RECOGNISING ACHIEVEMENT

OXFORD CAMBRIDGE AND RSA EXAMINATIONS Advanced GCE

CHEMISTRY (SALTERS) Chemistry by Design

Tuesday 28 JUNE 2005

2854

Morning

2 hours

Candidates answer on the question paper. Additional materials:

Data Sheet for Chemistry (Salters) Scientific calculator

Candidate

Centre Number Number

,_____ ____.I I I I I II I I I I

Candidate Name

TIME 2 hours

INSTRUCTIONS TO CANDIDATES

• Write your name in the space above.

• Write your Centre number and Candidate number in the boxes above.

• Answer all the questions.

• Write your answers in the spaces provided on the question paper.

• Read each question carefully and make sure you know what you have to do before starting your answer.

INFORMATION FOR CANDIDATES

• The number of marks is given in brackets [ ] at the end of each question or part question.

• You will be awarded marks for the quality of written communication

where this is indicated in the question.

• You may use a scientific calculator.

• You may use the Data Sheet for Chemistry (Salters).

• You are advised to show all the steps in any calculations.

FOR EXAMINER'S USE
Qu. Max. Mark
1 16
2 22
3 38
4 20
5 24
TOTAL 120 This question paper consists of 15 printed pages and 1 " hi 389.

SP (CW/KS) 875371/5 ©OCR 2005 [Y/100/3433)

Registered Charity Number: 1066969

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2

Answer all the questions.

1 Ammonium ions and ammonia are formed in the soil by several processes. These include fixation of atmospheric nitrogen in the root nodules of certain plants and mineralisation of organic nitrogen.

(a) The half-equation for the fixation of nitrogen in root nodules is shown below.

equation 1.1

(i) Give the oxidation states of nitrogen in

N2 .

NH4+ [2]

(ii) The half-reaction in equation 1.1 is called a reduction. Explain why .

............................................................................................................................... [1]

(iii) Draw a dot-cross diagram for the ammonium ion, showing the outer electron shells only.

(b) Urea is an organic nitrogen-containing compound that is found in the soil. Its formula is shown below.

urea

H H-N~A C-O

g

H-N B

\

H

(i) Give the values of the bond angles A and B in the urea molecule.

A .

B .

(ii) Urea is slowly hydrolysed in the soil. Suggest an equation for this hydrolysis.

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[2]

For Examiner's Use

[2]

[2]

3

(c) The rate equation for the reaction in (b) (ii) can be represented as shown below.

(i) What name is given to the term k in a rate equation?

............................................................................................................................... [1]

(ii) What effect does raising the temperature have on the value of k?

............................................................................................................................... [1]

(d) Nitrogen forms several oxides. One of these, N02, fits the acid-base trend of oxides across a period in the Periodic Table.

What can you predict about the acid-base character of N02 from the position of nitrogen in the Periodic Table? Explain your prediction .

...................................................................................................................................... [2]

(e) Another organic compound found in soil is 3-hydroxybenzoic acid.

O-H

3-hydroxybenzoic acid

(i) What name is given to a hydroxyl group attached to a benzene ring?

............................................................................................................................... [1]

(ii) Give the structural formula of the salt formed when 3-hydroxybenzoic acid reacts with sodium hydroxide solution. Show ionic charges.

[Total: 16]

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[2]

For Examiner's Use

4

2

Antifreeze solution is added to car radiators in winter to stop the water freezing and expanding, which can crack the cylinder block. Early antifreeze solutions contained methanol, CH30H, which tended to evaporate. Then ethane-1,2-diol, HO-CH2-CH2-QH, was used in antifreeze solutions as it has a higher boiling point. Both are very poisonous, however.

(a) Theory shows that 8 moles of solute are needed to lower the freezing point of 1 kg of water to -15 "C.

Compare the masses of methanol and ethane-1,2-diol which need to be dissolved in 1 kg of water to lower the freezing point to -15 "O,

Ar: C, 12; 0, 16; H, 1.0

(b) Water expands when it freezes because ice has an 'open' structure in which the molecules are held together by hydrogen bonds.

Draw a diagram to show three water molecules held in this open structure. Show partial charges.

(c) Methanol reacts in the eye to form methanal which causes blindness.

(i) Draw a full structural formula for methanal.

(ii) Classify the type of reaction by which methanol is converted to methanal .

