Semester One

Examination Period
ANSWERS
Faculty of Science

EXAM CODES: CHM1011 – Mock Exam # 3

TITLE OF PAPER: CHEMISTRY I

EXAM DURATION: 2 hours writing time

READING TIME: 10 minutes

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 Data Page
Useful equations Physical constants
Wave equation: c =  c = 2.998 x 108 ms-1
Einstein equation: E = h
h = 6.626 x 10-34 J.s
1 1 1
Rydberg equation: = 𝑅(𝑛2 − 𝑛2 )
𝜆 𝑎 𝑏
R = 1.097 x 107 m-1
Bond order = 1 (# bonding electrons - # anti-bonding electrons)
2 NA = 6.022  1023
Gases
R = 8.314 J/K/mol
IdealGas Equation: pV = nRT
= 0.08206 atm·L/mol·K
𝑛2 𝑎
Non-Ideal Gas Equation: (𝑝 + )(𝑉 − 𝑛𝑏) = nRT
𝑉2
1 atm = 1.013 x 105 Pa
Total Pressure =  Partial Pressures of Component Gases

Thermodynamics  1 bar = 1.0 x 105 Pa

ΔU = q + w G = H – TS Kw at 25 oC = 1.0 x 10-14

w = -pV Go = -RTlnK
0 oC = 273.15 K
q = mcT G = G + RT ln Q

Equilibria
[base]
Henderson-Hasselbach: pH = pKa + log
[acid]
E°cell = E°red - E°ox

Kinetics
Zero-order reaction: [A]t = [A]o - kt
First-order reaction: [A]t = [A]oexp(-kt)
1 1
Second-order reaction (only one reactant A): − [𝐴] = 𝑘𝑡
[𝐴]𝑡 0

Half-life: t1/2 = 0.693/k

Arrhenius equation: k = Ae-Ea/RT
𝑘2 −𝐸𝑎 1 1
ln ( ) = ( − )
𝑘1 𝑅 𝑇2 𝑇1
Question 1 (1 + 2 + 2 + 7 + 4 + 3 + 2 + 7 + 10 = 40 marks)

Chlorine is in group 17 of the periodic table and is found in many common products found in the
home, including table salt, plastics and bleach. The following questions are related to the chlorine
atom and associated molecules.

a) Write out the condensed electronic configuration of chlorine.

[Ne] 3s2 3p5 1 mark

b) Write out the molecular formula for these chlorine-containing salts:

i) Calcium Chloride CaCl2 1 mark

ii) Iron(III) Chloride FeCl3 1 mark

c) Why does group 17, where chlorine is found, have the most negative values for electron affinity?

Negative electron affinity values indicate that energy is produced by the reaction of the atom with an
extra electron. 1 mark
Group 17 elements require one more electron to have a stable outer shell (i.e like the noble gases),
thus the anion has lower energy than neutral element. 1 mark
Question 1 continued
d) Hydrochloric acid is a strong acid, which is found in nearly all chemistry laboratories. The
hydrogen atom in hydrochloric acid can emit photons of light in both the UV and visible spectrum,
including 656.3, 486.1, 434.1, 410.2, 397.0 and 388.9 nm.

i) What is the frequency of the 656.3 nm wavelength? Express your answer to 4 significant
figures.

𝑐 2.998×108
𝜈 = 𝜆 = 656.3×10−9 1 mark for correct substitution
𝜈 = 4.568 × 1014 Hz or s −1 0.5 marks for answer, 0.5 marks for units

Subtract 0.5 marks for incorrect significant figures

ii) What is the energy of a photon in the 434.1 nm line (in joules)?
Express your answer to four significant figures.
ℎ𝑐 6.626×10−34 × 2.998 × 108
𝐸= = 1 mark for correct substitution
𝜆 434.1×10−9

𝐸 = 4.576 × 10−19 J 0.5 marks for answer, 0.5 marks for units

Subtract 0.5 marks for incorrect significant figures

iii) Which line above corresponds to the n = 3 to n = 2 transition in atomic hydrogen. Justify
your choice and confirm this by calculating the energy of the transition.

