IUniversit ~"';H\,,\1 ifGlasgo

Degree Examination Level-2

Monday, 09th May 2011 2Y (EX1RGP)

2.00 - 4.00 p.m.

CHEMISTRY -

This examination

paper is subdivided into two separate sec

ns, labelled A and B; ript book. HREE questions from e attempted, in the left

each section should be answered in a separate examination

Answer ANY SIX questions

from SECTION

A and ANY

SECTION B. List the numbers of the questions, which you h

hand column of the grid on the front page of each script bo k. Write all answers in INK in the book ON RIGHT HAND PAGES ONLY and numb them carefully.

The use of programmable

calculators is NOT allowed. In ea

you use a calculator,

full credit may only be given if all relevant working is shown.

The marks [indicated marking scheme,

in square brackets] represent an a

roximate guide to the MR chemical shifts, a

which will be used. A table of proton

periodic table and a list of useful physical constants are dis layed on the last three pages of this examination. paper; molecular models may also be ed for this particular

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SECTION A: Attempt ANY SIX ques

ns

Question 1
has the formula C3HyBr.

A halogenoalkane

(8)

Compound C3HyBr exists as two isomers. Draw and n

e the two isomers.

[2]
(b) Upon recording a 1H NMR spectrum of one of the is mers, A, the following three peaks were observed; (i) (ii) (iii) 1.06 ppm (triplet) 1.81 ppm (multiplet) 3.47 ppm (triplet) 3H, 2H, 2H.

Use this information to positively identify the structur I formula of isomer A, giving full reasoning.

[3]

(c)

Predict the appearance

of the

1H

NMR spectrum

f the other isomer of

C3HyBr drawn in (a), isomer B. [Include details of r lative peaks areas and splitting required]. [3] patterns of the peaks but specific chemic I shift values are not

(d)

The mass spectrum of isomer A has two parent! m lecular peaks of equal intensity at mlz

= 122 and mlz = 124. Explain

this ob

rvation. [2]

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Question 2

(a)

What criteria must be fulfilled for a compound to be specific example of an aromatic hydrocarbon

romatic? Show ONE example of a

and ONE

heteroaromatic

compound. [4]

(b)

What will be the products of bromination of (i) cyclohe Briefly explain the difference in reactivity and includ mechanism for the bromination of benzene.

ne and (ii) benzene? in your answer a full

[3]

(c)

2 - Bromopyridine

(A)

undergoes (8).

reaction

with

di

ethylamine

to

yield

2-dimethylaminopyridine reaction.

Propose

a mechanis

for this substitution

U
N A

HBr

Br

[3]

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Question 3

The oxidation of S02 is used in important industrial processes, high temperature. The equilibrium constant for this reaction is 973 K. 2S02 (g) + 02 (g)

nd is carried out at und to be K

= 4.5 at

===-~2S03 (g)
02, 0.25 atm 02 and will proceed at 973 K G

(a)

For a starting mixture of gases, consisting of 0.5 atm 0.4 atm S03, determine in which direction this reactio by calculating the non - standard condition free energy

= ~Go

+ RTlnQ. [6]

(b)

At the lower temperature

of 273 K, the standard free kJ. For the sa

nergy change for this mixture of gases as action is driven more

reaction as written above is -141.6 above, determine

~G and state whether or not the

towards the product at this temperature. [3]

(c)

In light of your findings above, suggest reasons wh carried out industrially at the higher temperature.

this reaction might be

[1]

[Gas constantR

= 8.314

J K- mof ']

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Question 4

(a)

Draw fully labelled d-orbital splitting diagrams for a tra

ition metal ion in:

(i)

an octahedral ligand field, [2]

(ii)

a tetrahedral ligand field. [2]

(b)

What is the ligand field stabilization energy (LFSE) f complex in:

a high-spin

cobalt(ll)

(i)

an octahedral ligand field?

[2]
(ii) a tetrahedral ligand field?

[2]

(c)

Do your values for the LFSE explain why cobalt I) readily forms both octahedral and tetrahedral complexes? [2]

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Question 5 le synthesis from the ould contain no more

(a)

Consider compound A shown below. Suggest a poss compound shown in brackets. Your starting materials than SEVEN carbon atoms.

[6
A [4]
(b) Consider the partial reaction scheme shown below. 0 scribe how compound B can be selectively converted into structures C to E.
OH HO

0 0

~o
0

h-

HO

D B
OH

~O

E [6]

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Question 6

Employing conventional IUPAC shorthand notation for the rep

sentation of Galvanic

cells, consider the following cell, operating under standard con itions:

Cd(S) I C d

2+

(aq) 11

Ag

(aq) I

Ag(s).

