Topics in the November 2014 Exam Paper for CHEM1904

Click on the links for resources on each topic.

2014-N-2: Crystal Structures

2014-N-3: Intermolecular Forces and Phase BehaviourPhysical States and Phase DiagramsCrystal Structures

2014-N-4: Metal ComplexesCoordination Chemistry

2014-N-5: Metal ComplexesCoordination Chemistry

2014-N-6: Weak Acids and BasesCalculations Involving pKa

2014-N-7: Kinetics

2014-N-8: Carboxylic Acids and Derivatives

2014-N-9: AlkenesStereochemistry

2014-N-10: AlkenesStereochemistry

2014-N-11: AminesAromatic Compounds

2014-N-12: Aromatic Compounds

2014-N-13: Carboxylic Acids and Derivatives

November 2014

CC0162(a) 2014-N-1 Page 1 of 24

Confidential

SEAT NUMBER: ………………………………………

STUDENT ID: ………………………………………….

SURNAME: …………………………………………….

GIVEN NAMES: …………………………………..

CHEM1902 and CHEM1904 Chemistry 1B (Advanced) and Chemistry 1B (SSP)

Final Examination Semester 2, 2014

Time Allowed: Three hours + 10 minutes reading time

This examination paper consists of 24 pages

INSTRUCTIONS TO CANDIDATES 1. This is a closed book exam.

2. A simple calculator (programmable versions and PDA’s not allowed) may be taken into the exam room.

Make Model

3. The total score for this paper is 100. The possible score per page is shown in the adjacent table.

4. The paper comprises 30 multiple choice questions and 12 pages of short answer questions. ANSWER ALL QUESTIONS.

5. Follow the instructions on page 2 to record your answers to the multiple choice questions. Use a dark lead pencil so that you can erase errors made on the computer sheet.

6. Answer all short answer questions in the spaces provided on this question paper. Credit may not be given where there is insufficient evidence of the working required to obtain the solution.

7. Take care to write legibly. Write your final answers in ink, not pencil.

8. 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.

Marks Page(s) Max Gained Marker

2-9 30 MCQ

10 5

11 5

12 6

13 2

14 8

16 4

17 6

18 7

19 7

20 6

21 9

23 5

Total 100

Check Total

CC0162(a) 2014-N-2 Page 2 of 24

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• The cubic form of boron nitride (borazon) is the second-hardest material after diamond and it crystallizes with the structure shown below. The large spheres represent nitrogen atoms and the smaller spheres represent boron atoms.

From the unit cell shown above, determine the empirical formula of boron nitride.

Marks 5

Answer:

Determine the oxidation state of the boron atoms.

Answer:

The cubic form of boron nitride is more thermally stable in air than diamond. Provide a reasonable explanation for this observation.

CC0162(a) 2014-N-3 Page 3 of 24

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• A simplified phase diagram for iron is shown below, with the solid part divided into the body-centred cubic (BCC) and face-centred cubic (FCC) phases.

Which form of iron is stable at room temperature and pressure?

Marks 5

If molten iron is cooled slowly to around 1200 °C and then cooled rapidly to room temperature, the FCC form is obtained. Draw arrows on the phase diagram to indicate this process and explain why it leads to the FCC form as a metastable phase.

The line dividing the BCC and FCC forms is almost, but not quite vertical. Predict which way this line slopes and explain your answer.

CC0162(a) 2014-N-4 Page 4 of 24

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• In 2009, great excitement was generated amongst chemists worldwide with the report of a neutral Mo complex containing two bridging, anionic N-donor ligands. The structure of the complex is shown below. iPr = isopropyl = –CH(CH3)2

Name the complex by using standard IUPAC nomenclature. For simplicity, the name of the N-donor ligand (in its neutral form) can be shortened to “aminidate”.

Marks 6

The Mo complex above possesses an extremely short Mo–Mo bond (202 pm), much shorter than the bonding distance between Mo atoms in Mo metal (273 pm)! (a) Propose a reasonable explanation for the very short Mo–Mo bond length in the complex by adding d-electrons into the (partial) MO scheme shown below. (b) Determine the bond order for the metal-metal bond and re-draw the structure of the complex shown above indicating the actual bonding between the two Mo atoms.

