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.