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Name . Set ..

A2 Scheme B
CHEMISTRY

Homework
Booklet
2009-10

2009-10
Homework

page

Independent Study - Optical isomerism

Isomerism
Carbonyl Chemistry

4
5-6

Carboxylic Acids

7-8

Independent Study
Reaction Summaries and Biodiesel

10

Esters and Carboxylic Acid Derivatives


New Mass Spec and IR

13-14

NMR and Chromatography

15-16

Introductory Ideas About Benzene, C6H6


Alkenes vs Arenes

11-12

18
19-20

Phenols

21

Amines

22

Amides, Azo Dyes and Aromatic amines

23-24

Polymers and Amino Acids


Synthetic Reaction Schemes

25-26

Organic Synthesis

29-30

More Organic Synthesis

31-32

27-28

As well as completing your set homework task you should also work on the Independent Study
tasks on the next page.

Alevel Chemistry Independent Study (second year)


As with last year you are responsible for your own learning and going beyond the
restraints of the syllabus.
It is important that you know how Chemistry is relevant to contemporary issues and how it
influences the world around us.
The topics we would like you to focus on this year are;

Supramolecular chemistry.
The importance of Organic Synthesis in the Pharmaceutical industry.
The importance of understanding reaction mechanisms in drug synthesis.
The use of Combinatorial chemistry in drug research.
Chemical Analysis using Gas Chromatography (GC).
Chemical Analysis using Nuclear Magnetic Resonance (NMR) Spectroscopy.
We would like you to continue your notebook to record your independent study.
In it you should record;

Explanatory notes regarding each of the above topics.

Any articles in the news or in journals such as; New Scientist, Scientific American
and Chemistry Review, that relate to the above topics.

A list of useful websites you have found and use.

The A2 Chemistry pages on the RGS infonet contain context studies written by the exam
board for each topic. They are an ideal place to start your independent study.
You will continue to be graded on Independent study throughout the year and your
notebook will be assessed by your teacher.
We will be looking for evidence of interest, knowledge and reading around these areas of
Chemistry.

-1-

Independent Study Optical Isomerism


Research the following in your scrapbook.
Optical isomerism Chirality.
Enantiomers.
Issues with chirality in drug design.
Stereospecific drugs - Thalidomide.
Remember to record;

Explanatory notes regarding each of the above topics.

Any articles in the news or in journals such as; New Scientist, Scientific American
and Chemistry Review, that relate to the above topics.

A list of useful websites you have found and use.

-2-

Isomerism
Total /35

Chemistry for A2 Chapter 6 pg 79-85

1. Define: (a) Isomerism

(b) Structural isomerism

(c) Stereoisomerism

[3]

2. Explain clearly, but in words only, how (a) geometric and (b) optical isomerism occur.[2]
3. Use diagrams to clearly explain how (a) geometric and (b) optical isomerism occur.

[4]

4. Discuss the various types of isomerism using the following as examples. In each case state
the form(s) of isomerism present and draw structures of all possible isomers:
(a) C2H6O
[3]
(b) C2H2Cl2
[5]
(c) (CH3)(CH3CH2)(H)SiCl
[3]
5. (a) Why do enantiomers have identical physical properties?
(b) How can one distinguish between two enantiomers?
(c) Draw and give the name of the smallest alkane that exhibits optical isomerism.
6. Look at the sequence below.

[2]
[2]
[2]

OH

C
H3C

CN

CH3

Ethanal (A)

CN
H

(B)

.
OH
C
CH3

OH

Hydrolysis

CN

CH3

COOH
H

Latic Acid

(B)
.

(a) Draw a diagram of ethanal (A) which shows the 3D shape about the C=O bond. [1]
(b) Draw an isomer of (A)
[1]
(c) Draw both enantiomers of B.
[2]
(d) Hydrolysis of B results in a 50:50 mixture of the two enantiomers of lactic acid.
What name is given to such mixtures?
[1]
(e) From a stereochemical point of view, how does the natural synthesis of lactic acid in
muscles differ?
[1]
7. Explain why it is very important in drug research to account for chirality in compounds
having potential therapeutic activities?
[3]

-3-

Carbonyl Chemistry
Total /62

Chemistry for A2 Chapter 7 pg 86-95

1) Use systematic nomenclature to name the following carbonyl compounds:


a) HCHO
b) CH3COCH2CH3
c)
d)
e)
O

2) Draw the full structural and skeletal formulae of the following compounds:
a) butanal
b) pentan-2-one
c) 3-methylbutan-2-one

[5]

[6]

3) Which of the following alcohols can be oxidised to an aldehyde or a ketone?


