2208(a)

THE UNIVERSITY OF SYDNEY

CHEMISTRY 1B - CHEM1102
SECOND SEMESTER EXAMINATION

CONFIDENTIAL
NOVEMBER 2012

TIME ALLOWED: THREE HOURS

GIVE THE FOLLOWING INFORMATION IN BLOCK LETTERS

FAMILY
NAME
OTHER
NAMES

SID
NUMBER
TABLE
NUMBER

INSTRUCTIONS TO CANDIDATES
All questions are to be attempted. There
are 21 pages of examinable material.
Complete the written section of the
examination paper in INK.
Read each question carefully. Report the
appropriate answer and show all relevant
working in the space provided.
The total score for this paper is 100. The
possible score per page is shown in the
adjacent tables.

OFFICIAL USE ONLY

Multiple choice section
Marks
Pages

Max

2-8

29

Gained

Short answer section

Marks
Page

Max

Each new question of the short answer

section begins with a .

10

11

Only non-programmable, Universityapproved calculators may be used.

12

13

Students are warned that credit may not be

given, even for a correct answer, where
there is insufficient evidence of the working
required to obtain the solution.

14

15

17

Numerical values required for any question,

standard electrode reduction potentials, a
Periodic Table and some useful formulas
may be found on the separate data sheets.

18

19

20

Pages 16 and 24 are for rough working

only.

21

22

23

Total

71

Gained

Marker

CHEM1102

2012-N-2

2208(a)
Marks

What is the pH of a 0.100 M solution of sodium acetate?

The pKa of acetic acid is 4.76.

pH =
What is the ratio of acetate ion to acetic acid in this solution?

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

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CHEM1102

2012-N-3

2208(a)

Citric acid, C6H8O7, has three pKa values: pKa1 = 3.13, pKa2 = 4.76 and pKa3 = 6.40.
Explain, giving exact volumes and concentrations, how to make 1.0 L of a citratebased buffer with pH 5.58.

THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY.

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Marks

CHEM1102

2012-N-4

2208(a)
Marks

The phase diagram of carbon dioxide is shown below.

Identify the four phases, shown as 1 - 4, in the phase diagram.

1
2
3
4
What names are given to the two points A and B?
A
B
What are the physical characteristics of carbon dioxide in phase 4?

Why is the line between phases 1 and 2 almost vertical at pressures below 100 bar?

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CHEM1102

2012-N-5

2208(a)

The following three complex ions can all exhibit isomerism. Name the type of
isomerism involved in each case and draw the structures of the isomeric pairs.
ox = oxalate = C2O42

Marks

[CrCl2(NH3)4]+

[Fe(ox)3]3

[Co(NH3)3(OH2)3]3+

Give the systematic name of each of the following compounds.

en = ethylenediamine = 1,2-diaminoethane = NH2CH2CH2NH2
Cs2[PtF6]

[Co(en)2(NH3)2]Br3

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CHEM1102

2012-N-6

2208(a)

What are the structural differences between graphite and diamond and how do these
differences impact on their physical properties? Mention at least three physical
properties.

Describe the periodic trends of either atomic radius or of ionisation energy.

Explain the trend in the property selected.

THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY.

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Marks

CHEM1102

2012-N-7

2208(a)

Order either one of the two following sets of oxides in terms of increasing acidity.
Explain the reasons for your order.
1. HBrO4, H3AsO4, H2SeO4

Marks

2. HClO2, HClO, HClO4, HClO3.

A binary alloy has a face-centered cubic structure with atoms of element A in the
faces and atoms of element B at the corners. What is the formula of the alloy?
Explain your reasoning.

THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY.

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CHEM1102

2012-N-8

2208(a)

What is the solubility of scandium hydroxide, Sc(OH)3, (Ksp = 2 1030) in water?

Give your answer in g per 100 mL.

Marks

Answer:
How does the interplay of H and S affect the spontaneity of the phase change
between solid and liquid water?

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CHEM1102

2012-N-9

Consider the reaction

A(g) + B(g) + C(g) D(g)

data were obtained at 25 C.

2208(a)
for which the following

Experiment

Initial [A]
(mol L1)

Initial [B]
(mol L1)

Initial [C]
(mol L1)

Initial rate
(mol L1 s1)

0.0500

0.0500

0.1000

6.25 103

0.1000

0.0500

0.1000

1.25 102

0.1000

0.1000

0.1000

5.00 102

0.0500

0.0500

0.2000

6.25 103

Write the rate law and calculate the value of the rate constant.

THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY.

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Marks
3

CHEM1102

2012-N-10

2208(a)
Marks

Complete the following table.

STARTING MATERIAL

6
REAGENTS/
CONDITIONS

CONSTITUTIONAL
FORMULA(S) OF MAJOR
ORGANIC PRODUCT(S)

dilute H2SO4

1. NaOH
2. CH3Br

OH

concentrated H2SO4

O
OH

Cl

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CHEM1102

2012-N-11

2208(a)

Draw the structure of the organic product(s) formed when each of the following
compounds is treated with 4 M sodium hydroxide. The first two reactions proceed at
room temperature; the last one requires heating.
Compound

Organic Product(s)

THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY.

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Marks

CHEM1102

2012-N-12

2208(a)
Marks

Consider compound (P), whose structure is shown below.

Give the full name of compound (P) that unambiguously describes its stereochemistry.

When compound (P) reacts with bromine (Br2), two stereoisomers are formed. Draw
the structure of both products and label all stereogenic centres appropriately.

Devise a synthesis of the following compound from the starting material indicated.
Note that more than one step will be required. Indicate all necessary reagents and the
constitutional formulas of any intermediate compounds.

Page Total:

CHEM1102

2012-N-13

2208(a)

Devise a synthesis of the following compounds from the starting materials indicated.
Note that more than one step will be required. Indicate all necessary reagents and the
constitutional formulas of any intermediate compounds.
O

OH

Page Total:

Marks

CHEM1102

2012-N-14

2208(a)

Complete the mechanism for the following reaction. Give the structure of the
carbocation intermediate and indicate (using curly arrows) all the bonding changes
that occur.

THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY.

Page Total:

Marks

CHEM1102

2012-N-15

2208(a)

When HBr reacts with 1-pentene, three products, L, M and N, are formed. L and M
are enantiomers, whilst L and N (and M and N) are constitutional isomers. Give the
structures of these products and explain how they form? Discuss the relative amounts
of each product, paying attention to the regioselectivity and stereoselectivity of the
reaction.
Hint: You need to discuss important aspects of the reaction mechanism, including
the relative stabilities of any intermediates, but you do not need to give the full
mechanism using curly arrows.
L

THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY.

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Marks

2208(b)

November 2012

CHEM1102 - CHEMISTRY 1B

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
Fraction Prefix Symbol
103
milli
m
6
micro
10

109
10

12

nano

pico

Decimal multiples
Multiple Prefix Symbol
103
kilo
k
6
mega
M
10
109

giga

2208(b)

November 2012

CHEM1102 - CHEMISTRY 1B
Standard Reduction Potentials, E
Reaction
Co (aq) + e Co (aq)
3+

2+

Ce4+(aq) + e Ce3+(aq)

E / V
+1.82
+1.72

MnO4 (aq) + 8H (aq) + 5e Mn (aq) + 4H2O

+1.51

Au3+(aq) + 3e Au(s)

+1.50

Cl2 + 2e 2Cl (aq)

+1.36

O2 + 4H+(aq) + 4e 2H2O

+1.23

2+

Pt (aq) + 2e Pt(s)
2+

+1.18

MnO2(s) + 4H (aq) + e Mn
+

3+

+ 2H2O

+0.96

NO3(aq) + 4H+(aq) + 3e NO(g) + 2H2O

+0.96

Pd (aq) + 2e Pd(s)

+0.92

Ag+(aq) + e Ag(s)

+0.80

Fe (aq) + e Fe (aq)

+0.77

Cu (aq) + e Cu(s)

+0.53

2+

3+
+

2+

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)

Fe (aq) + 3e Fe(s)

0.04

Pb2+(aq) + 2e Pb(s)

0.13

Sn (aq) + 2e Sn(s)

0.14

Ni2+(aq) + 2e Ni(s)

0.24

Cd (aq) + 2e Cd(s)

0.40

Fe (aq) + 2e Fe(s)

0.44

Cr3+(aq) + 3e Cr(s)

0.74

Zn (aq) + 2e Zn(s)

0.76

2H2O + 2e H2(g) + 2OH(aq)

