November 2014

Topics in the November 2014 Exam Paper for CHEM1101

Click on the links for resources on each topic.

2014-N-2:

Wave Theory of Electrons and Resulting Atomic Energy Levels

Shape of Atomic Orbitals and Quantum Numbers
Filling Energy Levels in Atoms Larger than Hydrogen
Band Theory - MO in Solids

2014-N-3:

Periodic Table and the Periodic Trends

Wave Theory of Electrons and Resulting Atomic Energy Levels

2014-N-4:

Nuclear and Radiation Chemistry

2014-N-5:

Wave Theory of Electrons and Resulting Atomic Energy Levels

Atomic Electronic Spectroscopy

2014-N-7:

Lewis Structures
VSEPR
Types of Intermolecular Forces

2014-N-8:

Bonding - MO theory (H 2 )
Bonding - MO theory (larger molecules)

2014-N-9:

Thermochemistry

2014-N-10:

Chemical Equilibrium
First and Second Law of Thermodynamics

2014-N-11:

Gas Laws
Thermochemistry
First and Second Law of Thermodynamics

2014-N-12:

Chemical Equilibrium

2014-N-13:

Equilibrium and Thermochemistry in Industrial Processes

2014-N-14:

Electrochemistry
 November 2014

2014-N-15:

Electrolytic Cells

2014-N-16:

Electrochemistry
 CC0159(a) 2014-N-1 Page 1 of 28

Confidential

SEAT NUMBER:
STUDENT ID: .
SURNAME: .
GIVEN NAMES: ..

CHEM1101
Chemistry 1A

Final Examination
Semester 2, 2014

Time Allowed: Three hours + 10 minutes reading time

This examination paper consists of 28 pages.

INSTRUCTIONS TO CANDIDATES
Marks
1. This is a closed book exam.
Page(s) Max Gained Marker
2. A simple calculator (programmable versions and
PDAs not allowed) may be taken into the exam 2-10 28 MCQ
room. 11 6
Make Model 12 7
13 6
3. The total score for this paper is 100. The possible
score per page is shown in the adjacent table. 14 3
4. The paper comprises 28 multiple choice questions 15 3
and 15 pages of short answer questions.
ANSWER ALL QUESTIONS. 16 9
5. Follow the instructions on page 2 to record your 17 3
answers to the multiple choice questions. Use a
dark lead pencil so that you can erase errors made 19 2
on the computer sheet. 20 3
6. Answer all short answer questions in the spaces
provided on this question paper. Credit may not be 21 5
given where there is insufficient evidence of the 23 5
working required to obtain the solution.
24 4
7. Take care to write legibly. Write your final answers
in ink, not pencil. 25 6
8. Numerical values required for any question, 26 7
standard electrode reduction potentials, a Periodic
Table and some useful formulas may be found on 27 3
the separate data sheets.
Total 72
Check Total
CC0159(a) 2014-N-2 Page 2 of 28

Marks
Consider the 4p orbital shown below. Note that, for clarity, the nucleus of the atom is
3
not shown.

How many spherical and planar nodes does this orbital have?

Number of spherical nodes: Number of planar nodes:

Complete the following table to give a set of quantum numbers that describes an
electron in a 4p orbital.

Quantum number n

Value 4

What factors determine the lattice energy of an ionic crystal?

3

THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY.

Page Total: Pa
CC0159(a) 2014-N-3 Page 3 of 28

Marks
Electron affinity is the enthalpy change for the reaction A(g) + e A(g). 7
The graph below shows the trend in electron affinities for a sequence of elements in
the third row of the Periodic Table.

400"
350"
300"
H"/"kJ"mol1"
250"
200"
150"
100"
50"
0"
Al" Si" P" Si" Cl"

Give the electron configurations of the following atoms and singly-charged anions.
Use [Ne] to represent core electrons.
Atom Electron configuration Ion Electron configuration

Si Si
P P
S S
Explain why the value for the electron affinity of phosphorus is anomalous.

What trend would you expect for the electron affinities for Si, P and S? Explain
your answer.

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CC0159(a) 2014-N-4 Page 4 of 28

Marks
The isotope 27
60
Co undergoes radioactive decay to produce a stable isotope of nickel.
6
Give the balanced equation for this decay process.