In each case, state which type of carbonyl compound would be formed and draw its skeletal
formula.
a) CH3CH2CH(OH)CH(CH3)CH3
b) CH3C(CH3)2CH2OH
c) CH3CH2CH(CH3)CH(OH)CH3
[3]
4) Use the [O] notation to write balanced equations for the oxidations in 3a), 3b) and 3c). [6]
5) The following carbonyl compounds can be reduced to alcohols. In each case draw the
structural formula of the alcohol formed and state whether it is a primary or secondary alcohol.
a) CH3-CH2-CH2-CHO
b) CH3-CO-CH2-CH3
c) CH3-C(CH3)2-CO-CH3
[3]
d) Name the reagent and conditions needed to reduce the carbonyl groups in a) to c) to
alcohols.
[2]
6) Aldehydes and ketones undergo nucleophilic addition reactions with hydrogen cyanide in the
presence of alkali. Draw the structural formula for the products (include any isomers) of the
reaction between HCN and each of the following compounds.
a) CH3-CH2-CHO
[3]
b) CH3-CH2-CO-CH3
[3]
c) Using the compound in part a) as an example explain how the reaction is a nucleophilic
addition.
[1]

-4-

7) This question is about the 'Lily of the Valley' molecule used in perfumery:
CHO
H2C

CH

H2C

CH2
CH

HO

CH2

H3C

CH3

a) Suggest why 'Lily' is dissolved in propanol rather than water when sold as a perfume.
b) Classify the two functional groups present in 'Lily of the Valley'.
c) Draw the structure of the product formed when 'Lily' reacts with:
(i) warm acidified potassium dichromate
(ii) warm acidified potassium cyanide
(iii) lithium aluminium hydride in dry ether
d) Give the observation (from what, to what) when 'Lily' is reacted with:
(i) aqueous silver nitrate and excess ammonia
(ii) Fehling's or Benedicts solution
(iii)
acidified 2,4-dinitrophenolhydrazine
[2]
(iv)acidified potassium dichromate

[3]
[2]
[2]
[2]
[2]
[2]
[2]
[2]

8) Cinnamaldehyde is present in the spice cinnamon. It is used as a flavouring in biscuits, cakes


and mulled wine. The structure of cinnamaldehyde is :.

H
C
O

a) A sample of cinnamadehyde was refluxed with dilute sulphuric acid and potassium
dichromate (VI). Draw a displayed formula to show the structure of the product.

[2]

b) 2,4 Dinitrophenyl hydrazine is used as the test to show the presence of the carbonyl group in
cinnamaldehyde. Draw the structure of the organic compound formed from the test and give the
observations that you would expect.
[2]
c) Give the name and formula of the reagent which will reduce cinnamaldehyde to cinnamyl
alcohol.
[2]
OH

d) Describe a chemical test to show that cinnamaldehyde is an aldehyde and not a ketone.
Give the observations expected.
[3]

-5-

Carboxylic Acids
Total / 73

Chemistry for A2 Chapter 8 pg 96-100

1. Explain the following:


(a) Butanoic acid has a higher boiling point than butan-1-ol.
[2]
(b) Ethanoic acid is more acidic than ethanol.
[2]
(c) Carboxylic acids of short hydrocarbon chain are soluble in water but the solubility in
water rapidly decreases with increased chain length.
[2]
2. Write balanced symbol equations for the following reactions:
(a) propanoic acid + pentan-1-ol
(b) butanoic acid + phosphorous pentachloride
(c) methanoic acid + sodium hydrogen carbonate
(d) propanoic acid + lithium aluminium hydride

[3]
[3]
[3]
[3]

3. Give the reagents and conditions required for the following transformations:
a)
H

OH
O

b)

OH
OH

c)

O
C
N

d)

OH

OH

e)

Cl

CH3CH2CO2CH2CH2CH3

CH3CH2CO2H

f)

CH3OH
H

OH

[12]

4. Acid chorides can be made using either PCl5 or SCl2O. Explain which method is best.

-6-

[2]

5. Describe how you would purify an impure sample of solid octanoic acid by recystallisation. [5]
6. Consider the following reaction scheme:
H

Step 1

Step 2

OH

O
C
OH

a) Identify the intermediate B. (Hint B is made from the aldehyde A).


[2]
b) Give the reagents and essential reaction conditions required for:
i)
step 1
ii)
step 2
[4]
c) Name the final product C.
[1]
d) Name and draw the reaction mechanism that takes place in step 1.
[4]
e) The final product C is chiral. Label the chiral atom with an asterisk *.
[1]
f) Explain why the final product doesnt rotate plane polarised light, even though it is chiral.[2]
7. Citric acid is a natural carboxylic acid present in citrus fruits.
It is used as a flavouring and a food additive and is the acid component of many soft drinks.
O