1 1 1
= 𝑅 (𝑛2 − 𝑛2 )
𝜆 𝑎 𝑏

1 1 1
= 1.097 × 107 (22 − 32 ) 1 mark for correct substitution
𝜆
1
= 1.524 × 106
𝜆
𝜆 = 6.563 × 10−7 𝑚 1 mark
The wavelength 656.3nm represent the n=3 to n=2 emission line. 1 mark
Question 1 continued
e) Draw four lines below to match each of chlorine’s quantum number with its permitted values, and
its property.

Values Quantum Number Property

0, 1, 2, 3, … n Electron Spin

1, 2, 3, … l Size

½, -½ ml Orientation

… -2, -1, 0, 1, 2 … ms Shape

0.5 mark for each correct match between values and quantum number
0.5 mark for each correct match between property and quantum number

f) The diagram below represents the electron density for the 3s, 3p, and 3d atomic orbitals of chlorine.

Use this diagram to explain why the energy of the 3s atomic orbital is lower than the energy of the
3p atomic orbital.

The region pointed to here (1 mark) represent an electron in the 3s atomic orbital having more
penetration than the electron in 3p orbital. (1 mark)
Thus, 3s electron shields the 3p electron from the nucleus. 1 mark

g) Chlorine is in the same row as Silicon, but has a smaller radius. Explain why this is the case.

Zeff is higher for Cl than Si. 1 mark

Higher Zeff results in outer electrons being pulled closer towards nucleus (hence smaller radius). 1
mark
Question 1 continued
h) A compound containing chlorine is chlorate, ClO3-.

i) Draw a Lewis structure for ClO3-, being sure to show lone pairs and any formal charges.
Note that the chlorine atom is the central atom for this compound.

1 mark for Cl lone pair electrons

1 mark for 3 x O lone pair electrons
1 mark for 2 Cl=O bonds
1 mark for Cl-O bond

ii) What are the parent and molecular geometries of ClO3-?

Parent: tetrahedral 1 mark

Molecular: trigonal pyramidal 1 mark

iii) Does ClO3- have a dipole? Circle the correct answer

YES NO 1 mark

i) Rank the following covalent bonds in order from longest to shortest bond.

1. C-F, C-N, C-O, C-H

C-H > C-N > C-O > C-F 1 mark

2. C-N, C≡N, C=N

C-N > C=N > C≡N 1 mark
Question 1 continued
j) Phosgene, below, is a chlorine-containing compound used in the production of plastics. However,
it was also used as a chemical weapon due to its toxic nature. Using valence bond theory, draw the
hybridisation scheme for this molecule. Draw separate diagrams for the  and  bonding
arrangements. Include all hybrid orbitals and appropriate labels.

1 mark for each:

1. C – sp2 label
2. C – correct orbital drawing
3. 2 x Cl (single bond) – sp3 label
4. 2 x Cl (single bond) - correct orbital
drawing
5. 2 x Cl - lone pair electrons
6. 1 x O – sp2 label
7. 1 x O – correct orbital drawing
including lone pair electrons
8. σ labels (3 in total)
9. C-O –π bond correct
10. C-O – π bond label
Question 2 (1 + 2 + 6 + 1 = 10 marks)
Oxygen, O2, is an important homonuclear diatomic molecule for life.
(a) Identify which atomic orbitals are occupied for the valence electrons of an oxygen atom.

2s and 2p 1 mark

(b) What types of molecular orbitals may be formed by the overlap of two p atomic orbitals?
σ(2pz) and σ*(2pz) 1 mark
π(2px/2py) and π*(2px/2py) 1 mark

(d) Sketch the MO diagram for O2. Include all necessary labels, and arrows to indicate the electrons.
1 mark for each:
1. atomic orbital names
2. Molecular orbital σ
names (including atomic
orbitals) for 2s orbitals
3. Molecular orbital σ
names (including atomic
orbitals) for 2p orbitals
4. Molecular orbital π
names (including atomic
orbitals)
5. Number of electrons in
atomic orbital
6. Number of electrons in
Molecular orbital

(f) How does the MO diagram indicate whether this molecule is diamagnetic or paramagnetic?
paramagnetic – unpaired electrons 1 mark
Question 3 (2 + 2 = 4 marks)
A cylinder of oxygen gas has the initial pressure of 10.0 kPa at 25.0 °C. The cylinder is closed and
the gas can be viewed as ideal gas.

a) Calculate the density of the oxygen in the cylinder.

