 x 1023
2.108 x 10−25 x 1.674 x 10−27 2.108 x 10−25 x 1.674 x 10−27
𝜇𝐻𝐼 = 2.108 x 10−25 + 1.674 x 10−27 = 2.1247 𝑥 10−25
= 1.6608 x 10−27 𝑘𝑔 [1]

𝐼 = 𝜇𝑟 2 = 1.6608 x 10−27 x (160.4 x 10−12 )2 = 4.273 x 10−47 𝑘𝑔𝑚2 [𝟏]

ℏ ℎ 6.626 x 10−34
𝐵 = 4𝜋𝐼𝑐 = 8𝜋2 𝐼𝑐 = 8𝜋2 x 4.273 x 10−47 x 2.997 x108 = 655.3 𝑚−1 = 6.553 𝑐𝑚−1 [2]

Spacing between the first Stoke’s and first anti-Stoke’s lines = 12B = 78. 636 cm_1 [2]

Q. 3 (a) The compound R-12C14N shows stretching frequency at 2210 cm-1. Calculate force constant (k) for
CN bond?
 = 1.04 × 10-26 Kg 1M
1858.40 N/M 3M [4]
(b) Match the following compounds to the corresponding distinctive absorption peak(s) that are observed in
their respective IR spectrum. [3]
Ans
Compounds Absorption peak(s) (in cm-1)

i) (CH3)2C=CHCOCH3 r) 1690 and 1620

ii) CH3-CO-NH2 p) 1680, 3415 and 3520
iii) CH3CH2CH2CO2H q) 1710 and 3400 (broad band)

(c) Calculate the strength of the magnetic field required to observe NMR signal of a specific nucleus (𝑔𝑁 =
1.405) in a spectrometer that operates at 100 MHz.
B = 9.33 T [3]
(d) Two signals one at a frequency 510 Hz higher than that of TMS and other one at a frequency 280 Hz
lower than that of TMS are observed in the 1H NMR of a compound recorded on a 250 MHZ spectrometer.
Calculate chemical shifts of these two signals.
2.04 and -1.12 [1 + 1]
(e) Predict number of signals in the 1H NMR of (CH3)2CHOCH2CH2Br and mention their splitting
(multiplicity) pattern.
4 signals 1M
(CH3)2 –doublet 0.5 M
CH –septet 0.5 M
CH2CH2 eatch triplet 1M
(f) Provide structure of compound A (Molecular formula: C4H8O2) that is consistent with the spectral data
given below and assign all relevant peaks in IR and NMR.
IR: 1725 cm-1; 1H NMR:  3.52 (s, 3H), 2.65 (q, 2H), 0.98 (t, 3H). [5]

IR: 1725 cm-1 crabonyl group 1M

CH3CH2COOCH3 Correct structure 1M

OCH3  3.52 (s, 3H), 1M

COCH2 2.65 (q, 2H), 1M

CH2CH3 0.98 (t, 3H). 1M