OH

HO

OH
O

OH

a)
Write down the molecular formula for citric acid.
[1]
b) i) How would you show that citric acid was an acid?
[1]
ii) How would you show that citric acid was a weak acid?
[1]
c) Draw the skeletal formulae of the organic product formed when citric acid is treated
with an excess of the following reagents:
i)
aqueous sodium hydroxide solution.
ii)
phosphorus pentachloride.
iii)
ethanol and a trace of concentrated sulfuric acid.
iv)
lithium tetrahydridoaluminate(III).
[8]
d) Describe how you would determine the exact citric acid content in fruit, assuming that the only
acid present is citric acid.
[3]
e) In a typical experiment to find the citric acid content in a sample of fruit it was found that 25cm3
of a fruit solution reacted with exactly 14.3 cm3 of 0.01M sodium hydroxide solution. Calculate
the concentration of citric acid in the sample of fruit tested.
[3]
f) Many effervescent tablets (such as Alka-Seltzer) contain citric acid.
i) Explain why there is fizzing when Alka-Seltzer is put in water, given that the tablets also contain
sodium hydrogencarbonate (NaHCO3) (in addition to the painkiller aspirin).
[1]
ii) Write a balanced equation for the reaction that takes place.
[2]
iii) Why is water necessary for the reaction to start?
[2]

-7-

-8-

Independent Study
Reaction Summaries and Biodiesel
1)

Make a summary flow diagrams for the reactions of;


Aldehydes
Ketones
and Carboxylic Acids.
Remember to record;

2)

Reaction conditions and reagents.

Any mechanisms that you need to know.

Research the following in your scrapbook.


The formation of Biodiesel.
The greenness and carbon footprint of Biodiesel.
Remember to record the sources you have found and used.

-9-

Esters and Carboxylic Acid Derivatives


Total / 70

Chemistry for A2 Chapter 8 pg 101-108

1. Esters have characteristic floral or fruity smells. Two examples are given below;

B
O

Fragrance = Pears

Fragrance = Apples

a) Give the skeletal formulae and names of the carboxylic acid and alcohol required to make;
i) Ester A.
ii) Ester B.
[4]
b) Draw a labelled diagram of the apparatus that might be used to prepare one of the esters on a
small scale in the lab.
[3]
c) Since esterifications are equilibria reactions, what is the practical way of pulling the
equilibrium to the right hand side to increase the yield of the ester?
[2]
d) Describe two factors that would need to be considered if the technique to make the esters
needed to be scaled up to be made on a larger scale.
[2]
e) What is the relationship between the two esters A and B?
[1]
f) Apart form their use in food flavourings, give one other use of esters.
[1]
g) Give reagents and conditions used to make propylpentanoate.
[2]
h) Give the structure of 2,2-dimethylpropylmethanoate.
[1]
i) Glycerol (propan-1,2,3-triol) is a by-product in soap manufacture.
Explain why and include a balanced equation for the formation of soap.
[4]
2. Write balanced symbol equations for the following reactions:
(a) ethyl ethanoate + sodium hydroxide (heated under reflux)
(b) propanoic acid + phosphorous(V) chloride
(c) butanoyl chloride + concentrated ammonia
(d) methanoic acid + ethanol
(e) propyl ethanoate + hydrochloric acid (under reflux)

[3]
[3]
[3]
[3]
[3]

3. Positive Tollens and Fehlings tests result in the salts of carboxylic acids as by-products.
a) What type of compound do these two reagents test for?
[1]
b) What is the observation with Tollens reagent?
[1]
c) What sort of chemical change occurs to the organic sample when the test is positive?[1]
d) Why is the salt if the carboxylic acid formed?
[1]

-10-

4. Describe how you could use simple chemical tests to distinguish between the six unlabeled
bottles following compounds. Your plan must be logical and involve a minimal number of tests.
A

H2
C
H3C

H2
C
OH

H3C

H2
C

O
C

H3C

OC2H5

H2
C

O
H3C

C
H3C

CH3

O
C

H2
C

O
C

H3C

OH

O
C
Cl

[12]

5. Methyl benzoate (C6H5CO2CH3) can be prepared from methanol and benzoic acid as shown in the
equilibrium equation:
C6H5CO2H

+ CH3OH

C6H5CO2CH3 + H2O

An incomplete experimental procedure for the preparation of methyl benzoate is outlined below:

a)
b)
c)
d)
e)
f)
g)
h)
i)
j)
k)
l)

Put 10.0 g of benzoic acid and 20 cm3 of methanol into a 100 cm3 round-bottomed flask.
Add 2 cm3 of concentrated sulfuric acid and then fit a reflux condenser.
Heat the mixture under reflux, with an electrical heater, for 45 min.
After allowing the reaction vessel to cool to room temperature, pour the reaction mixture into a
separating funnel containing 40 cm3 of cold water.
Rinse the reaction flask with 20 cm3 hydrocarbon solvent and add the solvent to the contents of the
separating funnel.
After shaking and leaving to settle to form two layers, the aqueous layer is run off and the
hydrocarbon layer washed successively with water and sodium carbonate solution.
The hydrocarbon layer is then dried over a suitable compound and then filtered.
What is the purpose of the concentrated sulfuric acid in point 2?
Draw a labelled diagram of the apparatus used for heating the reaction mixture to reflux.
Why is the reaction mixture not simply heated in a beaker?
Why is an electrical heater used to heat the mixture, rather than a Bunsen?
After refluxing, why is the reaction mixture washed with water in the separating funnel (point 4)?
Why is the reaction flask rinsed with hydrocarbon solvent (point 5) and not water?
Why is the hydrocarbon layer washed with sodium carbonate in the separating funnel (point 7)?
Name a suitable compound for drying the hydrocarbon layer (point 7).
Having filtered the hydrocarbon layer to remove the drying agent, describe how you could obtain a
pure sample of methyl benzoate, given that it is a liquid at room temperature.
How might you test and verify the purity of the sample of methyl benzoate that you obtained?

