Topics in the June 2014 Exam Paper for CHEM1611

Click on the links for resources on each topic.

2014-J-2: Atomic StructureThe Periodic Table

2014-J-3: Chemical BondingThe Shapes of Molecules

2014-J-4: Chemical Bonding

2014-J-5: AlkenesAldehydes and KetonesAlcohols, Phenols, Ethers and ThiolsCarboxylic Acids and Derivatives

2014-J-6: Stereochemistry

2014-J-7: Aromatic HydrocarbonsAldehydes and KetonesCarboxylic Acids and DerivativesAlkenesAlcohols, Phenols, Ethers and Thiols

2014-J-8: Carbohydrates

2014-J-9: Amino Acids, Peptides and Proteins

2014-J-10: Amino Acids, Peptides and Proteins

2014-J-11: DNA and Nucleic Acids

June 2014

CHEM1611 2014-J-1 2216(a)

2216(a) THE UNIVERSITY OF SYDNEY

CHEM1611 - CHEMISTRY 1A (PHARMACY) FIRST SEMESTER EXAMINATION

CONFIDENTIAL JUNE 2014 TIME ALLOWED: THREE HOURS GIVE THE FOLLOWING INFORMATION IN BLOCK LETTERS

FAMILY NAME

SID NUMBER

OTHER NAMES

TABLE NUMBER

• All questions are to be attempted. There

are 18 pages of examinable material.

• Complete 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.

• Each new short answer question begins with a •.

• Only non-programmable, University- approved calculators may be used.

• 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.

• 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.

• Pages 10, 14, 16, 22 and 24 are for rough work only.

OFFICIAL USE ONLY Multiple choice section

Marks Pages Max Gained

2-9 31

Short answer section

Marks Page Max Gained Marker

11 7

12 12

13 5

15 10

17 6

18 8

19 6

20 5

21 3

23 7

Total 69

Check Total

CHEM1611 2014-J-2 2216(a)

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• Reaction of nitrogen-14 with a neutron forms two products, one of which is carbon-14. Radiocarbon dating involves the carbon-14 isotope which undergoes β-decay (emission of an electron from the nucleus). Write the two nuclear equations that illustrate the formation and decay of carbon-14.

Marks 2

14C formation:

14C decay:

• Complete the following table. 3

Orbital Principal quantum number, n

Angular momentum quantum number, l

Number of spherical nodes

Number of planar nodes

4s 0

1 1

3 2

• It requires 151 kJ mol–1 to break the bond in I2. What is the minimum wavelength of light needed to break this bond? Give your answer in nm.

2

Answer:

THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY.

CHEM1611 2014-J-3 2216(a)

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• Complete the following table. Marks

12

Molecule CO2 SO2

Draw a Lewis structure

Name the molecular geometry

Does the molecule have a dipole moment? Give a reason for your answer.

Give the hybridisation of the central atom.

Comment on the relative strength of a π-bond in carbon dioxide compared to a π-bond in sulfur dioxide.

Both oxides dissolve in water to give a weak acid. Choose one of the oxides and write balanced equations representing the formation of the corresponding weak acid and the dissociation of the acid into ions.

Use one of the molecules/ions from the above equations to illustrate the concept of resonance.

CHEM1611 2014-J-4 2216(a)

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• Carbon monoxide is a poisonous gas that may be obtained from incomplete combustion. Draw the Lewis structure of carbon monoxide and add the labels lone pair, σ-bond, π-bond as appropriate.

Marks 5

On the atoms below, draw and label the orbitals (atomic and/or hybridised) that give rise to the bonds and lone pairs on carbon monoxide and clearly show which orbitals overlap with each other and the type of bond that results.

C O

THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY.

CHEM1611 2014-J-5 2216(a)

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• Complete the following table. Make sure you complete the name of the starting material where indicated.

Marks 10

STARTING MATERIAL REAGENTS/ CONDITIONS

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

Name:

Br2 CCl4 solvent

Name:

1. LiAlH4 2. dilute HCl

Name:

dilute NaOH

6 M NaOH heat

Na2Cr2O7 in dilute sulfuric acid

Name:

excess CH3CH2OH conc. H2SO4 catalyst

heat

O

OH

O

NH2

HO

O

CHEM1611 2014-J-6 2216(a)

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• Orlistat (shown below) is a drug for obesity management which acts by inhibiting the absorption of dietary fats. Indicate all stereogenic centres on the structure below.

