22/08(a)

The University of Sydney

CHEMISTRY 1B - CHEM1102
SECOND SEMESTER EXAMINATION

CONFIDENTIAL
NOVEMBER 2009

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 19 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.

OFFICIAL USE ONLY

Multiple choice section
Marks
Pages

Max

2-9

33

Short answer section

Marks
Page

Max

The total score for this paper is 100. The

possible score per page is shown in the
adjacent tables.

10

11

Each new question of the short answer

section begins with a .

13

14

16

17

18

19

20

21

22

Total

67

Electronic calculators, including

programmable calculators, may be used.
Students are warned, however, that credit
may not be given, even for a correct
answer, where there is insufficient
evidence of the working required to obtain
the solution.

Numerical values required for any question,

standard electrode reduction potentials, a
Periodic Table and some useful formulas
may be found on the separate data sheet.
Pages 12, 15, 23 & 24 are for rough
working only.

Gained

Gained

Marker

CHEM1102

2009-N-2

Explain why H2SO4 is a stronger acid than H2SO3.

22/08(a)
Marks

Explain why compounds of d-block elements are frequently paramagnetic. Use

examples in your answer.

Provide a systematic name for cis-[Co(en)2Cl2]Cl. Is this complex chiral? Explain

your reasoning by drawing the structure of the complex.
en = NH2CH2CH2NH2 = ethane-1,2-diamine = ethylenediamine

CHEM1102

2009-N-3

Solution A consists of a 0.020 M aqueous solution of aspirin (acetylsalicylic acid,

C9H8O4) at 25 C. Calculate the pH of Solution A. The pKa of aspirin is 3.52.

Answer:
At 25 C, 1.00 L of Solution B consists of 4.04 g of sodium acetylsalicylate
(NaC9H7O4) dissolved in water. Calculate the pH of Solution B.

Answer:
Solution B (200.0 mL) is mixed with Solution A (400.0 mL) and water (200.0 mL) to
give Solution C. Calculate the pH of Solution C after equilibration at 25 C.

Answer:
If you wanted to adjust the pH of Solution C to be exactly
equal to 3.00, which component in the mixture would you
need to increase in concentration?

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Marks

CHEM1102

2009-N-4

Write a balanced chemical equation representing the dissolution of FeCO3 in water at

pH 7.

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Marks

Ignoring any hydrolysis of the ions, calculate the solubility (in g L1) of FeCO3 in
water at pH 7. The solubility product constant, Ksp, for FeCO3 is 2.1 1011.

Answer:
The concentration of iron in the ocean is one of the primary factors limiting the
growth rates of some basic life forms. The pH of the oceans before the Industrial
Revolution was around 8.22. What was the maximum concentration of Fe3+(aq) in
the ocean at this pH? The Ksp of Fe(OH)3 is 1 1039.

Answer:
Industrialisation has led to an increase in atmospheric CO2. What effect has this had
on the amount of Fe3+(aq) in sea water?

CHEM1102

2009-N-5

22/08(a)

Solid sulfur can exist in both rhombic and monoclinic forms. A portion of the phase
diagram for sulfur is reproduced schematically below.

Liquid

Pressure (mmHg)

Solid Rhombic
Solid
Monoclinic

o 0.027 mmHg
119
(119C,
C, 0.027 mm Hg)
o 0.0043 mmHg
96
(96C,
C, 0.0043 mm Hg)

Vapour

Temperature
(C) o
Temperature ( C)

How many triple points are there in the phase diagram?

What phases are in equilibrium at each of the triple points?

What phase is stable at room temperature

and 760 mmHg pressure?
Can monoclinic sulfur exist in equilibrium
with sulfur vapour at 1.0 atm pressure?
Which solid form of sulfur is more dense? Explain your reasoning.

Describe the phase changes that occur when sulfur at 0.01 mmHg is slowly warmed
from 90 C to 130 C.

Marks

CHEM1102

2009-N-6

An alloy is formed by combining elements A and B. The alloy has a face-centred

cubic structure, with atoms of A at the corners and atoms of B in the faces. What is
the formula of the alloy? Explain your reasoning.

22/08(a)
Marks

Answer:
Derive expressions for the equilibrium constants for the complexation of Pb2+ (K1)
and of Ca2+ (K2) by EDTA4.

Briefly explain why the chelating agent, EDTA, is administered as [Ca(EDTA)]2 to

treat lead poisoning and determine which of K1 or K2 must be greater for the therapy
to be effective.

CHEM1102

2009-N-7

22/08(a)
Marks

Consider compound F shown below.

8
F

Br
Assign the stereocentre in compound F as (R) or (S), explaining your reasoning.

Assign the double bond stereochemistry in compound F, explaining your reasoning.

Draw the enantiomer of compound F.

When compound F is reacted with hydrogen gas in the presence of a palladium

catalyst, two stereoisomeric products, G and H, are formed. Draw these products.

What word is used to describe the stereochemical relationship between G and H?

CHEM1102

2009-N-8

22/08(a)

Bromide A undergoes a reaction with hydroxide ions (OH) to produce alcohol C.

