CM1502

NATIONAL UNIVERSITY OF SINGAPORE

SEMESTER II EXAMINATION

CM1502 GENERAL AND PHYSICAL CHEMISTRY FOR ENGINEERS

APRIL/MAY 2011 - TIME ALLOWED: 2 HOURS

INSTRUCTIONS TO CANDIDATES

1. This examination paper contains FOUR (4) questions and comprises SEVEN (7)
pages.

2. Answer ALL questions.

3. Answer each question beginning on a FRESH page of the answer book.

4. This is a CLOSED BOOK exam.

5. Calculators ARE allowed.

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Question 1

a) 3 moles of carbon dioxide gas expands reversibly in a piston-container from 20 L

to 40 L in an isothermal process at 400 K. Calculate work, heat, change in internal

energy and change in enthalpy, considering van der Waals behaviour. [a = 3.59

atm L2 mol-2 and b = 0.0427 L mol-1].

(5 marks)

b) Calculate the change in entropy and Gibbs free energy of the system when 2

moles of water goes from 300 K and 1 atm to 310 K and 40 atm.

(6 marks)

c) A student mixes 0.3 moles of N2O4 (g) and 0.5 moles of NO2 (g) in a given system.

The equilibrium N2O4 (g) 2NO2 (g) was attained at 298 K and 2.0 atm. Given

that G for the gaseous reaction is 4.73 kJmol-1, find the equilibrium

concentrations of N2O4 and NO2.

(6 marks)

d) Methyl red has an acid form which is red and a base form which is yellow. What

form will be favoured at pH 4 and by what percentage, given its Ka of 7.9 x 10-6?

(4 marks)

e) Predict, with calculations, if the following cell at 298 K can light up a 1.5 V bulb.

Negative cell has F- (aq, 5 M) and F2 (g, 1 atm) and positive cell has F- (aq, 0.01 M)

and F2 (g, 1.5 atm).

(4 marks)

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Question 2

a) A piston-container which contains 2 moles of water at 393 K of 2 L expands

reversibly to 4 L. Will more work be done if the container was insulated or not

insulated? Show the calculations.

(5 marks)

b) A voltaic cell at 298 K has [MnO4-] = 0.50 molL-1; [Mn2+] = 0.10 molL-1; [H+] = 1

x10-3 molL-1; [Fe2+] = 0.01 molL-1 and [Fe3+] = 0.01 molL-1.

Ered (MnO4-/Mn2+) = +1.51 V and Ered (Fe3+/Fe2+) = +0.77 V.

i) Calculate the cell potential.

(3 marks)

ii) Calculate the voltage change if the pH is increased by 1 unit.

(3 marks)

iii) At what pH will be the electrons flow in the reverse direction?

(4 marks)

c) Predict and sketch the NMR spectra for 2-butanone. [Hint: the peak for the CH2

group has the highest chemical shift].

(5 marks)

d) Predict the structure of the compound using the following mass spectral data of the

last three peaks:

m/z Relative intensity

112 100
113 7.2
114 32

(5 marks)

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Question 3

a) For the following reaction between NO2 and O2 determine the rate law and the

value of the rate constant using the data given in the table below

2NO2 (g) + F2 (g) 2NO2F (g)

Experiment [NO2]0 / mol.dm-3 [F2]0 / mol.dm-3 Initial rate / mol.dm-3s-1

1 1.15 1.15 6.12 x 10-4

2 1.72 1.15 1.36 x 10-3

3 1.15 2.30 1.22 x 10-3

The initial concentrations of NO2 (g) and F2 (g) are given by [NO2]0 and [F2]0

(7 marks)

b) A first order reaction is 24% complete in 19.7 minutes. How long will the reaction

take to be 85.5% complete? Calculate the rate constant for the reaction.

(3 marks)

c) For the following elements, give the electronic configurations and state how many

unpaired electrons are present in the ground state configuration of the following

elements

(i) S (Sulfur, Z=16)

(ii) Ca (Calcium, Z=20)

(2 marks)

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d) Draw the molecular orbital energy level diagrams for B2 and B2+ and indicate

which between the two has unpaired electron(s)

(8 marks)

e) The first ionization energy of aluminium is smaller than that of magnesium.

Explain.

(2 marks)

f) Nitrogen exists as N2 and not N4 while Phosphorus exists as P4 and not P2. Explain.

(3 marks)

Question 4

a) Calculate the overall activation energy of a reaction, assuming that the reaction

proceeds by the following mechanism

Step 1: A + B C + D (fast equilibrium)

Step 2: 2C G + H (slow)

In step 1, the activation energies of the forward and reverse reactions are 130

kJ/mol and 90 kJ/mol respectively and the activation energy for step 2 is 190

kJ/mol.

(6 marks)

b) Indicate all the possible missing quantum numbers for the hydrogen atom if

n=3, l=2, ml=? , ms = ?

(2 marks)

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c) Give the Lewis structure and predict the shape of the molecule based on VSEPR

theory for the following molecules. If applicable, indicate all resonance structures,

formal charges and hybridization on the central atom. Indicate ALL lone pairs and

bond pairs of electrons.

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(i) ClO4 (ii) SF4

(8 marks)

d) The C C bond energy is 356 kJ/mol while Si Si bond energy is 226 kJ/mol.

Explain the difference in the bond energies.

(3 marks)

e) Draw the molecular orbital diagram of He2. Explain if the He2 molecule can exist

or not?

(4 marks)

+
f) Arrange the following in the order of increasing size: As, Sb, Se, Se .

(2 marks)

END OF PAPER

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