𝑚 𝑃𝑀 10 kPa×32g mol−1
= = 8.314 kPa.L.mol−1 .K−1 ×298K 1 mark for correct substitution
𝑉 𝑅𝑇
𝑚
= 0.129 g L−1 1 mark for answer + units
𝑉

b) Calculate the new pressure if the temperature of the cylinder increases to 50.0 °C.

𝑃1 𝑃2
= P1 = 10.0 kPa, T1 = 25 + 273, P2 = ?, T2 = 50 + 273
𝑇1 𝑇2

10.0 2 𝑃
= 323 1 mark for correct substitution
298

P2 = 10.8 kPa 1 mark for answer

Question 4 (5 marks)

Draw five lines to match the following five molecules with the five boiling points below. You
should consider the form of intermolecular bonding taking place in each example.

Molecule Boiling Point

Cl2 85 K
H2O 352 K
F2 239 K

373 K

330 K
Question 5 (3 + 1 = 4 marks)

An undergraduate student designed a “coffee-cup calorimeter” experiment to determine the

enthalpy of the following reaction:

H2SO4 (aq) + 2 KOH (aq)  K2SO4 (aq) + 2H2O (l)

50.0 mL of 1.00 M H2SO4 and 50.0 mL of 2.00 M KOH, both with a starting temperature of
25.0 oC, were combined in the calorimeter, and the temperature was measured to increase to
30.1 oC. The specific heat of water is 4.18 Jg-1K-1.

a) Assuming the solution has a density of 1.00 g cm-3, determine the energy produced by the
reaction, in Joules.

qcalorimeter = mcΔT

m = 100 g ((50mL + 50mL) x 1.00 g cm3)

c = 4.18
ΔT = 5.1K

qcalorimeter = 100 x 4.18 x 5.1 1 mark correct values

qcalorimeter = 2.13 x 103 J 1 mark answer

qcalorimeter = -qreaction
qreaction = - 2.13 x 103 J 1 mark

b) Determine H per mole of H2SO4.

n(H2SO4) = CV = 1 x 0.05L = 0.05 mol 0.5 mark

ΔH = -2.13 kJ / 0.05 = 42.6 kJ mol-1 0.5 mark

Question 6 (4 + 2 = 6 marks)
The species iodine trichloride (ICl3) can be synthesised according to the reaction shown below:
I2 (s) + 3 Cl2 (g) → 2 ICl3 (s)
The thermodynamic data for the species are:
Hf (kJ mol-1) ΔS (J mol-1K-1)
I2 (g) 62.26 260.6
I2 (s) 0.000 116.7
Cl2 (g) 0.000 223.0
ICl3 (s) -88.28 172.0
a) Calculate the Standard Gibbs Free Energy (G ) for the reaction at 25.0 C.

ΔHr = (2 x -88.28) – (0) = -176.6 kJ mol-1 1 mark

ΔSr = (2 x 172) – (116.7 + 3 x 223) = -441.7 J mol-1 K-1 1 mark

ΔG = ΔH - TΔS

ΔG = -176.6 – ((25+273) x -0.4417) 1 mark

ΔG = -44.97 kJ mol-1 1 mark

b) Is this reaction spontaneous at 25 C? Explain your answer.

Yes 1 mark
ΔG < 0 1 mark
Question 7 (3 marks)
For a reaction with H = -152.6 kJ mol-1 and S = -543.8 J K-1 mol-1 at 25 C, how will G
change if the reaction temperature is increased? Explain your answer.