The half-life of 60Co is 5 years. Calculate the value of the decay constant, , (in s1).

Answer:

What is the molar activity of 60Co (in Bq mol1)?

Answer:

Complete the graph below.

1.0
Fraction of 60Co remaining

0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0 5 10 15 20 25 30

Time (years)

Estimate from the graph the fraction of

60
Co remaining after 12 years.

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CC0159(a) 2014-N-5 Page 5 of 28

Marks
The diagram on the left of page 15 depicts the three lowest energy levels of the
3
hydrogen atom. Consider an excited hydrogen atom with an electron in the 3s orbital.

(A) Indicate all possible jumps this electron can make as the atom returns to the
ground state. One possible jump (a) is shown for you as an example.
(B) Calculate the energy associated with each of these jumps and mark it on the
diagram on the right on page 15. Label the transitions. Again, jump (a) is
shown as an example.

Working

List all of the transitions that are in the visible region and identify the colour
associated with each. For reference, the relationship between colours and
wavelengths is shown below.
UV violet blue green yellow orange red IR
400 450 490 560 590 630 700 nm

If the corresponding transitions were obtained from He+ instead of H, would they
occur at longer or shorter wavelengths? Give a reason for your answer.

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CC0159(a) 2014-N-6 Page 6 of 28

Energy levels of H atom Atomic Spectrum of H atom Marks

3

0"

(a)" (a)"n=3""""1" 200"

n"="3"

=50" n"="2"

150"

radia8on"energy"/"10=20"J"
=100"
energy"/"10=20"J"

100"

=150"

50"
=200"
n"="1"

0"
=250"

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CC0159(a) 2014-N-7 Page 7 of 28

Marks
Draw the Lewis structure of the following species. The central atom is underlined.
4
Give resonance structures where applicable and indicate whether the species has a
dipole moment?

Species Lewis structure Dipole moment

SF4
Yes / No

NO2 Yes / No

5
Complete the table concerning two of the isomers of C3H6O2. Identify the geometry
around each atom marked with an asterisk and the list the major intermolecular forces
present in the liquid.
Isomer A B

Chemical
structure

Geometry

Major
intermolecular
forces in liquid

The boiling point of isomer A is 141 C and that of isomer B is 60 C. Explain why
the boiling point of A is higher than B?

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CC0159(a) 2014-N-8 Page 8 of 28

Marks
The molecular orbital energy level diagrams for F2 and B2 are shown below. Fill in 3
the valence electrons for each species in its ground state. Hence calculate the bond
order for F2 and B2 and indicate whether these molecules are paramagnetic or
diamagnetic.
F2 B2

Bond order
Paramagnetic or
diamagnetic

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CC0159(a) 2014-N-9 Page 9 of 28

Marks
Lead shot was traditionally made by dropping molten lead into a tank of water. A
2
piece of lead, initially at 327 C is dropped into 200.0 mL of water raising its
temperature from 25 to 35 C. What was the weight of the lead?
Data: Specific heat capacity of Pb is 0.126 J K1g1
Specific heat capacity of H2O(l) is 4.184 J K1g1
The density of water is 1.0 g mL1

Answer:
THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY.

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CC0159(a) 2014-N-10 Page 10 of 28

Marks
Use the following equilibria: 2
2CH4(g) ! C2H6(g) + H2(g) K1 = 9.5 1013
CH4(g) + H2O(g) ! CH3OH(g) + H2(g) K2 = 2.8 1021
to calculate the equilibrium constant, K3, for the following reaction.
2CH3OH(g) + H2(g) ! C2H6(g) + 2H2O(g)
Show all working.

Answer:
1
The Second Law states that all observable processes must involve a net increase in
entropy. When liquid water freezes into ice at 0 C, the entropy of the water
decreases. Since the freezing of water is certainly observable, the processes must still
satisfy the Second Law. Provide a brief explanation of how this is so.

Page Total: Pa
CC0159(a) 2014-N-11 Page 11 of 28

Marks
Ethanol, C2H5OH(l), is increasingly being used as a fuel. Give the balanced chemical 5
equation for the combustion of ethanol in oxygen to produce carbon dioxide and
water.

