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Nmr spectroscopy

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Assignment - 1 Solutions

Nmr spectroscopy

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kishor
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Application of spectroscopic methods in molecular structure determination

Assignment 1 Solutions– General aspects of spectroscopic methods

Fundamental constants useful for calculations: (20 marks)


Speed of light = c = 3.0 x 108 ms-1, Planck’s constant = h = 6.626 x 10-34 Js and h/2 = 1.055 x 10-34 Js
Avogadro number = N = 6.022 x 1023 mol-1, Boltzmann constant = k = 1.381 x 10-23 JK-1
1 eV = 1.602 x 10-19 J and 1 wavenumber (cm-1) = 1.986 x 10-23 J

1. Phosphorescence spectroscopy is a absorption/emission/scatter spectroscopy. (Choose the correct


answer).
Ans. Emission Spectroscopy

2. If the FWHM of an infrared spectral line is 4000 cm-1, calculate the life time of the excited state.
Ans. Using the formula,
E. = h/2 , E= hc/λ
4 x 103 x 1.986 x 10-23 J x  = 1.055 x 10-34 Js
 = 1.328 x 10-15 s

3. Calculate the concentration of a solution which has molar absorptivity of 2.0 x 105 L mol-1 cm-1 at 500
nm with an absorbance of 0.4.
Ans. Using the formula,
A = cl
c = A/l = 0.4/2 x 105 L mol-1 cm-1 x 1 cm
c = 2 x 10-6 mol L-1

4. Among vibrational spectroscopy, UV-Vis spectroscopy, rotational spectroscopy and NMR


spectroscopy arrange them in the increasing order of sensitivity purely based on excess population
of the ground state with respect to the corresponding excited state. State reasons for your answer.
Ans. NMR spectroscopy < Rotational spectroscopy < Vibrational spectroscopy < UV-Vis spectroscopy
The energy difference between ground state and excited state of electronic, vibrational and
rotational state are in the order rotational< vibrational< electronic state. Thus, population difference is
high in electronic ground state than that of rotational ground state. The population difference is directly
proportional to the sensitivity of the spectroscopic technique. Hence, the sensitivity of the different
spectroscopic techniques are in the following order, NMR spectroscopy < Rotational spectroscopy <
Vibrational spectroscopy < UV-Vis spectroscopy

5. In vibrational spectroscopy it is the electric field vector/magnetic field vector of the electromagnetic
radiation that interacts with the molecules during vibrational excitation. (Choose the correct answer).
Ans. Electric field vector interacts during vibrational excitation.

6. Name a spectroscopic method that uses 400 MHz frequency of radiation as the excitation source.
Which region of the electromagnetic radiation is this frequency corresponds to?
Ans. Spectroscopic method: NMR spectroscopy
Region of electromagnetic radiation: Radio waves

7. Calculate energy per photon and energy per mole of photons of light of wavelength 200 nm and
another light of frequency 500 MHz. Report the values in eV and Joules mol-1, respectively.
Ans. E = h = hc/
(a) E = 6.626 x 10-34 Js x 3 x 108 m s-1/200 x 10-9 m
= 9.94 x 10-19 J/1.602 x 10-19 = 6.20 eV per photon
Energy per mole = 9.94 x 10-19 J x 6.023 x 1023 mol-1
= 5.99 x 105 J mol-1
(b) E = 6.626 x 10-34 Js x 500 x 106 s-1
= 3.31 x 10-25 J/1.602 x 10-19 = 2.07 x 10-6 eV per photon
Energy per mole = 3.31 x 10-25 J x 6.023 x 1023 mol-1
= 0.1994 J mol-1

8. The energy gap (E) between two electronic energy levels is 2.5 eV in a molecule. Calculate the
population ratio of molecules in excited state to the ground state (Nex/Ngr) of this electronic level at 25 oC
using Maxwell-Boltzmann distribution.
Ans. By Maxwell-Boltzmann distribution,
−∆𝐸
𝑁𝑒𝑥
Population ratio ⁄𝑁 = 𝑒 𝑘𝑇
𝑔𝑟

ΔE = 2.5 ×1.602 ×10-19 J


k = 1.381 × 10-23 J/K
T = 298 K
Thus, Population ratio (Nex/Ngr) = 5.43 × 10-43

9. Two peaks appeared at  2.0 ppm and 2.5 ppm in the NMR spectrum of a compound. Calculate their
chemical shift values in Hz in a 60 MHz instrument and in a 600 MHz instrument.
Ans.  2.0 ppm in a 60 MHz instrument = 2 × 60 Hz = 120 Hz
 2.5 ppm in a 60 MHz instrument = 2.5 × 60 Hz = 150 Hz
 2.0 ppm in a 600 MHz instrument = 2 × 600 Hz = 1200 Hz
 2.5 ppm in a 60 MHz instrument = 2.5 × 600 Hz = 1500 Hz

10. 1H NMR spectrum of a mixture containing o-nitrotoluene and p-nitrotoluene showed two peaks for
the methyl group in these compounds. The methyl peak of o-nitrotoluene appeared at d 2.5 ppm with
an integration (area under the peak) of 56 and the methyl peak of p-nitrotoluene appeared at d 2.3 ppm
with an integration of 28. Calculate the mole ratio of these two compounds in the mixture.
𝑜−𝑛𝑖𝑡𝑟𝑜𝑡𝑜𝑙𝑢𝑒𝑛𝑒 56
Ans. = = 2: 1
𝑝−𝑛𝑖𝑡𝑟𝑜𝑡𝑜𝑙𝑢𝑒𝑛𝑒 28

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