Chemistry 362 Dr. Jean M.

Standard

Problem Set 6 Solutions

l. Calculate the reduced mass in kg for the OH radical. The reduced mass for OH is

mO mH . mO + mH

To properly calculate the reduced mass since it correlates to a single molecule, the ISOTOPIC masses for 1 H and 16 O (the most abundant species) must! be used in order to get accurate values. The isotopic masses are available -27 in the CRC. They are mH = 1.0078 amu and mO = 15.9949 amu . Note that 1 amu = 1.660565 " 10 kg . For OH, ! ! mO mH = = mO + mH

(15.9949 amu)(1.0078 amu) $ 1.660565 " 10 #27 kg ' & ) 1amu (15.9949 amu +1.0078 amu) % (
= 1.5743 " 10 #27 kg .

! ! 2 . The harmonic vibrational frequency of HCl in wavenumbers is 2989.6 cm1. a . ) Calculate the energies of the first two vibrational levels in Joules. The vibrational energy in the harmonic oscillator picture is Ev = h" 0 v + 1 . 2 The harmonic frequency " 0 is defined as ! " 0 = # ec ! = 2989.6 cm$1 2.99793 % 1010 cm/s

)(

" 0 = 8.9626 % 10 s .
The ground state vibrational energy is therefore ! E0 = =
1 2 1 2

13 $1

h" 0

(6.62618 # 10

$34

Js 8.9626 # 1013 s $1

)(

E0 = 2.96939 # 10 $20 J .

2 2 a.) Continued The first excited state vibrational energy is

E1 = =

3 2 h" 0 3 2

(6.62618 # 10$34 Js)(8.9626 # 1013 s$1)

Is this

E1 = 8.90817 # 10 $20 J .
b . ) Determine the wavelength for a transition from the v=0 to the v=1 level. transition in ! the infrared region of the electromagn etic spectrum? The energy of a photon for a transition from the v=0 to v=1 level is Ephoton = "E = E1 # E0 =
3 2

h$ 0 #

1 2

h$ 0

Ephoton = h$ 0 . Since the energy of a photon is given by Ephoton = h" , the frequency of the transition from the first to the second vibrational level is ! ! Ephoton = h" 0 h" = h" 0 , or " = " 0 . c Since the wavelength of a photon is related to the frequency through the relation " = , the wavelength is # ! given by

" =
=

c #0 2.99793 $ 10 8 m/s 8.9626 $ 1013 s -1

" = 3.3449 $ 10 %6 m or 3345 nm.

This wavelength is in the infrared region of the spectrum. !

3 3 . The fundamental vibrational transition ( v = 0 " v = 1 ) for CO is 2170 cm1. Treat CO as a harmonic oscillator, and determine the harmonic force constant k in g/s2. In wavenumbers, the fundamental vibrational transition for a harmonic oscillator is given by !

"e =
where the harmonic frequency " 0 is defined as ! !

#0 , c

"0 =

1/ 2 1 $k' & ) . 2# % (

Using these two equations, we can solve for the force constant k, !
2 k = 4 " 2c 2# e .

In order to use this equation, we need the reduced mass. For CO, ! mCmO = = mC + mO

(12.0000 amu)(15.9949 amu) $ 1.660565 " 10 #24 g ' & ) 1amu (12.0000 amu +15.9949 amu) % (
= 1.1385 " 10 #23 g .

! Note that to properly calculate the reduced mass, the isotopic masses for 12C and 16O must be used in order to get an accurate value. ! Substituting the reduced mass into the expression for the force constant k, k = 4 " 2 2.997925 # 1010 cms $1

) (2170 cm ) (1.1385 # 10

$1 2

$23

k = 1.902 " 10 6 gs #2 . ! !

4 4 . A diatomic molecule HX (X is an unknown atom) has a harmonic vibrational force constant k = 9.6800 " 10 5 g/s2. The harmonic vibrational frequency in wavenumbers is 4143.3 cm1. a! . ) What is the reduced mass of the molecule? Using the relation for the harmonic frequency, 1 = 2# $ k '1/ 2 & ) , % (

"0
we can solve for the reduced mass , !

=
! or in terms of wavenumbers, !

k
2 4 " 2# 0

=
Substituting, !

k . 2 4" c #e
2 2

(9.6800 " 10 (

gs #2

)
#1 2

4 $ 2 2.997925 " 1010 cms

#1 2

) (4143.3cm )

= 1.5892 " 10 #24 g .