(a)

Using standard IUPAC convention, identify the catho e and the anode and state which is the positive and which is the negative el trode. [2]

(b)

Write the two half- reactions taking place within this cel

[2]

(c)

Show, by calculation, that this cell will operate sponta conditions.

ously under standard [2]

(d)

Calculate the equilibrium constant, K, for the cell react

n. [4]

[Standard electrode potentials: R = 8.314 J K-1 rnof':

r? Ci+/Cd

= -0.40 V,

r? Ag +/Ag
x

0.80 V; gas constant:

1 ,

Faraday constant: F = 9.649

10 C mor

zero on the

Celsius scale = 273.15 K]

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Question 7

Homosalate (A) shows sunscreen activity.

(a)

What

structural

features

of

homosalate

(A)

ar

responsible

for

its

effectiveness as a sunscreen?

[4]

(b)

Identify the chiral centres in homosalate (A) and assig or S to each centre. Clearly indicate the reasoning configuration in each case.

the configuration as R or the assignment of [4]

(c)

Draw the structures of the products of hydrolysis of ho

osalate (A). [2]

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Question 8

The structure of the anticancer drug melphalen (A) is drawn b

w.

~H2 H02C~

(YNl
A

CI

l...CI

(a)

Predict, with reasons, the predominant ionisation form hat melphalen (A) will exist as in aqueous solution at

pH = 7.
[3]

(b)

Would you expect melphalen (A) to be able to cross c

membranes? [3]

(c)

Melphalen (A) acts as a crossing linking agent of ON mechanism of its action.

Show the curly arrow [4]

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SECTION B: Attempt ANY THREE que tions

Question 9

Propanone

shows two UV absorption

maxima at A.1 = 1 ~

nm and a weaker

absorption at A.2

= 270

nm.

(a)

With reference to electronic transitions two absorption maxima are observed.

and molecul

orbitals, explain why

[3]

(b)

Calculate the energy (measured in joules) of a single of A.

hoton of UV radiation

= 190

nm. [2]

Question 10 Using chemical formulae and curly arrows, explain the nitr show the product(s) formed. Pay particular attention to the reaction occurs and give your rationalization, using resonanc on of anisole (A) and osition(s) in which the ormulae.

produc

s)

[5]

10

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Question 11

(a)

Explain with use of a simple diagram why the ent assumed to increase with increasing volume.

py of a gas can be [3]

(b)

Calculate the increase in entropy for the case that on expands from an initial volume of one litre to occupy a

mole of an ideal gas lume of ten litres. [2]

Question 12

Explain which of the following octahedrally coordinated tran ition metal ions would show a Jahn - Teller distortion: (a) (b) (c) chromium(III), copper(II), high-spin chromium(II). [5]

Question 13 eptide, indicating and provide a curly arrow

Consider the protected

peptide shown below. Redraw the

naming each of the protecting groups. Suggest reagents a mechanism for the removal of ONE of the protecting groups.

[5]

11

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Question 14

Methanol (CH30H) is sometimes used as antifreeze for the washer fluids. How many grams of methanol must be adde lower the freezing point to -10.0 QC?

ter in car windscreen to 5000 g of water to

[5]

[Freezing point depression constant for water: Kf = 1.86 K kg

01-

1 ]

Question 15

The structure of the antibacterial agent metronidazole (A) is sr

wn below.

A
(a) Giving your reasons, predict whether or not each nit basic. [3] gen atom in A will be

(b)

Predict, giving your reasoning, whether metronidazol at pH = 7.

will be soluble in water

[2]

12

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LIST OF 1H NMR CHEMICAL SI- FTS

I
Type of hydrogen Chemicalsh range (ppm)

C-CH3 C-CH C=C-C-H C == C-H Ar- C - H C=C-H -CH-OAr- H R - CH - NR - C (=0) - CH - C (= 0) - H - C (=0) - 0 - H Ar- 0 - H R-O-H Halogen - C - H N-H

0.8 1.0 1.6

1.1 1.6 1.9

2.5 ~ 2.7 2.2 -2.8 4.6 ~ 5.7 3.~ - 4.0 6.5

f-

8.5

2.~ - 2.9 2.( ~ 2.6 9.~ - 9.7 10.( -13.0 6.( -8.0 O.~ -6.0 3.~ - 4.1
I

OJ; - 3.0

Ar R

represents a benzene (aromatic) ring, characterizes an alkyl (aliphatic) chain.

