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Ans Q1. The Vibrational Frequency of

The document contains calculations and explanations related to spectroscopy. It discusses the vibrational frequency of H35Cl and H37Cl isotopes. It then calculates rotational and vibrational energies for symmetric tops like ammonia. Further calculations determine bond lengths, wavenumbers, and chemical shifts.

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Karthik Sharma
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Download as PDF, TXT or read online on Scribd
31 views

Ans Q1. The Vibrational Frequency of

The document contains calculations and explanations related to spectroscopy. It discusses the vibrational frequency of H35Cl and H37Cl isotopes. It then calculates rotational and vibrational energies for symmetric tops like ammonia. Further calculations determine bond lengths, wavenumbers, and chemical shifts.

Uploaded by

Karthik Sharma
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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Ans Q1.

The vibrational frequency of 1H35Cl is 2992 cm-1, which is given by


1/2
ν = 1/2πc (K/µ)

For the1H37Cl molecule,


*
ν = 1/2πc (K/µ*)1/2

Where the asterisk is used to indicate an isotopic substitution.

Now ν * / ν = [1/2πc (K/µ)1/2] / [1/2πc (K/µ*)1/2] = (µ / µ*)1/2

(µ / µ*)1/2 = (0.9722 gmol-1/0.9737 gmol-1)1/2 = 0.9992


* -1
ν /2992 cm = 0.9992
* -1
So ν = 2989.6 cm

Ans Q2. Ammonia is a symmetric rotor,

So A = h/8π2I and B = h/8π2I⊥

A = (6.626 x 10-34 Js)/ [8 X (3.14)2 X (4.413 X 10-47 kg m2)] = 1.90 X 1011 s-1

B = (6.626 x 10-34 Js)/ [8 X (3.14)2 X (2.806 X 10-47 kg m2)] = 2.99 X 1011 s-1

The energy level of a symmetric rotor is given by

EJ, K = hBJ(J+1) + h (A-B)K2

Where J = 0, 1, 2, ---- and K = +J ……0……..-J

The lowest nonzero value of the rotational energy has J = 1 and K = 1 for a symmetric
top. Therefore

E = [(6.626 x 10-34 Js) X (2.99 X 1011 s-1) X 1(1+1)] + {(6.626 x 10-34 Js) X [(1.9-2.99) x
1011 s-1] X 12} = 3.24 X 10-22 J
1/2
Ans Q3. ν = 1/2πc (K/µ)

The reduced mass of 1H35Cl, µ = mH mCl / (mH + mCl)


= (1.67 X 10-27 kg) X (5.81 X 10-26 kg)/ [(1.67 X 10-27) + (5.81 X 10-26)] kg
= 1.614 X 10-27 kg

2992 cm-1 = {1/[2 X 3.14 X (3 X 1010 cm s-1)]} X [k/(1.614 X 10-27 kg)]1/2

[k/(1.614 X 10-27 kg)]1/2 = 5.64 X 1014 s-1

So k = 513.4 kgs-1 = 513.4 Nm-1

The energy of separation between any two neighboring vibrational energy level = hν
= hc ν = 5.95 X 10-20 J

Ans Q4. The 1st line corresponds to an energy separation of 2B.

2B = 21.38 cm-1, So B = 10.69 cm-1

B = h/8π2Ic = (6.626 x 10-34 Js)/ [8 X (3.14)2 X I X (3 X 1010 cm s-1)] = 10.69 cm-1

Therefore I = 2.62 X 10-47 kg m2 = µ r2

Since µ = 1.614 X 10-27 kg

r2 = (2.62 X 10-47 kg m2)/ 1.614 X 10-27 kg = 1.62 X 10-20 m2

So r = 1.27 X 10-10 m = 127 pm

Ans Q5. The wavelength of the incident light is 336.732 nm = 336.732 X 10-7 cm

The wavenumber of the incident radiation ν i = 1/λ = 29697.2 cm-1

The waenumber of the observed line ν =29677.3 cm-1

The difference ν i - ν = 19.9 cm-1 = 2B(2J +3) = 2 X 1.99 (2J +3)

2J + 3 = 5
J=1
As per selection rule, since ∆J = ± 2, The Stokes line corresponds to the transition
J=1→J=3

Ans Q 6. The mass of the atoms are given, the reduced mass is

µ = mH mI / (mH + mI) = (1.67 X 10-27) X (2.11 X 10-25)/ (1.67 X 10-27) + (2.11 X 10-25)
= 1.65X 10-27 kg
The vibrational frequency, ν = 1/2π (K/µ)1/2 = [1/(2 X 3.14)] (313 Nm-1/1.65X 10-27
kg)1/2

= 6.977 X 1013 Hz

Correspondingly, The wavenumber ν = 2325 cm-1

The wavenumbers of the R branch lines of vibration-rotation spectrum is given by

νR = ν + 2B(J+1)

Hence the two R branch lines will appear at 2338.22 and 2351.44 cm-1, respectively.

Ans Q 7. Consider that the rotational constants for the 12C16O and 13C16O are B and B’
respectively.

2B = 3.84235 cm−1
B = 1.92118 cm−1

Similarly, 2B′ = 3. 67337 cm−1


B′ = 1.83669 cm−1

B/B′ = (h/8π2Ic) x (8π2I′c/h) = I′/I = µ′/ µ= 1.046

µ′/µ = 1.046 = (15.9994 m′/15.9994 + m′) x (12.011 + 15.9994 / 12.011 x 15.9994)

Hence m′ = 13.0128

Ans Q8.

The transmittance T corresponding to 5 mm cell is T = 0.16

Absorbance = - log T = - log0.16 = 0.80

Absorbance = ε [Cu2+] l = 0.80

Hence ε = 10.7 m-1cm-1


Absorbance at 600 nm in 0.1 cm cell = 10.7 m-1cm-1 X 0.15 M X 0.1 cm
= 0.161
0.161 = - log T

T = 0.69
So the percentage transmittance at 600 nm in 0.1 cm cell = 69 %
Ans Q 9. The resonating frequency ν for a magnetic field of 1.5 T can be calculated from
the expression
hν = gNµNB
gN and µN for proton are 5.586 and 5.051 X 10-27 JT-1 respectively.

So ν = [5.586 X (5.051 X 10-27 JT-1) X 1.5 T ] / 6.626 X 10-34 JS = 63.8 MHz.

The difference in the chemical shift in δ scale is 7.6 which is equal to a frequency
difference of 484.8 Hz.

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