[1]
[3]
[1]
[1]
[1]
[1]
[1]
[1]
[2]
[2]

4.6 g of pure methyl benzoate is produced in the reaction. Given that the methanol is present in excess
at the start of the reaction, calculate the percentage yield of the reaction.
[3]
Calculate and comment on the atom economy of the reaction.
[2]

-11-

IR and Mass Spec


Chemistry for A2 Chapter 9 pg 116-120

Total / 41

Answer Qu 1-4 on the activity on Jasmine on page 119 and 120 of Chemistry for A2.

[11]

1) a) In infrared spectroscopy, what is the region below 1500cm-1 called?


[1]
b) Explain how this region could be used to show that an unknown ketone was cyclohexanone
and not hexan-3-one.
[2]
c) Assign the peaks labelled in the infrared spectra below and identify the function groups
present in each compound.
[9]

III

-12-

2) The infrared and mass spectra of an unidentified organic compound Y are shown below;
Y decolourises bromine, but only in the presence of an iron catalyst.

a)
b i)
ii)

3)

Name the functional groups present in Y.


[2]
What is the RFM of compound Y?
[1]
Identify the fragments that are responsible for the mass spectrum peaks at;
m/e
122
m/e
105
m/e
77
m/e
51
[4]

The mass spectrum of methyl benzoate (C6H5COOCH3) is shown below:

a)

b)
c)

d)

What is the m/e value of;


i)
The M+, molecular (parent), ion?
ii)
The (M+1) peak?

[1]
[1]

Explain why this (M+1) peak occurs and why it is so small.


[2]
Suggest skeletal formulae for the fragments responsible for the peaks at:
i)
m/e
136
ii)
m/e
105
iii)
m/e
15
[3]
Describe two practical uses of mass spectroscopy.
[4]

-13-

NMR and Chromatography


Total / 54

Chemistry for A2 Chapter 9 pg 111-115 and 121-129

1) For each of the following compounds indicate the number of signals, and relative intensity
and multiplicity of each signal (using the n+1 rule) in its NMR spectrum.
a) CH3COCH3
b) CH3CH=CH2
c) CH2BrCHBrCH3
d) CH3CH2COOCH2CH3
[12]
2) Use the molecular formula and high resolution NMR spectra to identify the molecules below;
(Explain your answers fully).
a) C5H10O
[4]

b)

C2H4O

c)

C4H8O2

[4]

[4]

-14-

3. Quantitative analysis of compound B shows it to contain 22.2% C, 4.6% H and 73.2% Br by


mass. The mass spectrum and NMR spectrum are given below:

(a) Calculate the empirical formula of B.


[2]
(b) Explain which peak on the mass spectrum represents the molecular ion of B and write the
ions formula.
[2]
(c) Use the mass spectrum to deduce the relative molecular mass and hence give the molecular
formula of B.
[2]
(d) Determine the ratio of hydrogen atoms in each environment from the NMR data.
[1]
(e) Give the structure and hence name of B.
[4]
4 a) Briefly explain how Column chromatography is used to separate mixtures of organic
compounds.
[3]
b) What is meant by the retention time in gas chromatography and how can it be used to
identify the composition of a mixture of organic compounds?
[3]
c) Why is gas chromatography often combined with mass spectrometry?
[2]
5. Read the activity on pg 128-129 of Chemistry for A2 and answer questions 1-5.

-15-

[11]

-16-

Introductory Ideas About Benzene, C6H6


Total / 55

Chemistry for A2 Chapter 12 pg 180-188

1. Draw out all the structural isomers of C6H6 (think laterally here: anything goes as long as
carbon has four bonds and hydrogen has one).
[6]
2. For each of the following pieces of information, state the likely implication for the actual
structure of benzene:
a) all six carbon-carbon bonds are of identical length.
b) all bond angles are 120C.
[4]
3

a) The benzene molecule is said to contain delocalised -electrons.


Use a suitable diagram to show what this means.

[3]

b) Comment upon the following enthalpies of reaction;

[3]

Br

Br

CH

Br

CH

3Br2

CH

CH
Br

H = -57 kJmol-1

CH
CH

Br

Br
H2
C

H2
C
H2C

CH

H2C

CH

H2C

+ Br2

H2C

H = -95 kJmol-1

CH
C
H2

C
H2

Br
CH

Br

4. Draw and name all the isomers of formula C6H3Cl3. (Only consider compounds which
contain a benzene ring; use the hexagon notation to represent the ring on each case.) [6]
5. Draw the structural formulae of the following arenes:
a) 3-nitrochlorobenzene,
b) 1,4-dihydroxybenzene.

