Birla Institute of Technology and Science, Pilani - Hyderabad Campus
Semester-II, 2023-24
Model Solution-CHEM F111-General Chemistry
Comprehensive Examination (Closed Book)-Part B
Marks: 60 Maximum Time: 180 minutes Date: 12.05.2024
1. (a) IHD = 5 [0.5M]
IR = 3032 for sp2 C-H stretch, 1734 for C=O (of ester), 1170 for C-O stretch [3 x 0.5 = 1.5 M]
NMR common observation: 0.5 marks for identifying each NMR signal correctly [0.5 x 5 = 2.5M]
Possible structures: 1.5 marks for identifying the structure correctly [1.5 M]
(b)
(i) There are three proton NMR signals for this compound [0.5M]
(ii) Signal at a is seen as a singlet. Signal at b is seen as a quartet in the intensity ratio 1:3:3:1
and the signal at c is seen as a doublet in the intensity ratio 1:1. [0.5 x 3 = 1.5 M]
(iii) Proton a is the most deshielded proton. [0.5M]
(c) Yes [0.5 M]. We do observe negative chemical shift values [Link] TMS for a few compounds.
Some large unsaturated ring systems such as porphyrins and annulenes, where H atoms are located
inside the ring experience less field compared relative to the applied field and hence appear at
lower chemical shifts relative to the reference TMS. They appear 1 or 2 ppm beyond the TMS and
thus become negative. [1M]
(d)
has highest carbonyl stretching frequency as the CHO is not in conjugation. [1M]
has lowest carbonyl stretching frequency amongst all as the CHO
is in more extended conjugation. [1M]
(e) A vertical line for (P), v" = 0 to v' = 0 (not in any higher state). [1M ]
A vertical line for (Q), v" = 0 to v' = 2 [Transition in any higher state (ν' = 3) is ok but not at zero].
[1M ]
[1M]
2. (a) (i)
(ii)
(iii)
(iv)
[1M x 4 = 4M]
(b) Optical purity of the bromide = (28o/36o) x100 = 77.77%;
Optical purity of alcohol = 6o/10o x100 =60%;
Percentage inversion = 60/77 x100 =77.15;
% racemization =100-77.15 =22.85.
(Each value with the steps shown clearly carries 1 mark= total 4 marks for 4 steps)
(c) SN2 reactions involve back side attack by a strong nucleophile and hence it is total inversion
and not racemization. [1M]
(the above two highlighted key words should be mentioned to get full marks)
(d) (i)
C2 H5
(ii)
(iii)
[2M + 2M + 2M = 6M]
(Marks are only for structure of major product and should be encircled. If more than one
product is written, then the major product should be encircled or else no marks)
3. (a) d[C]/dt = k2 [B] [M];
Using steady state: d[M]/dt = k1 [A] [B] - k-1 [M] - k2 [B] [M] = 0 [1 M]
k1 [A] [B] = k-1 [M] + k2 [B] [M] ; k1 [A] [B] = [M] {k2 [B] + k-1}; ;
[M] = k1 [A] [B] / {k2 [B] + k-1}
[M] = k1 [A] [B] / k2 [B] if k2>>>k-1 [1M]
d[C]/dt = k2 [B] k1 [A] [B] / k2 [B] = k2 k1 [A] [B] / k2 = k2 k1 [A] [B] / k2 =k1 [A][B] [1M]
(b) (i) enantiomer with proper R/S justification as below [2M]
(ii) constitutional isomer because the linkages are different [2M]
(c) All are optically active [1.5M] and no inversion center of symmetry [0.5M].
(d)
[1M x 3 = 3M]
(e) It needs light. [1M]
Odd- photochemical-conrotation;
It needs asymmetrical orbital for in-phase overlap. It will be asymmetrical.
[1M]
It needs disrotation for out of phase orbital overlap [1M].
4. (a) Mn has 4s23d5 electronic configuration. Mn is in +3 oxidation state in [Mn(H 2O)6]3+
complex, therefore, it has 4 electrons in 3d orbital. Due to unsymmetrical filling of electrons
in the d orbital, this complex will undergo Jahn Teller distortions with z-elongation. Electronic
arrangement is given below.
[2M for showing JT distortion diagram and proper labelling + 1M for correct electron filling]
The structure of the complex will be distorted octahedral with two long bonds and four short bonds.
[2M for final correct structure with charge. 1M for correct structure drawing without +3 charge.
No marks if the structure drawing is missing]
(b)
1M for Ni metal ion electronic configuration, 1M for showing ligand electron filling, 1M for
determining hybridization, 1M for correct labelling of the orbitals.
[4M]
Ni will have two unpaired electrons in this complex and therefore by using the formula µ =
[n(n+2)]1/2 , where n = 2, the spin only magnetic moment value will be 2.82 BM. [1M]
(c) Co is in +2 oxidation state in CoCl64- complex.
Given, Δo for the complex = 18000 cm-1 = 18000/83.7 = 215 KJmol-1
So, CFSE for the complex = (-0.4x5 + 0.6x2) Δo = -0.8 Δo = -0.8 x 215 = -172 kJmol-1 [2M]
Δt for the CoCl42- complex = (4/9) x 215 = 95.55 kJmol-1. [1M]
CFSE for CoCl42- complex = (-0.6x4 + 0.4x3) = -1.2 Δt = -1.2 x 95.55 = -114.66 kJmol-1. [2M]
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