THIS QUESTION CONTINUES ON THE NEXT PAGE.

CC0162(a) 2014-N-5 Page 5 of 24

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Oxidation of the Mo complex by two electrons gives rise to a paramagnetic species in which the Mo–Mo distance increases significantly. Give a reasonable hypothesis for the bond-lengthening phenomenon.

Marks 2

Determine the number of unpaired electrons in the oxidised Mo complex.

THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY.

CC0162(a) 2014-N-6 Page 6 of 24

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• Boric acid, B(OH)3, is a weak acid (pKa = 9.24) that is used as a mild antiseptic and eye wash. Unusually, the Lewis acidity of the compound accounts for its Brønsted acidity. By using an appropriate chemical equation, show how this compound acts as a Brønsted acid in aqueous solution.

Marks 8

Solution A consists of a 0.60 M aqueous solution of boric acid at 25 °C. Calculate the pH of Solution A.

pH =

At 25 °C, 1.00 L of Solution B consists of 112 g of NaB(OH)4 dissolved in water. Calculate the pH of Solution B.

pH =

Using both Solutions A and B, calculate the volumes (mL) required to prepare a 1.0 L solution with a pH = 9.24.

Answer:

CC0162(a) 2014-N-7 Page 7 of 24

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THIS PAGE IS FOR ROUGH WORKING ONLY.

CC0162(a) 2014-N-8 Page 8 of 24

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• At a certain temperature the following data were collected for the decomposition of HI.

2HI → H2 + I2

Marks 4

Experiment Initial [HI] (mol L–1) Initial rate of reaction (mol L–1 s–1)

1 1.0 × 10–2 4.0 × 10–6

2 2.0 × 10–2 1.6 × 10–5

3 3.0 × 10–2 3.6 × 10–5

Determine the rate law for the reaction.

What is the value of the rate constant for the decomposition of HI?

Answer:

CC0162(a) 2014-N-9 Page 9 of 24

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• Consider the following reaction sequences beginning with the carboxylic acid, E.

Marks 6

Name compounds E and G.

E:

G:

Propose structures for compounds F, H and J.

F

H

J

Propose a mechanism for step (ii).

CC0162(a) 2014-N-10 Page 10 of 24

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• The elimination of H2O from alcohol A can form the isomeric alkenes B and C. Elimination of HBr from the alkyl halide D can generate the same alkenes.

Assign the absolute configuration of alcohol A. Show your working.

Marks 7

Name compound B fully.

Draw the enantiomer of A and a diastereoisomer of D.

enantiomer of A diastereoisomer of D

Propose a mechanism for the formation of B from A under the conditions shown.

THIS QUESTION CONTINUES ON THE NEXT PAGE.

CC0162(a) 2014-N-11 Page 11 of 24

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Explain why C is the minor product of this reaction. Marks 7

A diastereoisomer of B is also formed in these reactions. Draw its structure. Do you expect B or its diastereoisomer to be the major product formed when A undergoes the above elimination reaction? Explain your reasoning.

Propose a mechanism for the formation of C from D under the conditions shown.

Explain why C is the major product of this reaction.

What would be the major product if the enantiomer of D were exposed to the same reaction conditions?

CC0162(a) 2014-N-12 Page 12 of 24

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• Benzene, pyridine and pyrrole are all aromatic.

What three criteria must be met for a compound to be aromatic?

Marks 6

Apply your previous answer to explain the following.

Pyridine is basic but pyrrole is not.

The pKa of cyclopentadiene is much lower than that of cyclopentene.

CC0162(a) 2014-N-13 Page 13 of 24

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• Benzene can undergo an SEAr reaction with bromine, Br2, as shown below. Demonstrate your understanding of this reaction by adding curly arrows to complete the mechanism.

Marks 9

Explain what each part of the abbreviation SEAr means.

S =

E =

Ar =

Identify one nucleophile and one electrophile in the scheme above.

nucleophile

electrophile

Iron(III) bromide, FeBr3, is often added to the reaction shown above. Why?