................ : [1]

(iii) Use the Data Sheet to write down the formula of a reagent that would convert methanal back to methanol in the laboratory .

............................................................................................................................... [1]

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[3]

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[4]

[1 ]

5

(d) Ethane-1,2-diol is poisonous because it is oxidised in the body to ethanedioic acid, C2H204. Draw the full structural formula of ethanedioic acid.

(e) Ethanedioic acid removes vital calcium ions from solution in the bloodstream. It reacts to precipitate out calcium ethanedioate.

Ksp for calcium ethanedioate, CaC204, is 2.3 x 10-9 mol2 dm-6 at 298 K. (i) Write an expression for Ksp for calcium ethanedioate.

(ii) Calculate the concentration of calcium ions in a saturated solution of calcium ethanedioate.

calcium ion concentration = mol dm-3 [3]

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[2]

[2]

6

(f) Some data for ethane, ethane-1 ,2-diol and ethanedioic acid are shown in the table below.

compound melting point/DC boiling point/DC
ethane -183 -89
ethane-1,2-diol -12 198
ethanedioic acid 157 Use your understanding of structure and bonding to explain the states in which the three compounds exist at room temperature .

...................................................................................................................................... [5]

[Total: 22]

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3

The substance GHB was originally designed for use in sleeping pills. However, other drugrelated uses were found for the substance and its sale was restricted in 2003. GHB stands for gamma-hydroxybutyric acid, an old name for the structure shown below.

H H H

I I I ~O

H-O-C-C-C-C GHB

I I I "O-H

H H H

(a) (i) Name the two functional groups in GHB .

............................................................................................................................... [2]

(ii) Give the systematic name for GHB .

............................................................................................................................... [2]

(b) A substance known as GBl is converted into GHB in the body. Its structure is shown below.

H H

I I

C-C

I/~ ~\ GBl

C C=O

~~O/

(i) Name the functional group in GBL.

............................................................................................................................... [1]

(ii) Name the type of reaction by which GBl forms GHB in the body .

............................................................................................................................... [1]

(c) A molecule that has the same effect on the body as GHB is called 'GHB alcohol'. Its structure is shown below, together with the structure of GHB.

H H H

I I I ~O

H-O-C-C-C-C

I I I "O-H

H H H

H H H H

I I I I

H-O-C-C-C-C-O-H

I I I I

H H H H

GHB

GHBalcohol

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(i) On the molecule of GHB above, draw a ring round the largest part of the molecule

that could be the pharmacophore. [1]

(ii) Suggest why both of these molecules are able to bind to the same receptor site in the body. Name the intermolecular forces involved .

............................................................................................................................... [3]

(iii) Name a modern technique that allows chemists to view the possible ways in which a molecule can bind on to a receptor site .

............................................................................................................................... [1]

(iv) Give the reagents and conditions for making an organic acid from an alcohol in the laboratory .

............................................................................................................................... [3]

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For Examiner's Use

(d) In this question, two marks are available for the quality of the use and organisation of scientific terms.

The infrared spectrum of one of the compounds described in this question is shown below.

transmittance / %

100

...... / ~ /: ~~
~
~
-
- 80

60

40

20

4000 3500 3000 2500 2000 1500 1 000 500 wavenumber I crrr"

Use the Data Sheet to identify the substance, giving your reasoning. Then describe the proton n.m.r. spectrum of this compound .

...................................................................................................................................... [6]

Quality of Written Communication [2]

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For Examiner's Use

(e) GHB is a weak acid. Weak acids can be represented as HA.

(i) Write an equation to show how a weak acid HA behaves when dissolved in water.

(ii) Write an expression for the acidity constant Ka of an acid HA.

(iii) A 0.10 mol dm-3 solution of GHB has a pH of 2.9.

Calculate the value of Ka for GHB and give its units.

Ka = unit [4]

(f) A mixture of GHB and its sodium salt acts as a buffer solution.

(i) In this question, one mark is available for the quality of spelling, punctuation and grammar.

Explain the meaning of the term buffer solution and explain why buffer solutions are found in our bodies .

............................................................................................................................... [5]

Quality of Written Communication [1]

(ii) Calculate the pH of a buffer solution containing equal amounts of GHB and its sodium salt. If you have been unable to calculate the value of Ka for GHB in (e) (iii) above, assume that it is 1 x 10-5.