0.83

Cr (aq) + 2e Cr(s)

0.89

Al (aq) + 3e Al(s)

1.68

Sc3+(aq) + 3e Sc(s)

2.09

Mg (aq) + 2e Mg(s)

2.36

Na+(aq) + e Na(s)

2.71

Ca (aq) + 2e Ca(s)

2.87

Li (aq) + e Li(s)

3.04

3+

2+

2+

2+

2+

2+

3+

2+

2+

2208(b)

November 2012

CHEM1102 - CHEMISTRY 1B
Useful formulas
Quantum Chemistry

Electrochemistry

E = h = hc/

G = nFE

= h/mv

Moles of e = It/F

E = Z2ER(1/n2)

E = E (RT/nF) 2.303 logQ

= E (RT/nF) lnQ

x(mv) h/4
q = 4r2 5.67 108 T4

E = (RT/nF) 2.303 logK

= (RT/nF) lnK

T = 2.898 106 K nm

E = E

0.0592
logQ (at 25 C)
n

Acids and Bases

Gas Laws

pH = log[H+]

PV = nRT

pKw = pH + pOH = 14.00

(P + n2a/V2)(V nb) = nRT

pKw = pKa + pKb = 14.00

Ek = mv2

pH = pKa + log{[A] / [HA]}

Radioactivity

Kinetics

t = ln2/

t = ln2/k

A = N

k = AeEa/RT

ln(N0/Nt) = t

ln[A] = ln[A]o kt

14

C age = 8033 ln(A0/At) years

ln

k2
Ea 1
=
( - 1)
k1
R T1 T 2

Colligative Properties & Solutions

Thermodynamics & Equilibrium

= cRT

G = H TS

Psolution = Xsolvent Psolvent

G = G + RT lnQ

c = kp

G = RT lnK

Tf = Kfm

univS = R lnK

Tb = Kbm

Kp = Kc (RT)n

Miscellaneous

Mathematics

A = log

I
I0

If ax2 + bx + c = 0, then x =

A = cl
E = A

ln x = 2.303 log x
e2
4 0 r

NA

Area of circle = r2
Surface area of sphere = 4r2

b2 4ac
2a

10

11

12

13

14

15

16

17

18

HYDROGEN

HELIUM

He

1.008

4.003

LITHIUM

BERYLLIUM

BORON

CARBON

NITROGEN

OXYGEN

FLUORINE

NEON

Li

Be

Ne

6.941

9.012

10.81

12.01

14.01

16.00

19.00

20.18

10

12

13

14

15

16

17

18

MAGNESIUM

ALUMINIUM

SILICON

PHOSPHORUS

SULFUR

CHLORINE

ARGON

Na

Mg

Al

Si

Cl

Ar

22.99

24.31

26.98

28.09

30.97

32.07

35.45

39.95

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

Ca

Sc

Ti

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

Zr

Nb

Mo

Tc

Ru

Rh

Pd

Ag

Cd

In

Sn

Sb

Te

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

CAESIUM

BARIUM

72

73

74

75

76

77

78

79

80

81

82

83

84

85

86

HAFNIUM

TANTALUM

TUNGSTEN

RHENIUM

OSMIUM

IRIDIUM

PLATINUM

GOLD

MERCURY

THALLIUM

LEAD

BISMUTH

POLONIUM

ASTATINE

RADON

Cs

Ba

Hf

Ta

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
RADIUM

89-103 104
RUTHERFORDIUM

105

106

107

108

109

110

111

112

DUBNIUM

SEABORGIUM

BOHRIUM

HASSIUM

MEITNERIUM

DARMSTADTIUM

ROENTGENIUM

COPERNICIUM

Fr

Ra

Rf

Db

Sg

Bh

Hs

Mt

Ds

Rg

Cn

[223.0]

[226.0]

[261]

[262]

[266]

[262]

[265]

[266]

[271]

[272]

[283]

ACTINOIDS

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

La

Ce

Pr

Nd

Pm

Sm

Eu

Gd

Tb

Dy

Ho

Er

Tm

Yb

Lu

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

Ac

Th

Pa

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]

November 2012

LANTHANOID
S

CHEM1102 - CHEMISTRY 1B

11
SODIUM

FRANCIUM

2208(b)

PERIODIC TABLE OF THE ELEMENTS