2-Chloropyridine can undergo the following reaction with sodium cyanide.

This reaction also proceeds via a two-step mechanism and an ionic (i.e. charged) intermediate. Apply your understanding of organic reactions to propose a mechanism for this reaction.

If the reaction of benzene shown above is SEAr, how would you classify this reaction of chloropyridine?

CC0162(a) 2014-N-14 Page 14 of 24

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THIS PAGE IS FOR ROUGH WORKING ONLY.

CC0162(a) 2014-N-15 Page 15 of 24

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• Draw the conjugate bases for the following acids. Marks

5 S

T

U

V

Conjugate base of S

Conjugate base of T Conjugate base of U Conjugate base of V

Which of S and T is the stronger acid? Give a reason for your answer.

Which of U and V is the stronger acid? Give a reason for your answer.

CC0162(a) 2014-N-16 Page 16 of 24

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THIS PAGE IS FOR ROUGH WORKING ONLY.

CC0162(b) CHEM1902/1904 2014, Semester 2

DATA SHEET Physical constants Avogadro constant, NA = 6.022 × 1023 mol–1 Faraday constant, F = 96485 C mol–1 Planck constant, h = 6.626 × 10–34 J s Speed of light in vacuum, c = 2.998 × 108 m s–1 Rydberg constant, ER = 2.18 × 10–18 J Boltzmann constant, kB = 1.381 × 10–23 J K–1 Permittivity of a vacuum, ε0 = 8.854 × 10–12 C2 J–1 m–1 Gas constant, R = 8.314 J K–1 mol–1 = 0.08206 L atm K–1 mol–1 Charge of electron, e = 1.602 × 10–19 C Mass of electron, me = 9.1094 × 10–31 kg Mass of proton, mp = 1.6726 × 10–27 kg Mass of neutron, mn = 1.6749 × 10–27 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 cm–3 Conversion factors 1 atm = 760 mmHg = 101.3 kPa 1 Ci = 3.70 × 1010 Bq 0 °C = 273 K 1 Hz = 1 s–1 1 L = 10–3 m3 1 tonne = 103 kg 1 Å = 10–10 m 1 W = 1 J s–1 1 eV = 1.602 × 10–19 J

Decimal fractions Decimal multiples Fraction Prefix Symbol Multiple Prefix Symbol

10–3 milli m 103 kilo k 10–6 micro µ 106 mega M 10–9 nano n 109 giga G 10–12 pico p 1012 tera T

CC0162(b) CHEM1902/1904 2014, Semester 2

Standard Reduction Potentials, E°

Reaction E° / V Co3+(aq) + e– → Co2+(aq) +1.82 Ce4+(aq) + e– → Ce3+(aq) +1.72 MnO4

–(aq) + 8H+(aq) + 5e– → Mn2+(aq) + 4H2O +1.51 Au3+(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 MnO2(s) + 4H+(aq) + e– → Mn3+ + 2H2O +0.96 NO3

–(aq) + 4H+(aq) + 3e– → NO(g) + 2H2O +0.96 Pd2+(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) Fe3+(aq) + 3e– → Fe(s) –0.04 Pb2+(aq) + 2e– → Pb(s) –0.13 Sn2+(aq) + 2e– → Sn(s) –0.14 Ni2+(aq) + 2e– → Ni(s) –0.24 Cd2+(aq) + 2e– → Cd(s) –0.40 Fe2+(aq) + 2e– → Fe(s) –0.44 Cr3+(aq) + 3e– → Cr(s) –0.74 Zn2+(aq) + 2e– → Zn(s) –0.76 2H2O + 2e– → H2(g) + 2OH–(aq) –0.83 (–0.41 at pH = 7) Cr2+(aq) + 2e– → Cr(s) –0.89 Al3+(aq) + 3e– → Al(s) –1.68 Sc3+(aq) + 3e– → Sc(s) –2.09 Mg2+(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

