Mark Scheme (Results) Summer 2008

GCE

GCE Chemistry Nuffield (6254/01)

Edexcel Limited. Registered in England and Wales No. 4496750 Registered Office: One90 High Holborn, London WC1V 7BH

General Marking Guidance

All candidates must receive the same treatment. Examiners must mark the first candidate in exactly the same way as they mark the last. Mark schemes should be applied positively. Candidates must be rewarded for what they have shown they can do rather than penalised for omissions. Examiners should mark according to the mark scheme not according to their perception of where the grade boundaries may lie. There is no ceiling on achievement. All marks on the mark scheme should be used appropriately. All the marks on the mark scheme are designed to be awarded. Examiners should always award full marks if deserved, i.e. if the answer matches the mark scheme. Examiners should also be prepared to award zero marks if the candidates response is not worthy of credit according to the mark scheme. Where some judgement is required, mark schemes will provide the principles by which marks will be awarded and exemplification may be limited. When examiners are in doubt regarding the application of the mark scheme to a candidates response, the team leader must be consulted. Crossed out work should be marked UNLESS the candidate has replaced it with an alternative response.

Using the mark scheme 1 2 3 4 5 / means that the responses are alternatives and either answer should receive full credit. ( ) means that a phrase/word is not essential for the award of the mark, but helps the examiner to get the sense of the expected answer. [ ] words inside square brackets are instructions or guidance for examiners. Phrases/words in bold indicate that the meaning of the phrase or the actual word is essential to the answer. ecf/TE/cq (error carried forward) means that a wrong answer given in an earlier part of a question is used correctly in answer to a later part of the same question.

6254_01 0806

Question Number 1 (a)

Correct Answer Any three from Titrate with (sodium) thiosulphate to measure concentration of I2. Titrate with an alkali/base (eg sodium hydroxide) to measure concentration of H+/acid. Titrate with silver ions to measure I Measure colour change (colorimetry) as iodine is coloured [colour changes not needed] Use pH (meter) to measure H+/acidity Measure conductivity as (2) ions on RHS IGNORE any reference to quenching

Acceptable Answers

Reject Dilatometry I

Mark 3

IGNORE indicators unless inappropriate e.g. starch Addition of starch to give colour If incorrect colours given, then no mark. Benedicts solution to give colour Electrolysis Measure volume of hydrogen Acceptable Answers Reject Alkali/base/sodium hydroxide Ice/ice-cold water to slow the reaction max 1 Acceptable Answers Could compare experiments 1 and 3 Cold water Mark 2

Question Number 1 (b)

Correct Answer Add sodium (hydrogen)carbonate (1) which neutralises/reacts with/removes the H+ (1) 2nd mark awarded only if an alkali added

Question Number 1 (c)(i)

Correct Answer First order (1) In exp 2 and exp 3 / concentrations of iodine and H+ remain constant (1) propanone concentration increases by 1.5 times and the rate also increases by 1.5 times (1)

Reject

Mark 3

Question Number 1 (c)(ii)

Correct Answer Zero (order) / 0 (order)

Acceptable Answers Zeroth (order)

Reject

Mark 1

6254_01 0806

Question Number 1 (c)(iii)

Correct Answer Rate = k[H+][CH3COCH3] ALLOW TE from (i) and (ii) IGNORE state symbols

Acceptable Answers Rate = k[H+][CH3COCH3][I2]0 R or r for rate K for rate constant

Reject

Mark 1

Question Number 1 (c)(iv)

Correct Answer H+ and CH3COCH3 IGNORE state symbols

Acceptable Answers Names, [], displayed formula ALLOW TE from rate equation in (iii) Acceptable Answers

Reject

Mark 1

Question Number 1 (c)(v)

Correct Answer CH3COCH3 + H+ CH3C+OHCH3 (1) + can appear anywhere on formula + sign must appear on the product for the 1st mark The (positive) hydrogen ion is attracted to the lone pair of electrons / on the oxygen atom (in the propanone). (1)