Complete the mechanism by adding curly arrows to illustrate the bonding changes
that take place in the conversion of A to B and from B to C.

Br
OH
Br

OH

What is the name of the reaction taking place when A is converted to C via
carbocation intermediate B?

What is the stereochemical outcome of this reaction? Give reasons for your answer.

OH
H
C

D
O

Alcohol C can be further reacted with reagent D to generate ester E. Provide a

structure of a suitable reagent D for the synthesis of ester E from alcohol C.

Marks

CHEM1102

2009-N-9

22/08(a)
Marks

Consider the following reaction sequence.

6
O
OH

K
Reagent A

Reagent B

O
+

HCl

Compound K below can be converted into two different intermediates, L and M,

which can react together to give compound N and the inorganic byproduct HCl.
Give the reagents A and B and draw the structure of the intermediates L and M.
A

CHEM1102

2009-N-10

Give the constitutional formula(s) of the organic products formed in each of the
following reactions

NH2
OCH3
O

Br
NaCN

O
4 M NaOH
O

heat

THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY.

22/08(a)
Marks

CHEM1102

2009-N-11

22/08(a)

Sketch the resonances you would expect to observe for protons HB and HC in the
1
H NMR spectrum of compound X. Ensure that the approximate chemical shifts,
as well as peak splittings and signal integrations are incorporated in your answer.
(The resonance for HA is provided as a guide.)

O HB

HB

HA
HA

HC

O
HA

HC

HC

HA, singlet,
Integration = 3

THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY.

Marks

CHEM1102

2009-N-12

22/08(a)

Devise a synthesis of propylbenzene (V) using propanal (T) and bromobenzene (U)
as starting materials. Provide any intermediate structures and reagents.
(Hint: More than one step is required.)

Br

O
H
T

Marks

22/08(b)

November 2009
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 Pa = 1 N m2 = 1 kg m1 s2

0 C = 273 K

1 Ci = 3.70 1010 Bq

1 L = 103 m3

1 Hz = 1 s1

1 = 1010 m

1 tonne = 103 kg

1 eV = 1.602 1019 J

1 W = 1 J s1

Decimal fractions
Fraction
103
106
9

10
1012

Prefix
milli
micro
nano
pico

Decimal multiples

Symbol
m

n
p

Multiple
103
106
109
1012

Prefix Symbol
kilo
k
mega
M
giga
tera

G
T

22/08(b)

November 2009
CHEM1102 - CHEMISTRY 1B

Standard Reduction Potentials, E

Reaction
S2O8

+ 2e 2SO4

E / V
+2.01

Co (aq) + e Co2+(aq)

+1.82

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

+1.72

MnO4(aq) + 8H+(aq) + 5e Mn2+(aq) + 4H2O

+1.51

Au (aq) + 3e Au(s)

+1.50

Cl2(g) + 2e 2Cl(aq)

+1.36

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

+1.23

Br2 + 2e 2Br (aq)

+1.10

MnO2(s) + 4H+(aq) + e Mn3+(aq) + 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

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

Sn (aq) + 2e Sn (aq)

+0.15

2H (aq) + 2e H2(g)

0 (by definition)

Fe3+(aq) + 3e Fe(s)

0.04

Pb (aq) + 2e Pb(s)

0.13

Sn (aq) + 2e Sn(s)

0.14

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

0.24

Co (aq) + 2e Co(s)

0.28

Fe (aq) + 2e Fe(s)

0.44

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

0.74

3+

3+

2+

4+

2+

2+

2+

2+

2+

Zn (aq) + 2e Zn(s)
2+

0.76

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

0.83

Cr2+(aq) + 2e Cr(s)

0.89

Al3+(aq) + 3e Al(s)

1.68

Mg (aq) + 2e Mg(s)

2.36

Na+(aq) + e Na(s)

2.71

Ca2+(aq) + 2e Ca(s)

2.87

Li (aq) + e Li(s)

3.04

2+

22/08(b)

November 2009
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

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

14

C age = 8033 ln(A0/At) years

ln

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

Colligative Properties and Solutions

Thermodynamics and 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

b2 4ac
2a

ln x = 2.303 log x
e2
4 0 r

NA

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

10

11

12

13

14

15

16

17

18

HYDROGEN

HELIUM

He

1.008

4.003

BERYLLIUM

BORON

CARBON

NITROGEN

OXYGEN

FLUORINE

10
NEON

Li

Be

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

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

FRANCIUM

RADIUM

89-103 104
RUTHERFORDIUM

105

106

107

108

109

110

111

DUBNIUM

SEABORGIUM

BOHRIUM

HASSIUM

MEITNERIUM

DARMSTADTIUM

ROENTGENIUM

Fr

Ra

Rf

Db

Sg

Bh

Hs

Mt

Ds

Rg

[223.0]

[226.0]

[261]

[262]

[266]

[262]

[265]

[266]

[271]

[272]

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 2009

LANTHANOID
S

CHEM1102 - CHEMISTRY 1B

3
LITHIUM

22/08(b)

PERIODIC TABLE OF THE ELEMENTS