CC0162(b) CHEM1902/1904 2014, Semester 2

Useful formulas

Thermodynamics & Equilibrium

ΔU = q + w = q – pΔV

ΔG° = ΔH° – TΔS°

ΔG = ΔG° + RT lnQ

ΔG° = –RT lnK

ΔunivS° = R lnK

2

1 2 1

1 1ln = ( )K HK R T T

−Δ °−

Electrochemistry

ΔG° = –nFE°

Moles of e– = It/F

E = E° – (RT/nF) × 2.303 logQ

= E° – (RT/nF) × lnQ

E° = (RT/nF) × 2.303 logK

= (RT/nF) × lnK

E = E° – 0.0592n

logQ (at 25 °C)

Acids and Bases

pKw = pH + pOH = 14.00

pKw = pKa + pKb = 14.00

pH = pKa + log{[A–] / [HA]}

Gas Laws

PV = nRT (P + n2a/V2)(V – nb) = nRT

Ek = ½mv2

Radioactivity

t½ = ln2/λ

A = λN

ln(N0/Nt) = λt 14C age = 8033 ln(A0/At) years

Kinetics

t½ = ln2/k k = Ae–Ea/RT

ln[A] = ln[A]o – kt

2

1 1 2

1 1ln = ( )ak Ek R T T

−

Mathematics

If ax2 + bx + c = 0, then x = 2b b 4ac

2a− ± −

ln x = 2.303 log x

Area of circle = πr2

Surface area of sphere = 4πr2

Volume of sphere = 4/3 πr3

Quantum Chemistry

E = hν = hc/λ

λ = h/mv

E = –Z2ER(1/n2)

Δx⋅Δ(mv) ≥ h/4π

q = 4πr2 × 5.67 × 10–8 × T4

T λ = 2.898 × 106 K nm

Miscellaneous

A = –log0

II

A = εcl

E = –A2

04erπε

NA

Colligative Properties & Solutions

Π = cRT Psolution = Xsolvent × P°solvent c = kp ΔTf = Kfm

ΔTb = Kbm

PER

IOD

IC T

AB

LE

OF T

HE

EL

EM

EN

TS

1

2 3

4 5

6 7

8 9

10 11

12 13

14 15

16 17

18

1 H

YD

RO

GE

N

H

1.008

2 H

EL

IUM

He

4.003 3

LIT

HIU

M

Li

6.941

4 B

ER

YL

LIU

M

Be

9.012

5 B

OR

ON

B

10.81

6 C

AR

BO

N

C

12.01

7 N

ITR

OG

EN

N

14.01

8 O

XY

GE

N

O

16.00

9 FL

UO

RIN

E

F 19.00

10 N

EO

N

Ne

20.18 11

SOD

IUM

Na

22.99

12 M

AG

NE

SIUM

Mg

24.31

13 A

LU

MIN

IUM

Al

26.98

14 SIL

ICO

N

Si 28.09

15 PH

OSPH

OR

US

P 30.97

16 SU

LFU

R

S 32.07

17 C

HL

OR

INE

Cl

35.45

18 A

RG

ON

Ar

39.95 19

POT

ASSIU

M

K

39.10

20 C

AL

CIU

M

Ca

40.08

21 SC

AN

DIU

M

Sc 44.96

22 T

ITA

NIU

M

Ti

47.88

23 V

AN

AD

IUM

V

50.94

24 C

HR

OM

IUM

Cr

52.00

25 M

AN

GA

NE

SE

Mn

54.94

26 IR

ON

Fe 55.85

27 C

OB

AL

T

Co

58.93

28 N

ICK

EL

Ni

58.69

29 C

OPPE

R

Cu

63.55

30 Z

INC

Zn

65.39

31 G

AL

LIU

M

Ga

69.72

32 G

ER

MA

NIU

M

Ge

72.59

33 A

RSE

NIC

As

74.92

34 SE

LE

NIU

M

Se 78.96

35 B

RO

MIN

E

Br

79.90

36 K

RY

PTO

N

Kr

83.80 37

RU

BID

IUM

Rb

85.47

38 ST

RO

NT

IUM

Sr 87.62

39 Y

TT

RIU

M Y

88.91

40 Z

IRC

ON

IUM

Zr

91.22

41 N

IOB

IUM

Nb

92.91

42 M

OL

YB

DE

NU

M

Mo

95.94

43 T

EC

HN

ET

IUM

Tc

[98.91]

