CHE4802

September Examination 2022

UNIVERSITY EXAMINATIONS

October/September 2022

CHE4802

Physical Chemistry IV

100 Marks

Duration 3 Hours
EXAMINERS

First Examiner: Prof TE Motaung

Second Examiner: Dr B Dladla

Third Examiner: Prof N Moloto

This is a closed book examination.

Use a ball point pen, preferably black.

This question paper consists of 10 pages.

A Resource section appears on pages 6 and 7.

Annexure A on pages 8 to 10 contains the instructions to submit

the answers.

The use of a non-programmable calculator is permissible

Instructions:

Name ALL symbols used.

Use ONLY SI units unless otherwise instructed.

Each question counts 25 Marks. Answer ALL FOUR questions

Upon submission remember to tick the Honesty Declaration.

To submit your answers, follow the instructions in ANNEXURE A from

page 8 to 10.
 CHE4802
September Examination 2022
Question 1[25]

Consider the SF6 molecule with SF bond length 1.561nm and the atomic mass
1.1
of fluorine 18.9984mu and of sulphur is 32.065mu. Calculate the minimum
energy required to start the rotation of the molecule.
[3]

Consider the carbonate ion, CO32−.

1.2
3

i) Setup and solve the Hückel secular equations for the π-electrons. [2]

ii) Express the energies in terms of the Coulomb integrals α0 and αc as well as
the resonance integral β. [2]

iii) Determine the delocalization energy. [2]

1.3 The electronic ground level of Cl is 2P3/2 and a 2P1/2 level lies 881 cm-1 there above.
Calculate the electronic contribution to the heat capacity of Cl atoms at 500 K.
[6]

1.4 Describe how the mean energy of a system composed of two levels varies with

temperature. [4]

1.4 A photon of wavelength 58.4 nm strikes a sample of xenon, upon which an

electron is ejected with a speed of 1.79 × 106 m/s. Calculate the ionization
energy of xenon. [6]

Question 2[25]

2.1 Show that the x and y components of angular momentum are related to the z

component by the commutation relation [5]

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 CHE4802
September Examination 2022

2.2 You know that the wavenumbers of the rotational transition J = 1← 0 for 1H35Cl and
2
H35Cl are 20.8784 and 10.7840cm-1, respectively. Accurate atomic masses are
1.007825u and 2.0140 u for 1H and 2H, respectively. The mass of 35Cl is

34.96885 amu. Conclude based on this information that the bond lengths are the same

or different. [12]

2.3 Explain under what circumstances identical particles may be regarded as

distinguishable. [2]

2.4 Derive an expression for molar entropy of an equally spaced three-level system,

where the spacing is ε. [6]

Question 3[25]

Absorptions in the v =1←0 vibration-rotation spectrum of 1H35Cl were observed at

3.1 the

wavenumbers (cm-1) below.

a) Assign to each transition the correct rotational quantum number. [4]

b) Use the method of combination differences to determine the rotational

constants of the two vibrational levels. [4]

2998.05 2981.05 2963.35 2944.99 2925.92

2906.25 2865.14 2843.63 2821.59 2799.00

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 CHE4802
September Examination 2022

3.2 Consider ultraviolet radiation of wavelength 200 nm passing through 1.50 mm of a

solution of absorbing substance at concentration 0.717 mmol dm-3. Transmission was

found to be 61.5%. Calculate the molar absorption coefficient of the solute at 400 nm

and express your answer in cm2 /mol. [5]

3.3 Show which of the following transitions between terms are allowed in the normal
electronic emission spectrum of a many-electron atom:

a. 2
→2
[2]

b. 3
→3
[2]

c. 3
→1
[2]

3.4 Consider two conformations A and B of a molecule with 6.0 kJ/mol energy

difference. Calculate the proportion of molecules in conformation B at 273 K, if a

third conformation lies 0.3 kJ/mol above B. Treat each conformation energy level as

non-degenerate. [6]

Question 4[25]

4.1 Sketch the appearance of the 1H-NMR spectrum of diethyl ether using J = 6.97 Hz in

a spectrometer operating at

i) 400 MHz. [10]

ii) 650 MHz. [10]

The chemical shift of the CH3 protons is 1.16 and that of the CH2 protons is 3.36.

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 CHE4802
September Examination 2022

4.2 Give all mathematical expressions involved in a capillary action [5]

END
 CHE4802
September Examination 2022
DATA

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 CHE4802
September Examination 2022

Constant Symbol Value Units

8
Speed of Light c 2.99792458 × 10 m/s

Elementary charge e 1.602176565 × 10-19 C

-34
Planck’s constant h 6.62606957 × 10 Js

Boltzmann’s constant k 1.3806488 × 10-23 J/K

mol-1
23
Avogadro’s constant NA 6.02214129 × 10
Gas constant R = NA k 8.3144621 J/K-1 mol-1
Mass
-31
• Electron me 9.10938291 × 10 kg
• Proton mp 1.672621777 × 10-27 kg
• Neutron mn 1.674927351 × 10-27 kg
• Atomic mass constant mu 1.660538921 × 10-27 kg

1.097373157 × 105
Rydberg constant RH cm -1
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CHE4802
September Examination 2022
ANNEXURE A

1. HOW TO SUBMIT YOUR ANSWER FILE

Follow these steps to submit your examination answer file.

1. Access myExams at https://myexams.ac.za/portal and login using your

student number and myUnisa password.

2. Go to your specific examination site through the site tabs on the horizontal
navigation bar. Also check your Sites link in the top right-hand corner if you do
not find the site on the horizontal navigation bar.

3. Once the site has loaded, select the eAssessment tool from the left-
navigation menu

4. The list of all available assessments in the site will be displayed.

5. Select the assessment for which you want to upload the examination answer
file by clicking on the title of the assessment in the list. A new page will open.

6. Submit your examination answer file

Depending on the assessment criteria, you may be allowed to attach a file or

perhaps multiple files.

Under Attachments, click the Choose File button to browse for a file on your
device.
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 CHE4802
September Examination 2022

Once you have attached your answer file, the name of the file, as well as the file size
and upload time stamp will be displayed under Attachments.

Tip: You may click Remove to remove the attachment if you selected the wrong file.

Tip: Select the honour pledge. Students MUST check the honour pledge before
submission if it appears on the screen. A student will not be able to submit the
assessment if he/she did not check the honour pledge.

When you are ready and satisfied that you have correct answer file, click the Submit
button to complete your assessment submission.

Tip: If you are not yet ready to submit, you may click Preview to preview the
submission, or Save Draft to save your submission and submit it later. Click Cancel
to exit the assessment without saving or submitting.

2. Submission confirmation

Once you have submitted your assessment, you will receive a confirmation
message on the screen. Make a screen copy for your records.

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 CHE4802
September Examination 2022
In addition, if you have opted to receive email notifications, you will also receive an
email confirmation of your submission.

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