Use the standard enthalpies of formation given below to calculate the molar heat of
combustion of gaseous ethanol. Show all working.

Compound C2H5OH(g) CO2(g) H2O(g)

fH / kJ mol1 235.3 393.5 285.8

Answer:

Calculate the volume change when 150 g of liquid ethanol is burnt in an engine at
1500 C and 2.0 atm pressure. Assume all gases behave as ideal gases. Show all
working.

Answer:

Why can the volume occupied by the liquid ethanol be ignored in this calculation?

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CC0159(a) 2014-N-12 Page 12 of 28

Marks
The standard Gibbs free energy of the following reaction is +69.73 kJ mol1.
5
COCl2(g) ! CO(g) + Cl2(g)
What is the expression for the equilibrium constant, Kp, for this reaction?

Calculate the value of the equilibrium constant at 298 K.

Kp =

In which direction will this reaction proceed if a mixture of gases is made with:
PCOCl2 = 1.00 atm; PCl2 = 0.01 atm; PCO = 0.50 atm? Show working.

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CC0159(a) 2014-N-13 Page 13 of 28

Marks
The diagram below represents the equilibrium constant Kp associated with the
4
formation of the four oxides indicated.
50

4
/3Al + O2 2/3Al2O3
40

lnKp
30 2Sn + O2 2SnO
2Zn + O 2 2ZnO

20

2C + O2 2CO
10

0
0 200 400 600 800 1000

Temperature (C)

Using the equilibrium constant data above, describe the reaction that proceeds under
the following conditions. If you think no reaction will occur, write no reaction.

CO and Sn are combined at 400 C

Al and SnO are combined at 400 C

C and ZnO are mixed at 900 C

Which oxide has the largest (most negative) enthalpy of formation?

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CC0159(a) 2014-N-14 Page 14 of 28

Marks
An electrochemical cell consisting of a Ni2+/Ni half-cell with unknown [Ni2+] and a 6
Cu2+/Cu half-cell with [Cu2+] = 2.5 M has a cell voltage of 0.64 V at 298 K. What is
the initial concentration of Ni2+ in the Ni2+/Ni half-cell?

Answer:

Calculate the equilibrium constant for the reaction at 25 C.

Answer:

Calculate the standard Gibbs free energy change for the reaction at 25 C.

Answer:

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CC0159(a) 2014-N-15 Page 15 of 28

Marks
Chlorine)is)produced)by)the)electrolysis)of)an)aqueous)sodium)chloride)solution)
7
using)inert)electrodes. What products are formed at the anode and cathode? Explain
your answer.

Answer:

Write a balanced equation for the overall reaction of the electrolytic cell.

Assuming a [Cl] of 1.0 M and no overpotential, what would be the minimum voltage
required to drive the overall cell reaction at pH 14? Assume gases are at 1 atm.

Answer:

Considering the cell potentials suggest a reason ruthenium oxide electrodes are
employed in this reaction rather than carbon electrodes.

Page Total: Pa
CC0159(a) 2014-N-16 Page 16 of 28

Marks
What is the voltage of a concentration cell constructed from two beakers containing
3
2.5 M CuSO4 and 0.025 M CuSO4 at 298 K?

Answer:

Explain the changes necessary for the cell to reach equilibrium.

THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY.

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CC0159(a) 2014-N-17 Page 17 of 28

THIS PAGE IS FOR ROUGH WORKING ONLY

Page Total: Pa
CC0159(b) CHEM1101 2014, Semester 2

DATA SHEET
Physical constants
Avogadro constant, NA = 6.022 1023 mol1
Faraday constant, F = 96485 C mol1
Planck constant, h = 6.626 1034 J s
Speed of light in vacuum, c = 2.998 108 m s1
Rydberg constant, ER = 2.18 1018 J
Boltzmann constant, kB = 1.381 1023 J K1
Permittivity of a vacuum, 0 = 8.854 1012 C2 J1 m1
Gas constant, R = 8.314 J K1 mol1
= 0.08206 L atm K1 mol1
Charge of electron, e = 1.602 1019 C
Mass of electron, me = 9.1094 1031 kg
Mass of proton, mp = 1.6726 1027 kg
Mass of neutron, mn = 1.6749 1027 kg