ΔG = ΔH – TΔS 1 mark

If ΔH is negative and ΔS is negative, then ΔG can be either negative or positive depending on

temperature. 1 mark
The higher the temperature, ΔG will become more positive, to a point where it will be non-
spontaneous (ΔG>0) 1 mark

Question 8 (2 + 2 + 4 = 8 marks)
The following reaction is at equilibrium:
4NH3 (g) + 3O2 (g) ⇌ 6H2O (g) + 2N2 (g)

a) Explain how the equilibrium will shift if:

i. Four moles of helium gas is added

no change 1 mark

ii. A match is burnt inside the container

O2 will be consumed, therefore equilibrium will shift left 1 mark

b) Write out the equilibrium expression, Kc, for this reaction:

[𝐻 𝑂]6 [𝑁2 ]2
2
𝐾𝑐 = [𝑁𝐻 4 [𝑂 ]3
1 mark for correct indices, 1 mark for correct species
3] 2

b) What is the pH of a 0.250 M NH3 aqueous solution when it has reached equilibrium?
(Kb = 1.80 × 10-5). Use the ICE table.

NH3(g) + H2O(l) ⇌ NH4+(aq) + OH-(aq)

NH3 NH4+ OH-

initial 0.250 0 0
change -x +x +x
equilibrium 0.25-x +x +x
1 mark for table

[𝑁𝐻4+ ][𝑂𝐻 − ] (𝑥)(𝑥)

𝐾𝑏 = = 1.80 × 10−5 = (0.25−𝑥) 1 mark for equilibrium expression
[𝑁𝐻3 ]

assume x is very small: 0.25 – x ≈ 0.25

(𝑥)(𝑥)
1.80 × 10−5 = (0.25) x = 2.12 x 10-3 = [OH-] 1 mark

pH = -log[H3O+] [H3O+]= 1.0 x 10-14 / 2.12 x 10-3 0.5 mark

pH = -log (4.72 x 10-12) = 11.3 0.5 mark
Question 9 (1 + 3 + 2 = 7 marks)

Copper (I) thiocyanate (CuSCN) is a sparingly soluble salt. (Ksp = 1.77 x 10-13).

a) Write out the Ksp expression.

Ksp = [Cu+][SCN-] 1 mark

b) Determine how many grams of CuSCN would dissolve into a 1.00 L of water.

Ksp = [Cu+][SCN-] = 1.77 x 10-13

As Cu+ and SCN- are 1:1 mole ratio, substitute each concentration by ‘x’

(x).(x) = 1.77 x 10-13

x = 4.21 x 10-7 1 mark

Therefore 4.21 x 10-7 moles of CuSCN dissolves in 1.0L of water. 1 mark

m(CuSCN) = 4.21 x 10-7 x 121.63 = 5.12 x 10-5g 1 mark

c) Would you expect a more or less CuSCN to dissolve in 1.00 L of a 0.100 M solution of
ammonium thiocyanate compared to 1.00 L of water? Explain your answer.

Less due to the common ion effect 1 mark

Ksp = [Cu+][SCN-] = 1.77 x 10-13

if [SCN-] = 0.1M, then [Cu+] = 1.77 x 10-12 M 1 mark
Question 10 (2 + 4 = 6 marks)
A buffer solution containing 0.250 M acetic acid (pKa = 4.74) and 0.500 M sodium acetate is
prepared in a 250 mL volumetric flask.
a) Determine the pH of this buffer solution.

[base] 0.500
pH = pK a + log [acid] = 4.74 + 0.250 1 mark

pH = 5.04 1 mark

b) An experiment requires a buffer of pH = 7.50. Solutions of 0.500 M KH2PO4 and 0.500 M

K2HPO4 were prepared. What volumes of each are required to make up a 2.00L of buffer?
pKa (H2PO4-) = 7.21

Make 'x' = volume of KH2PO4 required (acid)

Make '(2.00 - x)' = volume of K2HPO4 required (base)

Use C1V1 = C2V2

KH2PO4
C1 = 0.50, V1 = x, C2 = [acid], V2 = 2.00
0.50𝑥
[acid] = 1 mark
2.00

K2HPO4
C1 = 0.50, V1 = 2.0-x, C2 = [base], V2 = 2.00
0.50(2.0−𝑥)
[base] = 1 mark
2.00

0.5(2.0−𝑥)
[base]
pH = pK a + log [acid] = 7.21 + log 2.0
0.5𝑥 = 7.50 1 mark
2.0
x = 0.678 L
Therefore volume acid required = 0.678 L and volume of base is 2.0-0.678 = 1.322L 1 mark
Question 11 (2 + 2 = 4 marks)
a) The concentration of a reactant decreased from 0.290 mol L-1 to 0.140 mol L-1 in 5 minutes.
Calculate the average rate of the reaction.