[2]

6. Draw the skeletal formulae of the following arenes:


a) 2,4,6-triethylmethylbenzene,
b) 1,2,5-tribromobenzene,
c) Phenylethene. (Note phenyl means a substituted benzene ring).

[3]

7. Give the name(s) and structural formula(e) of the product(s), if any, obtained when benzene
is reacted with:
a) Bromine water,
b) Bromine in the presence of an iron catalyst,
c) Hydrogen gas and a Nickel catalyst at 200oC.
d) Concentrated (fuming) sulphuric acid.
[8]
8. Read the activity on g 190-191 of Chemistry for A2.
Draw a labelled diagram of the apparatus used to chlorinate benzene and answer questions
1-6 on pg 191.
[20]

-17-

Alkenes vs Arenes
Chemistry for A2 Chapter 12 pg 185-192

Total / 60

1. Explain why:
a) both alkenes and benzenes undergo electrophilic reactions.
b) alkenes tend to undergo addition reactions.
c) arenes tend to undergo substitution reactions.

[6]

2. Draw the mechanism for the electrophilic addition reaction between propene and bromine.
[3]
3. Draw the mechanism for the electrophilic substitution reaction between methyl benzene and
bromine with an iron catalyst.
[4]
4. Consider the molecule below:

CH3
C

C
H

a) There are three different types of carbon-carbon bonds present.


List them in order of increasing bond length.

[1]

b) Draw the likely product when the molecule is reacted with:


(i)
one mole equivalent of hydrogen on nickel.
(ii)
a mixture of conc sulphuric and conc nitric acids.
(iii)
bromine water.
(iv)
itself, under pressure in the presence of a catalyst.
(v)
fuming sulphuric acid.
(vi)
propanoyl chloride and aluminium trichloride.
(vii) 2-chloropropane and aluminium trichloride.
(viii) Acidified potassium manganate(VI).

[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]

c) The molecule exhibits stereoisomerism.


(i)
What type?
(ii)
How does it arise?
(iii)
Draw the other isomer.

[2]
[2]
[2]

5. The enthalpy of combustion of ethyne (C2H2) is 1300 kJ/mol and that for benzene (C6H6)
is 3300 kJ/mol. Does this make benzene more, or less, stable than predicted?
Explain your answer.
[3]

-18-

6. Two reactions of benzene are summarised in the diagram;


H2
C
H2C

CH2

CH3CH2Cl

H2C

CH2

+ C

CH2CH3

C
H2

Benzene

a) What is the meaning of the circle in the diagram of both benzene and substance E? [2]
b) Name the substances A to E:

[5]

c) Name the type of reaction involved in the formation of A.

[1]

d) Name the type of reaction involved in the formation of E

[2]

e) Draw the mechanism for reaction involved in the formation of E from benzene.

[4]

7. TNT can be made from benzene in the three step synthesis below.
O2 N

Step 1

NO2

Step 3

Step 2

TNT
NO2

NO2

a) Suggest suitable reagents and conditions for Step 1.

[2]

b) Suggest suitable reagents and conditions for Step 2.

[3]

c) Explain why careful temperature control is needed in Step 2.

[2]

-19-

Phenols
Total / 50

Chemistry for A2 Chapter 12 pg 193-196

1. Look at the molecules below:


Thymol (oil of thyme)
Eugenol (oil of cloves)
OH

OH

CH3

CH3

CH
CH3

H3C

H2 C
CH
CH2

a) In general terms, suggest why these compounds have not entirely dissimilar smells.
b) Explain why Thymol and Eugenol are slightly soluble in water.
c) Draw the structure of the product formed when Thymol reacts with:
(i)
sodium metal.
(ii)
sodium hydroxide.
d) Draw a possible product when Eugenol is reacted with:
(i)
a mixture of conc sulphuric and conc nitric acids.
(ii)
excess liquid bromine (in the absence of bright light).

[2]
[2]
[2]
[2]
[2]
[3]

2. When phenol is reacted with dilute nitric acid, a mixture of 2- and 2, 4-dinitrophenol is formed.
a) Explain why 2- and 2,4-dinitrophenol are formed.
[2]
b) Suggest why the nitration of phenol requires miler conditions than the nitration of benzene.
[3]
c) Draw and name the mechanism for the conversion of phenol into 4-nitrophenol.
[4]

3. Read the activity on pg 194-195 of Chemistry for A2.


Draw the
equations
in
the2160]
cumene
process
answer
questions
onAr
pg
195.
300
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2430
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1620
61
25710
140
I1228
760
5240
6176
5708
6500
1696
1228
2020
80
1890
20
2430]
1350]
2140
2410]
2140]
1600]
1330]
2160]
1620]
1350]
1380]
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12
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4720
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8 I 760
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[18] 6
4. An alternative two step method of making phenol is shown below.
o Benzene is heated under reflux with concentrated sulphuric acid for several hours.
o

The product is then heated with molten sodium hydroxide, phenol is produced.
OH

SO 3H

+NaOH

a) Discuss why the cumene process is the preferred manufacturing process for the production of
phenol.
[7]
b) Predict all the possible final products when methylbenzene is heated under reflux with conc
sulphuric acid and then heated with molten sodium hydroxide.
[3]