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pH = [2]

[Total: 38] [Turn over

[2]

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[2]

4 Ammonia is a very important chemical. Large quantities are produced in Britain every year.

(a) Give one reason why it is important to make ammonia .

...................................................................................................................................... [1]

When ammonia is manufactured, hydrogen is needed as part of the feedstock.

(b) Name the gas that forms the rest of the feedstock for making ammonia .

...................................................................................................................................... [1]

(e) The hydrogen feedstock is produced from methane by steam reforming as shown below.

equation 4.1

(i) Write an expression for Kp for the reaction in equation 4.1.

(ii) At the temperature of the reaction, Kp = 292 atm2.

The partial pressures of some of the gases present in an equilibrium mixture at this temperature are given in the table.

gas partial pressure I atm
CH4 5.00
H2O 5.00
H2 12.0 Calculate the partial pressure of carbon monoxide under these conditions. Give your answer to a suitable number of significant figures.

Peo = atm [3]

(d) (i) Use Le Chatelier's principle to predict the effect of decreasing the total pressure on the yield of hydrogen in equation 4.1 .

............................................................................................................................... [3]

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[2]

(ii) Suggest a reason why a pressure of around 30 atm is used for the process .

............................................................................................................................... [1]

(e) The mixture of gases from the reaction in equation 4.1 is mixed with more steam and passed over a hot iron catalyst. The carbon monoxide is converted to carbon dioxide.

(i) Write an equation for the reaction of carbon monoxide with steam.

(ii) Suggest two reasons why the carbon monoxide is not released into the atmosphere .

............................................................................................................................... [2]

(f) (i) Predict. the sign of ~S:ys for the forward reaction in equation 4.1. Explain your reasoning.

equation 4.1

............................................................................................................................... [2]

(ii) Use the entropy data given in the table below to calculate the value of ~S:YS (with the correct sign) for the forward reaction in equation 4.1.

compound S-& I J K-1 mor '
CH4(g) +186
H2O(g) +189
CO (g) +198
H2(g) +131 ~S:yS = J K-1 mor ' [3]

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[Total: 20] [Turn over

[2]

For Examiner's Use

5 The dye Disperse Yellow 7 dyes polyesters but not cotton.

HO

OH

Disperse Yellow 7

(a) How many carbon and hydrogen atoms are there in a molecule of Disperse Yellow 7?

carbon atoms .

hydrogen atoms [2]

(b) Why does a yellow substance look yellow?

...................................................................................................................................... [2]

(c) The dye molecule has delocalised electrons.

(i) Explain what is meant by the term delocalisation .

............................................................................................................................... [2]

(ii) Over which parts of the molecule does the delocalisation occur?

............................................................................................................................... [3]

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. .:1-5" I~

(iii) The answer to part (ii) describes the chromophore of the molecule.

Increasing the length of the chromophore in a dye molecule decreases the frequency of the light absorbed. Suggest an explanation for this in terms of energy levels .

............................................................................................................................... [2]

(d) (i) Suggest the reagents and conditions that might be used to substitute another CH3 group into one of the aromatic rings in Disperse Yellow 7 .

............................................................................................................................... [3]

(ii) Explain why this is described as a substitution reaction .

............................................................................................................................... [2]

(iii) Circle a word in the list below that describes the mechanism of this substitution reaction.

electrophilic

nucleophilic

radical

(e) Disperse Yellow 7 can be made by the following route.

G-N=N-o-NH, stepl~ CompoundY

step 2

Disperse Yellow 7

(i) In step 1, the amine group is reacted with cold nitrous acid. Name the type of compound that is formed (compound V) .

............................................................................................................................... [1]

(ii) In step 2, compound Y is coupled with another reagent. Draw the structure of this reagent.

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[1 ]

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[2]

.:1-6 1"5

HO

OH

Disperse Yellow 7

(f) The structure of cotton can be represented as shown below.

OH OH CH20H OH OH

-1-1 cotton I fibre I 1:--

-I--IHI--I--

CH20H OH OH CH20H

The structure of polyester can be represented as shown below.

o 0

-O-~-o~o-LO-

Use your understanding of intermolecular forces to explain why Disperse Yellow 7 dyes polyester much better than it dyes cotton.

...................................................................................................................................... [4]

[Total: 24]

END OF QUESTION PAPER

OCR has made every effort to trace the copyright holders 01 items used in this Question Paper, but il we have inadvertently overlooked any, we apologise.

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