Marks 6

How many different diastereoisomers are possible for Orlistat?

Select one of the stereogenic centres and draw the isomer with the (R)-configuration.

List the functional groups present in Orlistat.

Is Orlistat likely to be soluble in water? Why?

Orlistat

CHEM1611 2014-J-7 2216(a)

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• Show clearly the reagents you would use to carry out the following chemical conversions. Note that more than one step is required and you should indicate all necessary steps and the constitutional formulas of any intermediate compounds.

Marks 8

CHEM1611 2014-J-8 2216(a)

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• The open chain form of D-mannose has the structure shown.

Draw the Haworth projection of β-D-mannopyranose.

Marks 6

Draw the major organic product of the reaction of D-mannose with the following reagents.

What is a reducing sugar?

Give the Haworth formula of a non-reducing disaccharide that yields D-mannose as the only product on acid hydrolysis.

CHEM1611 2014-J-9 2216(a)

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• Alanine (ala) and lysine (lys) are two amino acids with the structures given below as Fischer projections. The pKa values of the conjugate acid forms of the different functional groups are indicated.

Draw the structure of the dipeptide ala-lys in its zwitterionic form.

Marks 5

Would you expect the dipeptide to be acidic, neutral or basic? Give a brief reason for your choice.

Estimate the isoelectric point of the dipeptide.

Answer:

CHEM1611 2014-J-10 2216(a)

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• Draw all products from the acid hydrolysis of the following dipeptide, indicating the correct charge state under these conditions.

Marks 3

THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY.

CHEM1611 2014-J-11 2216(a)

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• The following species represent some of the building blocks of RNA. Marks

7

N

N

NH2

OH

OH

HHO OH

H H

OHON

N

O

NH2

N

N

cytosine guanine

O PO

O

O

phosphateribofuranose

H

H H

Is the sugar depicted the α or the β form? Circle the correct answer. α β

Is the sugar depicted a reducing sugar or a non-reducing sugar? Circle the correct answer. reducing non-reducing

Indicate on the above structure the ‘anomeric’ carbon atom that gives rise to the α or the β form.

Draw the Fischer projection of D-ribose.

Using a selection of the species given, draw a nucleoside and a nucleotide.

nucleoside

nucleotide

2216(b) June 2014 CHEM1611 - CHEMISTRY 1A (PHARMACY)

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 = 1.013 bar 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 1 J = 1 kg m2 s–2

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

2216(b) June 2014 CHEM1611 - CHEMISTRY 1A (PHARMACY)

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 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 NO3

–(aq) + 10H+(aq) + 8e– → NH4+(aq) + 3H2O +0.88

Ag+(aq) + e– → Ag(s) +0.80 Fe3+(aq) + e– → Fe2+(aq) +0.77 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) –0.126 Sn2+(aq) + 2e– → Sn(s) –0.136 Ni2+(aq) + 2e– → Ni(s) –0.24 Co2+(aq) + 2e– → Co(s) –0.28 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 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

2216(b) June 2014 CHEM1611 - CHEMISTRY 1A (PHARMACY)

Useful formulas

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

Electrochemistry

ΔG° = –nFE°

Moles of e– = It/F

E = E° – (RT/nF) × lnQ

E° = (RT/nF) × lnK

E = E° – 0.0592n

logQ (at 25 °C)

Acids and Bases

pH = –log[H+]

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

Colligative Properties & Solutions

Π = cRT

Psolution = Xsolvent × P°solvent c = kp

ΔTf = Kfm

ΔTb = Kbm

Thermodynamics & Equilibrium

ΔG° = ΔH° – TΔS°

ΔG = ΔG° + RT lnQ

ΔG° = –RT lnK

ΔunivS° = R lnK

Kp = Kc100( )

nRT Δ

Miscellaneous

A = –log0

II

A = εcl

E = –A2

04erπε

NA

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

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

[263]

105 D

UB

NIU

M

Db

[268]

106 SE

AB

OR

GIU

M

Sg [271]

107 B

OH

RIU

M

Bh

[274]

108 H

ASSIU

M

Hs

[270]

109 M

EIT

NE

RIU

M

Mt

[278]

110 D

AR

MST

AD

TIU

M

Ds

[281]

111 R

OE

NT

GE

NIU

M

Rg

[281]

112 C

OPE

RN

ICIU

M

Cn

[285]

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]

2216(b) CHEM1611 June 2014