-20-

Amines
Total / 60

A2 Chemistry Chapter 13 pg 198-203

1) Draw the full structural and skeletal formulae of the following compounds:
a) pentylamine b) 2-methylbutyl methylamine
c) dimethyl ethylamine
2) Classify the three amines above as either tertiary, secondary or primary

[6]

[3]

3) Explain why tertiary amines are not very soluble in water and are limited in their reactivity.
[3]
4) Give an explanation of the relative basicities of ammonia, ethylamine and phenylamine. [3]
5) . Explain the following:
(a) Ethylamine has a higher boiling point than ethane.
[2]
(b) Propylamine has a lower boiling point than propan-1-ol.
[2]
(c) Amines of short hydrocarbon chain are soluble in water but the solubility in water rapidly
decreases with increased chain length.
[2]
6) Write balanced equations for the following reactions:
(a)
Cl

+ concentrated NH3

(b)
(c)

NH2

Heat
(Sealed tube)

[2]

HC l

[2]

CH3NH2

[2]

O
C
Cl

7) a) Describe what happens when ethylamine is added to copper(II) ions in CuSO4.


b) What is observed during the reaction in part a).
8)

[2]
[1]

Adrenaline has the structure shown below.

OH
CH

CH2

H
N

CH3

HO

a)
b)
c)
d)
e)
9)

OH

What is the molecular formula of adrenaline.


Name the functional groups in adrenaline.
Identify the chiral carbon in adrenaline and hence draw both optical isomers.
How can the two optical isomers be differentiated between in the lab?
Explain why only one isomer is biochemically active.
Read the activity on Paracetamol pg 202 of Chemistry for A2.
-21-

[1]
[3]
[3]
[1]
[2]

Draw the skeletal formulae of aspirin and paracetamol and answer questions 1-6.

-22-

[20]

Amides, Azo Dyes and Aromatic amines


Chemistry for A2 Chapter 13 pg 199-205

Total / 45

1. . Explain the following:


a) Ethanamide is soluble in water. Draw a diagram to explain your answer.
b) Hexanamide is insoluble in water.

[2]
[2]

2. Explain why amides are unreactive.

[2]

3. Sunset Yellow is used as a food colourant (E110) in sweets, orange squash and jams. It is
produced by the following reactions:
HO

Na O3S

NH2

mix with

Na O3S

NaO3S

c)
4.

SO3

e)
f)
g)

Na

What type of compound is Sunset Yellow?


[1]
What reagent must compound B be treated with and under what conditions in order to
make compound C, before C is added to D to produce Sunset Yellow?
[3]
The sodium sulphonate (SO3-Na+) groups have little effect on the colour of Sunset Yellow.
Suggest a reason why these groups are needed in the molecule.
[2]
Phenylazobenzene has the structure shown below.
N

a)
b)
c)
d)

Sunset Yellow

a)
b)

OH

What is the molecular formula of Phenylazobenzene?


Phenylazobenzene exhibits stereoisomerism. Explain why?
Draw the cis isomer of Phenylazobenzene.
Phenylazobenzene is an orange dye.
What feature of the molecule makes it absorb certain frequencies of visible light?

[1]
[3]
[2]
[2]

Suggest why this dye interacts better with non-ionic fibres such as polyester rather than
ionic fibres such as acrylic. Hint: intermolecular forces?
[2]
The wash-fastness of dyed fabrics can be likened to a tug-of-war between fibre and water.
Explain this statement using phenylazobenzene as the example.
[3]
Give details of how you would synthesise this azo-dye in the lab from benzene. [5]
Mechanisms are not required but you should give any particular experimental conditions.

-23-

5. An active ingredient in many sunscreen creams is 4-aminobenzoic acid.


C O O H

N H

It can be prepared as described below.


o

To 15 g of 4-nitrobenzoic acid, in a flask fitted with a reflux condenser, add 35 g of


powdered tin and 75 cm3 of concentrated hydrochloric acid.

Heat the mixture until the reaction commences, remove the flame and shake the flask
gently from time to time. After about 20 minutes cool and decant the liquid into a
beaker, wash the residual tin with 15 cm3 of water and add the washings to the beaker.

Add concentrated ammonia solution until the solution is just alkaline, filter off the
precipitate of hydrated tin oxide, wash it well with water and add these washings to the
filtrate.

Acidify the filtrate with concentrated ethanoic acid and evaporate on a water bath until
crystals commence to separate.

Cool in ice, filter the crystals at the pump and dry in a steam oven.

The yield of 4-aminobenzoic acid, melting temperature 192 C, is 12 g.