44 R

UT

HE

NIU

M

Ru

101.07

45 R

HO

DIU

M

Rh

102.91

46 PA

LL

AD

IUM

Pd 106.4

47 SIL

VE

R

Ag

107.87

48 C

AD

MIU

M

Cd

112.40

49 IN

DIU

M

In 114.82

50 T

IN

Sn 118.69

51 A

NT

IMO

NY

Sb 121.75

52 T

EL

LU

RIU

M

Te

127.60

53 IO

DIN

E

I 126.90

54 X

EN

ON

Xe

131.30 55

CA

ESIU

M

Cs

132.91

56 B

AR

IUM

Ba

137.34

57-71 72

HA

FNIU

M

Hf

178.49

73 T

AN

TA

LU

M

Ta

180.95

74 T

UN

GST

EN

W

183.85

75 R

HE

NIU

M

Re

186.2

76 O

SMIU

M

Os

190.2

77 IR

IDIU

M

Ir 192.22

78 PL

AT

INU

M

Pt 195.09

79 G

OL

D

Au

196.97

80 M

ER

CU

RY

Hg

200.59

81 T

HA

LL

IUM

Tl

204.37

82 L

EA

D

Pb 207.2

83 B

ISMU

TH

Bi

208.98

84 PO

LO

NIU

M

Po [210.0]

85 A

STA

TIN

E

At

[210.0]

86 R

AD

ON

Rn

[222.0] 87

FRA

NC

IUM

Fr [223.0]

88 R

AD

IUM

Ra

[226.0] 89-103 104

RU

TH

ER

FOR

DIU

M

Rf

[261]

105 D

UB

NIU

M

Db

[262]

106 SE

AB

OR

GIU

M

Sg [266]

107 B

OH

RIU

M

Bh

[262]

108 H

ASSIU

M

Hs

[265]

109 M

EIT

NE

RIU

M

Mt

[266]

110 D

AR

MST

AD

TIU

M

Ds

[271]

111 R

OE

NT

GE

NIU

M

Rg

[272]

112 C

OPE

RN

ICIU

M

Cn

[283]

114

FLE

RO

VIU

M

Fl [289]

116

LIV

ER

MO

RIU

M

Lv

[293]

LAN

THA

NO

IDS

57 L

AN

TH

AN

UM

La

138.91

58 C

ER

IUM

Ce

140.12

59 PR

ASE

OD

YM

IUM

Pr 140.91

60 N

EO

DY

MIU

M

Nd

144.24

61 PR

OM

ET

HIU

M

Pm

[144.9]

62 SA

MA

RIU

M

Sm

150.4

63 E

UR

OPIU

M

Eu

151.96

64 G

AD

OL

INIU

M

Gd

157.25

65 T

ER

BIU

M

Tb

158.93

66 D

YSPR

OSIU

M

Dy

162.50

67 H

OL

MIU

M

Ho

164.93

68 E

RB

IUM

Er

167.26

69 T

HU

LIU

M

Tm

168.93

70 Y

TT

ER

BIU

M

Yb

173.04

71 L

UT

ET

IUM

Lu

174.97

AC

TINO

IDS

89 A

CT

INIU

M

Ac

[227.0]

90 T

HO

RIU

M

Th

232.04

91 PR

OT

AC

TIN

IUM

Pa [231.0]

92 U

RA

NIU

M

U

238.03

93 N

EPT

UN

IUM

Np

[237.0]

94 PL

UT

ON

IUM

Pu [239.1]

95 A

ME

RIC

IUM

Am

[243.1]

96 C

UR

IUM

Cm

[247.1]

97 B

ER

KE

LL

IUM

Bk

[247.1]

98 C

AL

IFOR

NIU

M

Cf

[252.1]

99 E

INST

EIN

IUM

Es

[252.1]

100 FE

RM

IUM

Fm

[257.1]

101 M

EN

DE

LE

VIU

M

Md

[256.1]

102 N

OB

EL

IUM

No

[259.1]

103 L

AW

RE

NC

IUM

Lr

[260.1]

CC0162(b) CHEM1902/1904 2014, Semester 2