! !

4. b.) What atom is X? In units of amu,

$ ' 1amu = 1.5892 " 10 #24 g& ) #24 % 1.660565 " 10 g (

= 0.9570 amu .
! The definition of the reduced mass for the HX molecule is !

=
Solving for mX , ! mX = !

m H mX . m H + mX

mH . mH "

5 4 b.) Continued Substituting the value calculated for

and m H = 1.0078 amu ,

!
! !

mX = !

( 0.9570 amu) (1.0078 amu) (1.0078 amu " 0.9570 amu)

mX = 18.99 amu ; therefore, X = F.

5 . Determine the ratio of populations of the v=1 and v=0 levels of the CO molecule at 300 K. The harmonic vibrational frequency is 2170.2 cm1. Repeat your calculation for 1000 K. The population ratio is given by the Maxwell-Boltzmann equation, n1 g " E "E / k T = 1 e ( 1 0) B , n0 g0 where n j is the population, g j is the degeneracy factor (=1 for harmonic oscillators), E j is the energy, k B is the Boltzmann constant, and T is ! the temperature. oscillator is defined as ! The energy of a harmonic ! Ev = h" 0 ( v + 1/ 2) , so the energy difference is ! E1 " E0 = h# 0 . ! !

Substituting, the population ratio at 300 K becomes ! n1 = exp{"h# 0 / k BT } n0 % 6.62618 $ 10 "34 Js 6.50610 $ 1013 s -1 ' = exp &" 1.38066 $ 10 "23 J/K ( 300 K) ' ( n1 = 0.00003. n0

)(

' )) * ' +

6 5 . Continued The population of the v=1 level at 300 K is almost negligible (0.003% of the v=0 population). Also notice that in the calculation, the harmonic frequency " 0 is obtained by taking the value in wavenumbers (2170.2 cm1) times the speed of light,

" 0 = c# e ! = 2.99793 $ 1010 cm/s 2170.2 cm%1

)(

" 0 = 6.50610 $ 10 s .
At 1000 K, the population ratio is ! n1 = exp{"h# 0 / k BT } n0 % 6.62618 $ 10 "34 Js 6.50610 $ 1013 s -1 ' = exp &" 1.38066 $ 10 "23 J/K (1000 K) ' ( n1 = 0.044 . n0

13 %1

)(

' )) * ' +

At 1000 K, the population of the v=1 level has increased to about 4.4% of the v=0 population. !

6 . Refer to the handout on vibrations. Assume that the vibrational force constant does not change upon isotopic substitution, k HCl = k DCl . a . ) Using the values from the handout, calculate the ratio of the experimental harmonic frequencies for HCl and ! DCl, " 0 (HCl) / " 0 (DCl) .
#1 #1 From the handout, " e ( HCl) = 2989.6 cm and " e ( DCl) = 2989.6 cm . We have from the definition that " e = # 0 / c , so therefore " 0 != c# e .

The ratio ! of harmonic frequencies is ! ! " 0 (HCl) c# e (HCl) # e (HCl) . = = " 0 (DCl) c# e (DCl) # e (DCl) Substituting the experimental harmonic frequencies, !

" 0 (HCl) 2989.6 cm#1 = " 0 (DCl) 2144.7 cm#1 " 0 (HCl) = 1.394 " 0 (DCl)

7 6 . Continued b.) Using the definition of the harmonic frequency in terms of the force constant and reduced mass predict the theoretical value of the frequency ratio. Does it agree with the experimental result? By definition, the harmonic frequency " 0 is given by
1/ 2 1 $k' & ) . 2# % (

"0 =

Therefore, the ratio of frequencies can be written ! $k '1/ 2 HCl & ) " 0 (HCl) % HCl ( = . 1/ 2 " 0 (DCl) 1 $ k DCl ' & ) 2 # % DCl ( 1 2#

Assuming that k HCl = k DCl , this equation simplifies to ! ! # &1/ 2 " 0 (HCl) = % DCl ( . " 0 (DCl) $ HCl '

Using the isotopic masses m H = 1.0078 amu , mD = 2.0140 amu , and m35Cl = 34.9689 amu leads to the amu and DCl = 1.9043amu . Substituting into the harmonic reduced mass values of HCl = 0.97957 ! frequency ratio leads to ! ! ! ! # &1/ 2 " (HCl) 1.9043amu ! 0 = % ( " 0 (DCl) $ 0.97957 amu ' " 0 (HCl) = 1.394 . " 0 (DCl)

Thus, the theoretical result agrees with the experimental result for the harmonic frequency ratio. !