13

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18
I 2

ls

H
Hy<trogen
1-0079 3

2s

li
Uthium
6941 11

Be
Beryllium
9-01218 12

PERIODIC TABLE OF THE ELEMENTS

He
13
5

14
G

15
7

16
8

17
9

~Iium
4-0026 10

B
Boron
lD-81
13

C
Carbon
12{)11 14

N
Nltroqen
140067 15

0
Oxyg<n
159994 16

F
Buorine
18-9984 17

Ne
Neon
2D-179
18

2p

3s

Na
Sodium
22-98977 19

Mg
Magn6ium
24-305 20

AI
3 3d. 4d.
21 Sd

Si
Silicon
28-0855 32

P
Phosphorus
30-9738 J3

S
Sulfur
32{)6 34

Cl
Chlcrlne
35"'53 35

AI'
Argon
39948 36

3p

4
22

5
23

G
2.

7
25

8
26

9
27

10
28

11
29

12
30

Aluminium
26-9815 31

45

K
Potassium
39-0983 37

Ca
Calcium
4<>08 38

Se
Scandium
44-9559 39

Ti
Titanium
47-88 40

V
Vanadium
50-9415 41

Cr Mn
Chromium
51-996 42

Fe
Iron
55-847 44

Co
Cobalt
589332 45

Ni Cu
Nickel
5869 46

Zn
Zinc
65-38 48

Ga
Gallium 6!H2
49

Ge
Gc:rmanium
7259 SO

As
A~nic
749216 51

Se
Selenium 19-90.(
52

Br
Bromine
79904 53

Kr
Krvpton
8380 54

4p

Manganese:
54-938 43

Copper
63546 47

Ss

Rb
Rubidium
85-4678 55

Sr
Strontium
87-61 56

y
Yttrium
88-9059 57

Zr
Zirconium
9122 72

Nb Mo
Niobium
929064 73

Te
Iectmetium
(98) 75

Ru
Ruthenium IOHJ7
76

Rh
Rhodium
1029055 77

Pd
P3l1adium
10642 78

Ag
Silver 107868 79

Cd
Cadmium
112'41 80

In Sn
Indium
1104-82 81

Sb
Antimony
121'75 83

Te
Ielturium
127'60 8.

1
Iodine
126-9045 85

Xe
Xenon
13129 86

5p

Molybc:knum
9594 7'

Ton
118-69 82

Gs

Cs
Cesium
132-9054 87

Ba 'La
Barium
13733 88 Lanthanum 1389055 89

Hf
Hafnium
171H9 104

Ta
Tantalum
180-9479 105

W
Iungsten
183-8S 106

Re
Rhenium
186207 107

Os
Osmium 190-2 108

Ir Pt
Iridium 192-22 109

Au
Gold 1969665

Hg
Mc:rcury 20059

TI
Thallium
204-383

Pb
lc:ad 2072

Bi
Bismuth 2089804

Po
Polonium
[209)

At
Astatine
[210)

Rn
Radon
(222)

Gp

Platinum
195-08

7s

Fr
Francium
(223)

Ra Ae
Radium
22&0254 Actinium

Rf
Rulhert"ordum
(261) ~r' 59

Db
Oubnium
[262)

Sg
Seaborqium
(263) 61

Bh
Bohrium
[264) 62

Hs
Hassium
(265) 63

Mt
Meirnerfum
(268) 64

) mass numbers of most stable isotope

227-0278

-~
60 65 66 67 68 69 70 1

58

4f

Ce
Cc:rium
140-12 90

Pr Nd
;
14O-!lO77

Pm
Promethium
(145) 93

Sm
Samarium
150-36 94

Eu
Europium
151-96 95

Gd
Gadolinium
157-25 96

Tb
Terbium
158'9254 97

Dy
Dysprosium
162'SO 98

Ho
Holmium
164-9304 99

Er Tm
Erbium
16726

Yb
Ytterbium
173{)4 102

Lu
lutetium 174967 103

Neodymium
144-24

Thulium
168'9342

ACTlNIUM SERIES
91 92 100 101

(5 :::0

5f

Th
Thorium 232.0381

Pa
Protactinium
0231.0359

U
Uranium
238.()389

Np
Neptunium
1.37-0482

Pu Am
Plutonium
(244)

Cm
Curium 1247)

Bk
Berkelium
(2471

Cf
Catifomium
1251)

Es Fm
Einsteinium (252) Fermium (257)

Md
~ndc:!('.vlum
12581

No
Nobelium (259)

Lr
Lawrencium
(260)

< m

Ameri<:ium
(243)