(After A Textbook of Practical Organic Chemistry by A. E. Vogel)

(a) Suggest reasons for each of the following:


(i) the use of a mixture of tin and hydrochloric acid;
(1)
(ii) heating the mixture but then taking the flame away;
(2)
(iii) the use of a reflux condenser;
(1)
(iv) adding ammonia;
(1)
(v) adding ethanoic acid.
(2)
(b) Calculate the percentage yield of 4-aminobenzoic acid from 4-nitrobenzoic acid, (NO 2)C6H4COOH.
(3)
(c) 4-aminobenzoic acid can be converted into benzocaine, a local anaesthetic which is used to relieve
the pain of sunburn.
O

O C H 2C H

N H

(i) Suggest reagents and conditions for carrying out this conversion.
(2)
(ii) Name the type of reaction involved in this step.
(1)
(d) A better local anaesthetic than benzocaine is novocaine,

-24-

H
O

O
C

CH

C H

C H 2C H

C H 2C H

C l
N H

which can be injected into tissues.


State with a reason what feature of novocaine, absent in benzocaine, might be responsible for its
solubility in non-fatty tissue.
(2)
(Total 15 marks)

-25-

Polymers and Amino Acids


Total / 70

Chemistry for A2 Chapter 14 pg 207-221

1 a) Explain the differences between addition and condensation polymerisation.


b) Draw the structure of polypropene making the repeat unit clear.
c) Draw the mechanism for the formation of polypropene from propene.
2.

[4]
[2]
[4]

Read the activity on Covering the O2 pg 218 of Chemistry for A2.


Answer questions 1-8.

3.

[15]

Terylene is the UK trademark for the polyester formed between ethane-1,2-diol and terephthalic acid.
O

O
HO

HO

CH2

CH2

OH

OH

ethane-1,2-diol

terephthalic acid

a) Use the structures of the monomers above to draw the structure of the polyester formed by the
elimination of three water molecules.
[4]
b) Suggest why polyesters such as this have a high tensile strength and give a consequential
use for such polymers.
[4]
4.

Read the activity on Monitoring and synthesising polyamides pg 222 of Chemistry for A2.
Answer questions 1 and 3.
[16]

5 a) Draw the structure of the repeat unit of nylon 6,6 (formed from 1,6-diaminohexane
and hexan-1,6-dioic acid).
[4]
b) Suggest why this sort of polyamide lends itself, like Terylene, to being drawn into thin fibres. [2]
c) Nylon has a greater tensile strength than polyesters, however. Explain what further intermolecular
force is responsible for this with a suitable diagram and give a consequential use of nylon. [4]
d)
Explain why polyester fibres are better at absorbing sweat and water than polyamide fibres.[3]
6.

Three amino acids are shown below.


a)
b)
c)
d)
e)
f)
g)
h)
i)

Explain why glycine is the only amino acid that isnt chiral.
Draw the two enantiomeric forms of valine
Explain why L-serine is over 100 times cheaper than D- serine.
Draw the structural formula of the dipeptide Val-Ser
[2]
Draw the structural formula of another dipeptide formed between Val and Ser.
Draw the structure of glycine in an acidic solution.
Draw the structure of glycine in an alkaline solution.
Draw the zwitterionic form of glycine.
Explain why amino acids are solids at room temperature.

-26-

[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]

Synthetic Reaction Schemes


Total / 50

Chemistry for A2 Chapter 15 pg 232-233

1. Read the activity on Converting one functional group to another pg 233 of Chemistry for A2.
Answer questions 1 and 2.
[15]
2. a) Use the information in the scheme below to deduce the structures of A to I.
b) Identify the two compounds that have chiral carbons.

A
C
I

[2]

is C5H10O and has an absorption at 1700 cm 1 in the infra red.


has pH 3 in aqueous solution.
does not react with acidified potassium dichromate.

conc sulphuric
acid, 180oC

C2H5
C

CH2

H3C

conc sulphuric
acid, 180oC
dichromate/acid

I
A

[Ag(NH3)2]+

Ag

dichromate/acid
NaBH4 (aq)

HCN

reflux with aq acid


NaOH

G
dichromate/acid

-27-

[18]

3. Use the information in the scheme below to answer the questions that follow.

SCHEME B
CH2CH3

H
H

CH2CH3

(b)

C
C

(c)

N
N

(a)
(d)

a)

Give the reagents and an explanatory mechanism for step a).

C6H5

n
[4]

b) Write equations to show how this azo-dye in step b) could be formed from ethylbenzene
and nitrobenzene.
[3]
c i) What sort of reaction is Step c?

[1]

ii) Explain carefully how aqueous bromine reacts with phenylethene.


d i) Draw the structural formula of poly(phenylethene).

[3]
[2]

ii) Give two reasons why addition polymers like poly(phenylethene) are difficult to dispose of.
[2]

-28-

Organic Synthesis
Total / 57

Chemistry for A2 Chapter 15 pg 225-244

1. Design synthetic routes for the following conversions, giving the reagents and conditions
needed for each step.
H2
C

H2
C

Cl

a) H3C

H3C

C
H2

O
C
H

OH

b)

CH
H3C

HO

CH3

H3C

C
CH3

HO

Br

CN

H3C

CH3

O
C

c)

CH
H3C

CH

CH3
H3C

CH3
CH3
H2C
C

d)

HO3S

[16]
2.