Properties of matter
Volume of 1 mole of ideal gas at 1 atm and 25 C = 24.5 L
Volume of 1 mole of ideal gas at 1 atm and 0 C = 22.4 L
Density of water at 298 K = 0.997 g cm3

Conversion factors
1 atm = 760 mmHg = 101.3 kPa 1 Ci = 3.70 1010 Bq
0 C = 273 K 1 Hz = 1 s1
1 L = 103 m3 1 tonne = 103 kg
1 = 1010 m 1 W = 1 J s1
1 eV = 1.602 1019 J

Decimal fractions Decimal multiples

Fraction Prefix Symbol Multiple Prefix Symbol
103 milli m 103 kilo k
6 6
10 micro 10 mega M
109 nano n 109 giga G
1012 pico p 1012 tera T
CC0159(b) CHEM1101 2014, Semester 2

Standard Reduction Potentials, E

Reaction E / V
3+ 2+
Co (aq) + e Co (aq) +1.82
Ce4+(aq) + e Ce3+(aq) +1.72
+ 2+
MnO4 (aq) + 8H (aq) + 5e Mn (aq) + 4H2O +1.51
3+
Au (aq) + 3e Au(s) +1.50

Cl2 + 2e 2Cl (aq) +1.36
+
O2 + 4H (aq) + 4e 2H2O +1.23 (+0.82 at pH = 7)
Pt2+(aq) + 2e Pt(s) +1.18
+ 3+
MnO2(s) + 4H (aq) + e Mn + 2H2O +0.96
+
NO3 (aq) + 4H (aq) + 3e NO(g) + 2H2O +0.96
2+
Pd (aq) + 2e Pd(s) +0.92
+
Ag (aq) + e Ag(s) +0.80
Fe3+(aq) + e Fe2+(aq) +0.77

I2(aq) + 2e 2I (aq) +0.62
+
Cu (aq) + e Cu(s) +0.53
Cu2+(aq) + 2e Cu(s) +0.34
+ +
BiO (aq) + 2H (aq) + 3e Bi(s) + H2O +0.32
Sn4+(aq) + 2e Sn2+(aq) +0.15
+
2H (aq) + 2e H2(g) 0 (by definition)
3+
Fe (aq) + 3e Fe(s) 0.04
Pb2+(aq) + 2e Pb(s) 0.13
2+
Sn (aq) + 2e Sn(s) 0.14
Ni2+(aq) + 2e Ni(s) 0.24
2+
Cd (aq) + 2e Cd(s) 0.40
2+
Fe (aq) + 2e Fe(s) 0.44
Cr3+(aq) + 3e Cr(s) 0.74
2+
Zn (aq) + 2e Zn(s) 0.76

2H2O + 2e H2(g) + 2OH (aq) 0.83 (0.41 at pH = 7)
2+
Cr (aq) + 2e Cr(s) 0.89
3+
Al (aq) + 3e Al(s) 1.68
Sc3+(aq) + 3e Sc(s) 2.09
2+
Mg (aq) + 2e Mg(s) 2.36
+
Na (aq) + e Na(s) 2.71
2+
Ca (aq) + 2e Ca(s) 2.87
+
Li (aq) + e Li(s) 3.04
CC0159(b) CHEM1101 2014, Semester 2

Useful formulas

Thermodynamics & Equilibrium Electrochemistry

U = q + w = q pV G = nFE
G = H TS Moles of e = It/F
G = G + RT lnQ E = E (RT/nF) 2.303 logQ
G = RT lnK = E (RT/nF) lnQ
univS = R lnK E = (RT/nF) 2.303 logK
K2 H 1 = (RT/nF) lnK
ln = ( 1)
K1 R T2 T1 0.0592
E = E logQ (at 25 C)
n

Acids and Bases Gas Laws

pKw = pH + pOH = 14.00 PV = nRT
pKw = pKa + pKb = 14.00 (P + n2a/V2)(V nb) = nRT
pH = pKa + log{[A] / [HA]} Ek = mv2

Radioactivity Kinetics
t = ln2/ t = ln2/k
A = N k = AeEa/RT
ln(N0/Nt) = t ln[A] = ln[A]o kt
k2 Ea 1
( 1)
14
C age = 8033 ln(A0/At) years
ln =
k1 R T1 T2