8 7 . Consider the diatomic molecule LiH to be an anharmonic oscillator. Use the spectroscopic constants given in the handout on vibrations and determine: a . ) the fundamental vibrational transition.
#1 From the handout, for LiH, " e = 1405.7 cm and x e = 0.0165 . For an anharmonic oscillator, the vibrational levels in wavenumbers are given by

"v = ! " e ( v + 1 2) # " e x e ( v + 1 2) .

The fundamental transition corresponds to v = 0 " v = 1 . This transition is ! 2 2 " 0 #1 = "1 $ " 0 = " e ( 3 2) $ " e x e ( 3 2) $ " e ( 1 2) $ " e x e ( 1 2) ! " 0 #1 = " e $ 2" e x e

] [

" 0 #1 = 1405.7 cm$1 $ 2 1405.7 cm$1 ( 0.0165) " 0 #1 = 1359.3cm

$1

b . ) the first and second overtone transitions. The first overtone transition is v = 0 " v = 2 .

" 0 # 2 = " 2 $ " 0 = " e ( 5 2) $ " e x e ( 5 2) ! " 0 # 2 = 2" e $ 6" e x e " 0 # 2 = 2672.2 cm$1

] $ [" (
e

$ " e x e ( 1 2)

The second ! overtone transition is v = 0 " v = 3 .

" 0 # 3 = " 3 $ " 0 = " e ( 7 2) $ " e x e ( 7 2) ! " 0 # 3 = 3" e $ 12" e x e " 0 # 3 = 3938.8 cm$1

] $ [" (
e

$ " e x e ( 1 2)

9 8 . Calculate ! E in Joules, " in s1, and # in cm1 for the J = 4 CO. The rotational constant is B e = 1.931 cm1.

! 5 rotational transition of

For a rotational transition with "J = 1 , we have from the handout that "E = 2 hcBe J ' . For the J = 4 " 5 transition, J " = 4 and J ' = 5 . Substituting, "E = 2 hcBe J ' ! ! ! = 2 6.62618 # 10 "E = 3.8359 # 10
$22

$34

! ! 10 $1 $1 Js 2.99793 # 10 cms 1.931cm ( 5)

)(

)(

J.

Note that the speed of light is expressed in cm/s in order for the units of cm to cancel with the units of the rotational constant. ! To get the frequency of the transition, we use

" =

#E 3.8359 $ 10 %22 J = , h 6.62618 $ 10 %34 Js

" = 5.7889 $ 1011 s %1.

And, to get the wavenumbers of the transition, we use !

" =

# 5.7889 $ 1011 s %1 = , c 2.99793 $ 1010 cms %1

" = 19.31cm%1.

10 9 . For the rotational spectrum of H127I, starting with r e = 1.63 , calculate: a . ) the reduced mass, (kg) The isotopic masses are m H = 1.0078 amu and mI "127 = 126.9004 amu (from the CRC). The reduced mass is therefore ! = m H mI = m H + mI amu)(126.9004 amu) (1.0078 ! 1.660565 " 10 #27 kg/amu) (1.0078 amu +126.9004 amu) (

= 1.6603 " 10 #27 kg.

b . ) the moment of inertia, I (kg m2) ! I = re2 = 1.6603 " 10 #27 kg 1.63 " 10 #10 m I = 4.41 " 10 #47 kg m2 .

)(

c . ) the rotational constant, B e (cm1) ! Be 6.62618 # 10 $34 Js & 1m ) h = = % ( + 8" 2cI 8 " 2 2.99793 # 10 8 ms $1 4.41 # 10 $47 kg m2 ' 100 cm *

)(

Be = 6.35 cm .

$1

! d.) the rotational energies, E J (Joules), for J = 0, 1, and 2 The rotational energy levels are EJ = hcBe J (J + 1) . The factor hcBe for the HI molecule is hcBe = 6.62618 " 10 #34 Js 2.99793 " 10 8 ms #1 635m#1 ! ! hcBe = 1.26 " 10 #22 J .

