Birla Institute of Technology & Science, Pilani, Raj.

-333 031
I Semester, 2019-20

Course No.: CHEM F111 Course title: GENERAL CHEMISTRY Max. marks: 15

Tutorial Problem Set 3 based on Lecture Nos.: 23 – 31 in the course handout

Instructions to the students: The following problems should be solved as home assignment within a
week of distribution. The respective tutorial hour instructor will assign any one problem as a closed
book test in the pre-assigned hour. Given, R = 8.314 J/(mol.K)

Q. No. 1. (a) What is/are the driving force (s) behind the following conversion, from complex I to
complex II? Calculate the overall formation constant (β) in "log10" form for complex II at 40 oC, if the
standard enthalpy and entropy changes are -8.1 kJ/mol and 0.152 kJ/mol, respectively? [2+5]
3+ 3+
[Co(NH3)6] + 3(1,10 phen) [Co(1,10 phen)3] + 6NH3
complex I complex II

(b) The electronic spectrum of K3[CoF6] complex shows absorption values at 10,200 cm-1 and 14,500 cm-
1
. How can you account for the presence of two bands in the electronic spectrum of K3[CoF6] complex?
Theoretically how many band (s) is/are possible in the electronic spectrum of K3[CoF6] complex. Specify
all the possible transitions in light of ground state term using Mulliken symbols. [3+2+3]

Q. No. 2. (a) Example of few six coordinated high-spin octahedral complexes are FeF2, K3[CoF6],
[Fe(H2O)6]3+, and [Cr(H2O)6]2+. Which of the above complex (s) shows pale color and why? [4]

(b) 1 ml of a 0.01 M metal solution and 1 ml of a 0.03 M ligand solution were mixed. The final
concentration of the metal complex (ML3) was 0.005 M. Calculate the overall stability constant (β3) of
the complex? [4]

(c) Theoretically how many band (s) is/are expected in the electronic spectrum of the following
complexes. Assign the electronic transition (s) in light of ground state term of metal ion using Mulliken
symbol. The order of levels in an octahedral field arising from Mulliken symbols for spectroscopic term,
S: A1g, P: T1g, and D: Eg > T2g. [7]
2- 4-
(i) [CuCl4] (ii) [Cr(CN)6] (iii) [CuCl]

Q. No. 3. (a) The magnetic moment of 31P is equal to 1.1305 nuclear magnetons i.e., 1.1305 μN. Calculate
its magnetogyric ratio and the g-factor. Given, μN = 5.05 × 10-27 J/T and nuclear spin of 31P is 1/2. [7]

(b) The chemical shift of the CH3 protons in acetaldehyde is δ = 2.20 and that of the CHO proton is 9.80.
What is the difference in local magnetic field between the two regions of the molecule when the applied
field is (i) 1.2 T and (ii) 5.0 T? [8]

1
Q. No. 4. (a) A proton jumps between two sites with δ = 4.8. At what rate of interconversion will the two
signals collapse to a single line in a spectrometer operating a 550 MHz? [5]

(b) The benzene radical anion has g = 2.0025. At what field should you search for resonance in a
spectrometer operating at (i) 9.302 GHz and (ii) 33.67 GHz? [5]

(c) The resonance from a group of protons in a polypeptide is observed at δ = 6.33. What is the difference
in the frequency of this resonance from that of TMS in a spectrometer operating at 500.0 MHz? [5]

Q. No. 5. (a) Given the following compound: CH3CH(CH3)COOCH2Br. Answer the following questions
pertaining to its 1HNMR spectrum: (i) How many signals will be observed in its 1HNMR spectrum? (b)
What will be the multiplicity of each signal? (ii) Which set of protons will appear most downfield?
[2+3+2]

(b) An unknown organic compound with molecular formula C3H6O2 shows the following 1HNMR
spectrum: : 8.50 (s, 1H), 4.21 (q, 2H), 1.30 (t, 3H). (i) Predict a reasonable structure of the compound.
(ii) Indicate which set of protons has what chemical shift. (iii) The compound is expected to show how
many signals in its 13CNMR spectrum? [3+3+2]

Q. No. 6. (a) A compound having molecular formula C8H10O2 shows the following spectral data:
1
HNMR: doubletdoublet, 2H); broad singlet, 1H);quartet, 2H);triplet,
3H). IR (important peaks): 3300 cm-1 (broad); 1100 cm-1 (strong). Predict the structure of the compound
and state which NMR peak is due to which set of protons. [4+4]

(b) (i) The 1HNMR spectrum of a compound C3H5ON shows the following absorptions: 5.8 (singlet,
1H); 6.2 (triplet, 2H); 7.4 (triplet). Predict a reasonable structure for the compound. (ii) How many
13
CNMR signals would you expect from the following compounds? Label each carbon clearly by
drawing structures: (x) Methylcyclopentane (y) 2-Methylbut-2-ene (iii) State the total no. of signals that
will be observed in the 1HNMR spectrum of the compound shown below. Also show the multiplicities of
each of those signals. [2+3+2]

2
Q. No. 7. (a) (i) Draw the possible chair conformation/s for cis-1,3- dihydroxycyclohexane and label the
axial and equatorial substituents. (ii) Among these conformations, identify the most stable conformation
and explain briefly why it is so. [3+4]

(b) Which of the two 1,3,5-trimethylcyclohexanes (shown below) would you expect to be more stable
and why? Draw appropriate conformations to explain your answer. [8]

Q. No. 8. (a) (i) Draw highest and lowest energy conformations using Newman projections for 2,3-
dimethylbutane by viewing along C2-C3 bond. (ii) Determine the energy difference (kJ/mol) between the
two conformations (Given that interaction energy cost kJ/mol: Me-Me gauche = 3.8 kJ/mol, Me-Et
gauche = 4.2 kJ/mol, Me-H eclipse = 6.0 kJ/mol, Et-H eclipse = 6.4 kJ/mol, Me-Me eclipse = 11.0
kJ/mol, Me-Et eclipse = 12.0 kJ/mol, and H-H eclipse = 4.0 kJ/mol, Me-H gauche = 0; Et-H gauche = 0)
[4+4]

(b) Compound A (C6H8) reacts with two molar equivalents of hydrogen in the presence of a catalyst to
produce B (C6H12). The proton-decoupled 13CNMR spectrum of A consists of two singlets, one at  26.0
and one at  124.5. In the 13C spectrum of A the signal at  26.0 appears as a CH2 group and the one at 
124.5 appears as a CH group. (i) Propose structures for A and B. (ii) How many signals would be
obtained for the 1HNMR spectrum of A and B respectively? [5+2]

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