Read the activity on Thalidomide pg 241 of Chemistry for A2.


Answer questions 1 to 9 on pg 241-242.
For question 3 just draw the skeletal formula of thalidomide rather than using a model kit.
[25]

-29-

3.

Adrenalin is a hormone which raises blood pressure, increases the depth of breathing and
delays fatigue in muscles, thus allowing people to show great strength under stress.
Benzedrine is a pharmaceutical which stimulates the central nervous system in a
similar manner to adrenalin.
H O
C H

C H (C H 3)

N H

H O

B e n z e d rin e

H
C H (O H )

CH

C H

A d re n a lin

a i)

Draw the skeletal formula of Benzedrine and mark with a (*) any asymmetric
carbon atom that causes chirality.
ii) Draw the skeletal formulae of the two enantiomeric forms of Benzedrine.

[2]
[2]

b)

[2]

Suggest why adrenalin is more soluble in water than is benzedrine.

c) Give the structural formulae of the organic products obtained when benzedrine reacts
with:
i) an aqueous acid such as dilute hydrochloric acid;
ii) ethanoyl chloride in the absence of a catalyst;
iii) excess ethanoyl chloride in the presence of the catalyst anhydrous AlCl3.
[4]
d)

Comment on any issues that may arise if a drug company wanted to scale up a
synthetic scheme to make Benzedrine form benzene by the tonne.

Challenge of the week Youve gotta be good to do this one!


e) Design a synthetic pathway to make Benzedrine from benzene.
Include all the reagents and conditions needed. (Hint it may take over 5 steps!).

-30-

[5]

[10]

More Organic Synthesis


Total / 42

A2 Chemistry Chapter 15 pg 299-305

1.

The reaction sequence below shows a method that could be used to convert benzene into
benzoic acid.

a i) Name the reagent and catalyst that could be used to convert benzene into A in Step 1. [2]
ii) Name the type of reaction in Step 1 and its mechanism.
[2]
iii) Write an equation to show how the catalyst interacts with the reagent in Step 1 and
explain how this helps the reaction to take place.
[2]
b i) B has several isomers.
Draw the structural formula of ONE of these isomers, and give its systematic name.
[2]
ii) Name the reagent and catalyst you would use to try to make your isomer from A.
[2]
c i) Name the type and mechanism of the reaction in Step 3.
[2]
ii) By considering halogenoalkane B, suggest whether the reaction in Step 3 is first or second
order. Justify your answer. Draw the mechanism that you suggest.
[2]
d) What type of reaction is Step 4?
[1]
e) Suggest TWO reactions in which you would observe the same results when carried out
with either compound C or benzoic acid.
Describe what you would see in each of the two reactions.
[4]
2.

Vanillin, the main ingredient of vanilla essence, is one of the commonest flavouring
ingredients found in foods. Synthetic vanillin, which is identical to natural vanillin, can be
manufactured from methoxybenzene. One synthetic route is shown below:
SO 3H

O C H

O H

O C H

O H

O C H

O C H

CH O
m e th o x y b e n z e n e

2 -m e th o x y b e n z e n e
s u lp h o n ic a c id

2 -m e th o x y p h e n o l

v a n illin

a i) Name the reagent which converts methoxybenzene to 2-methoxybenzene sulphonic acid.


ii) Name the type of reaction which occurs and its mechanism.

b)

[3]

After the final stage, in which 2-methoxyphenol is converted to vanillin, the impure
product can be purified by recrystallisation. In this process the solid is dissolved in the
minimum volume of hot water. The mixture is then filtered whilst still hot.
The filtrate is cooled in an ice bath to produce crystals of vanillin.
These can be removed by filtration and dried.
i) Why is the minimum volume of hot water used?
[1]
ii) The impure vanillin may contain soluble and insoluble impurities.
Describe how each of these is removed during recrystallisation.
[2]
iii) How would you check the purity of the vanillin after recrystallisation, other than by using
an infrared spectrometer.
[2]

-31-

c)

In order to establish whether or not vanillin had been formed, two infrared spectra were
obtained: a sample of pure 2-methoxyphenol and a sample of the product.
Study the spectra and data below.
In fr a re d S p e c tr u m o f 2 -M e th o x y p h e n o l
100
80
T ra n s m itta n c e
/%

60
40
20
3000

2000
W avenum ber/cm

1000
1

In fr a re d S p e c tr u m o f P ro d u c t
100
T ra n s m itta n c e
/%

80
60
40
3000

2000
W avenum ber/cm

1000
1

Comment as to whether any vanillin is likely to have been formed during the process.
Support your answer with relevant evidence.
[2]
3.

Thiols are organic sulphur compounds that undergo similar reactions to alcohols.
Phosphines are organic nitrogen compounds that undergo similar reactions to amines.
Design synthetic routes for the following conversions, giving the reagents and conditions needed
for each step.
i)

H
P

OH

ii)

[3]
S

Br

iii)

[5]

H
P

SH

-32-

[5]