)(

)(

Using this factor, the rotational energy levels may be calculated for J = 0, 1, and 2. These values are listed in the table. ! J 0 1 2 ! ! ! EJ (J) 0 2.52 " 10 #22 7.56 " 10 #22

11 9. Continued e . ) the transition frequencies " (s1) and wavenumbers # (cm1) for transitions from J" J' with J' = 1, 2, and 3 (and ! J = 1).

For transitions with "J = 1 and from J " " J ' , the expression for the transition frequency is " = 2cBe J ' , and the transition in wavenumbers is " = 2Be J ' . Using these expressions, the results are listed in the table below. ! ! !

J'
1 2

! ( J" " J ' ) Transition

" (s #1 )
3.81 " 1011 ! ! ! 7.61 " 1011 1.14 " 10
12

" (cm#1)
12.7 ! 25.4 38.1

"1 1 " 2 2 " 3

0

f . ) the spacing in frequency (! " ) and in wavenumbers (! # ) between adjacent spectral ! lines. The adjacent rotational line spacing is "# = 2cBe in frequency and "# = 2 Be in wavenumbers. For HI, "# = 2cBe = 2 2.99793 $ 1010 cms %1 6.35cm%1 , ! ! or "# = 3.81 $ 1011 s %1 .
$1 and "# = 2 Be = 2 6.35cm

)(

= 12.7 cm$1 .

! !

12 1 0 . From experiment, the rotational constants for H35Cl and D35Cl are B e = 10.591 cm1 and 5.448 cm1, respectively. What is the experimental ratio, B e (DCl) / B e (HCl)? Use the definition of B e to predict the theoretical ratio. The experimental ratio of rotational constants is Be ( DCl) 5.448 cm"1 = = 0.5144 . Be ( HCl) 10.591cm"1 h From the definition of the rotational constant, Be = , the theoretical ratio of rotational constants should 8" 2cI ! be h ! 2 Be ( DCl) 8 " c I ( DCl) I ( HCl) = = . h Be ( HCl) I ( DCl) 8 " 2c I ( HCl)
2 Since the moment of inertia I for a diatomic molecule is defined as I = re , we have ! Be ( DCl) r2 = HCl e2,HCl = HCl . Be ( HCl) DCl DCl ! re,DCl

The equilibrium bond lengths cancel out of this expression because they are independent of isotopic substitution; that is, re,HCl = ! re,DCl . To calculate the reduced masses, we have from the CRC, mH = 1.0078 amu , mD = 2.0140 amu , and m35Cl = 34.9689 amu . The reduced masses are calculated as HCl = 0.97957 amu and DCl = 1.9043 amu . ! Substituting, the theoretical ratio is ! ! !

! ! Be ( DCl) 0.97957 amu = HCl = Be ( HCl) DCl 1.9043amu or Be ( DCl) = 0.5144 . Be ( HCl)

Therefore, the experimental and theoretical ratios are in agreement. !

13 1 1 . The first two rotational transitions (0 ! 1 and 1 ! 2) in wavenumbers for LiH are 15.0262 and 30.0524 cm1, respectively. Determine the moment of inertia I (in kg m2) and the equilibrium bond length r e (in ). The spacing "# in wavenumbers between adjacent lines in a rotational spectrum is "# = 2 Be . Therefore, Be = or Be "# 30.0524 cm$1 $ 15.0262 cm$1 = , 2 2 ! = 7.5131cm$1 .

Once the rotational constant is calculated, the moment of inertia can be obtained from ! I = 6.62618 # 10 $34 Js h = 8" 2cBe 8 " 2 2.99793 # 1010 cms $1 7.5131cm$1

)(

I = 3.7259 # 10

$47

kg m .

2 Finally, from the definition of the moment of inertia, I = re , we can solve for the equilibrium bond length re , !

! !

" I %1/ 2 re = $ ' . # &

To calculate the reduced mass, we use the isotopic masses, m H = 1.0078 amu and mLi = 7.0160 amu , to get #27 LiH = 1.4633 " 10 #27 kg (using the conversion factor 1 amu = 1.660565 " 10 kg). Substituting, ! re
2 %1/ 2 ! " I %1/ 2 ! " 3.7259 ( 10 )47 kg m = $ ' = $! ' )27 # & # 1.4633 ( 10 kg &

re = 1.596 ( 10 )10 m = 1.596 .