Mathematics Quantum Chemistry

b b2 4ac E = h = hc/
If ax2 + bx + c = 0, then x =
2a = h/mv
ln x = 2.303 log x E = Z2ER(1/n2)
Area of circle = r2 x(mv) h/4
Surface area of sphere = 4r2 q = 4r2 5.67 108 T4
Volume of sphere = 4/3 r3 T = 2.898 106 K nm

Miscellaneous Colligative Properties & Solutions

I = cRT
A = log
I0 Psolution = Xsolvent Psolvent
A = cl c = kp
e2 Tf = Kfm
E = A NA
4 0 r Tb = Kbm
 CC0159(b)
PERIODIC TABLE OF THE ELEMENTS
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
1 2
HYDROGEN HELIUM
H He
1.008 4.003
3 4 5 6 7 8 9 10
LITHIUM BERYLLIUM BORON CARBON NITROGEN OXYGEN FLUORINE NEON
Li Be B C N O F Ne
6.941 9.012 10.81 12.01 14.01 16.00 19.00 20.18
11 12 13 14 15 16 17 18
SODIUM MAGNESIUM ALUMINIUM SILICON PHOSPHORUS SULFUR CHLORINE ARGON
Na Mg Al Si P S Cl Ar
22.99 24.31 26.98 28.09 30.97 32.07 35.45 39.95

CHEM1101
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
POTASSIUM CALCIUM SCANDIUM TITANIUM VANADIUM CHROMIUM MANGANESE IRON COBALT NICKEL COPPER ZINC GALLIUM GERMANIUM ARSENIC SELENIUM BROMINE KRYPTON
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.10 40.08 44.96 47.88 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.39 69.72 72.59 74.92 78.96 79.90 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
RUBIDIUM STRONTIUM YTTRIUM ZIRCONIUM NIOBIUM MOLYBDENUM TECHNETIUM RUTHENIUM RHODIUM PALLADIUM SILVER CADMIUM INDIUM TIN ANTIMONY TELLURIUM IODINE XENON
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 88.91 91.22 92.91 95.94 [98.91] 101.07 102.91 106.4 107.87 112.40 114.82 118.69 121.75 127.60 126.90 131.30
55 56 57-71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
CAESIUM BARIUM HAFNIUM TANTALUM TUNGSTEN RHENIUM OSMIUM IRIDIUM PLATINUM GOLD MERCURY THALLIUM LEAD BISMUTH POLONIUM ASTATINE RADON
Cs Ba Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.91 137.34 178.49 180.95 183.85 186.2 190.2 192.22 195.09 196.97 200.59 204.37 207.2 208.98 [210.0] [210.0] [222.0]
87 88 89-103 104 105 106 107 108 109 110 111 112 114 116
FRANCIUM RADIUM RUTHERFORDIUM DUBNIUM SEABORGIUM BOHRIUM HASSIUM MEITNERIUM DARMSTADTIUM ROENTGENIUM COPERNICIUM FLEROVIUM LIVERMORIUM
Fr Ra Rf Db Sg Bh Hs Mt Ds Rg Cn Fl Lv
[223.0] [226.0] [261] [262] [266] [262] [265] [266] [271] [272] [283] [289] [293]
57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
LANTHANUM CERIUM PRASEODYMIUM NEODYMIUM PROMETHIUM SAMARIUM EUROPIUM GADOLINIUM TERBIUM DYSPROSIUM HOLMIUM ERBIUM THULIUM YTTERBIUM LUTETIUM
LANTHANOIDS
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

2014, Semester 2
138.91 140.12 140.91 144.24 [144.9] 150.4 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.04 174.97
89 90 91 92 93 94 95 96 97 98 99 100 101 102 103
ACTINIUM THORIUM PROTACTINIUM URANIUM NEPTUNIUM PLUTONIUM AMERICIUM CURIUM BERKELLIUM CALIFORNIUM EINSTEINIUM FERMIUM MENDELEVIUM NOBELIUM LAWRENCIUM
ACTINOIDS
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
[227.0] 232.04 [231.0] 238.03 [237.0] [239.1] [243.1] [247.1] [247.1] [252.1] [252.1] [257.1] [256.1] [259.1] [260.1]