0.140−0.290
Rate = 1 mark
5−0
-1
Rate = 0.0300 M min 1 mark (note: rates cannot be negative)

b) Assuming this is a zero order reaction, determine the concentration of the reactant after 3 further
minutes.

[A]t = [A]o - kt

As it is a zero order reaction, Rate = k, t = 3 min, [A]o = 0.140

[A]t = 0.140 – 0.03 x 3 1 mark

[A]t = 0.0500 M 1 mark

Question 12 (2 marks)
A successful reaction takes place when the molecules have an effective collision. State 2 factors
that are needed to make a collision an effective collision.

Sufficient kinetic energy 1 mark

Correct orientation of the molecules 1 mark
Question 13 (2 + 1 + 2 + 1 + 2 + 2 = 10 marks)
The method of initial rates was used to follow the rate of the following reaction:
A + 2B → C + 3D
The following data were collected:
Expt [A] (mol L-1) [B] (mol L-1) Initial Rate of consumption
of A (mol L-1 s-1)
1 0.020 0.020 0.16
2 0.040 0.020 0.64
3 0.040 0.060 0.64
4 0.010 0.050 x
a) What is the order of the reaction with respect to the reactants A and B?

Rate order A = 2 1 mark

Rate order B = 0 1 mark

b) Write out the rate law for this reaction.

Rate = k [A]2 1 mark

c) Calculate the value of the rate constant, k (remember to include units for k in your answer).

Use the first row of data

0.16 = k (0.02)2
k = 400 M-1 s-1

d) What is the initial rate of formation of D in experiment 1?

Rate(A) Rate(D)
=
1 3
0.16
Rate(D) = 1 × 3 = 0.48 M s−1 1 mark

e) Determine the value x that would be measured in Experiment 4.

Rate = 400 [A]2

Rate = 400 (0.01)2
Rate = 0.040 M s-1

f) How would the observed rates change if a catalyst was added to the system?

Rates will increase 1 mark

Catalyst will decrease activation energy (Ea) of reaction. 1 mark
Question 14 (1 + 3 = 4 marks)

The decomposition of C2H5Cl has the following rate law: rate = k [C2H5Cl].
At 550°C, k = 3.20 x 10-2 s-1.
a) What is the half-life of this reaction of 550°C?

0.693 0.693
𝑡1/2 = = = 21.7sec
𝑘 3.20 × 10−2

b) If the concentration of C2H5Cl is 0.0100 M after 1.00 min, what was the initial concentration?

[𝐴]𝑡 = [𝐴]0 𝑒 −𝑘𝑡

−2
0.0100 = [𝐴]0 𝑒 −3.2×10 ×60 1 mark correct substitution, 1 mark for correct t
[A]0 = 0.0682 M 1 mark

Question 15 (2 + 5 = 7 marks)

a) Balance the incomplete half cell:

BrO3-(aq) ⇌ Br-(aq) + OH- (aq) E° = 0.61V.

BrO3- (aq) + 3H2O (l) + 6e- ⇌ Br- (aq) + 6OH- (aq)

1 mark for addition of H2O and balancing H and O atoms
1 mark for addition of electrons to balance charge

b) Answer the following questions based on the above equation and the information below.

Au3+(aq) + 3e- ⇌ Au (s) E° = 1.42 V

Cu+(aq) + e- ⇌ Cu (s) E° = 0.522 V

i) If you had a solution of Br-, which chemical species in the above reactions will oxidize it
spontaneously? Explain why.

Au3+. 1 mark
Spontaneous reaction is a galvanic cell where E0 > 0 1 mark

ii) If you mix some Cu wire in the Br- solution, would a redox reaction take place?

No as they are both in reduced forms 1 mark

iii) What is the voltage required for the non-spontaneous reaction (electrolytic) to take place
in a Br- solution?
Reaction of Cu+/Cu (reduction) with BrO3-/Br- (oxidation)
E°cell = E°red - E°ox = 0.522-0.61 = -0.088 V 1 mark
Thus need more than 0.088V for reaction to occur 1 mark

END OF PAPER