Reject No TE from earlier parts

Mark 2

Question Number 2 (a)(i)

Correct Answer Contains two double bonds /2 C=C / 1 x C=C and 1 x C=O

Acceptable Answers Triple bond

Reject A double bond Does not contain a benzene ring Alkene Double bonds

Mark 1

6254_01 0806

Question Number 2 (a)(ii)

Correct Answer Does not contain an OH group

Acceptable Answers Not an alcohol OR Not an hydroxyl OR hydroxyl OR Not an alcohol nor a carboxylic acid/nor a phenol Acceptable Answers Acceptable Answers C=O

Reject Not a hydroxide

Mark 1

Not a carboxylic acid Not a phenol Reject Mark 1 Reject Mark 1

Question Number 2 (a)(iii) Question Number 2 (a)(iv)

Correct Answer Contains one C=C/ a C=C bond Correct Answer Aldehyde or ketone (both needed) OR carbonyl compound Correct Answer Aldehyde

Question Number 2 (a)(v)

Acceptable Answers CHO OR

Reject

Mark 1

H C O
Question Number 2 (a)(vi) Correct Answer Has the same two groups across (on opposite sides) a C=C Correct Answer Alkene and aldehyde groups anywhere in molecule [but must have 6 carbons, 10 hydrogens and 1 oxygen] (1) Trans and rest of molecule (1)
H H H H H C C C C C C H H H H O H

Acceptable Answers May be shown in a diagram OR in (vii) Acceptable Answers

Reject

Mark 1

Question Number 2 (a)(vii)

Reject

Mark 2

CH3CH2CH2

6254_01 0806

Question Number 2 (b)(i)

Correct Answer Nickel / platinum and hydrogen (1) Lithium tetrahydridoaluminate((III)) (1) Either order

Acceptable Answers formulae Lithium aluminium hydride Ignore solvent unless water then reject Sodium tetrahydridoborate((III)) /borohydride Acceptable Answers Hydroxyl OR hydroxy Acceptable Answers More ways of arranging energy in a liquid because of translation/rotation energy Acceptable Answers +(0).2156 kJ mol-1 K-1 OR +0.216 kJ mol-1 K-1

Reject Sodium and ethanol

Mark 2

Question Number 2 (b)(ii)

Correct Answer (primary) alcohol

Reject OH OR hydroxide OR OH Reject Just more ways of arranging energy

Mark 1

Question Number 3 (a)(i)

Correct Answer Liquids are more disordered than solids/ solids are more ordered than liquids/ solids are less disordered than liquids / liquids are less ordered than solids Correct Answer (165 + 217.1 166.5 =) + 215.6 OR +216 (J mol-1 K-1) + sign essential

Mark 1

Question Number 3 (a)(ii)

Reject 215 J mol-1 K-1 0.215 kJ mol-1 K-1

Mark 1

Question Number 3 (a)(iii)

Correct Answer Yes because The products include a gas (1) One mole/molecule goes to two moles/molecules (1)

Acceptable Answers Solid goes to liquid and gas for first mark

Reject

Mark 2

1 reactant goes to 2 products does not get 2nd mark Acceptable Answers - 0.415 kJ mol-1 K-1 -415.4 J mol-1 K-1 final answer with no working (2) Allow j for J 6254_01 0806 Reject Full calculator display eg -415.4362416 more than 2 dp e.g. -415.436 Mark 2

Question Number 3 (b)

Correct Answer S surroundings = -H T OR -123800 (1) 298 = - 415 J mol-1 K-1 (1)

Question Number 3 (c)(i)

Correct Answer Stotal = -415 + 216 = -199 or -199.8 or -200) (J mol-1 K-1) IGNORE 4th significant figure Correct Answer reactants predominate / equilibrium lies well to the left OR Equilibrium completely to the left

Acceptable Answers -0.199 kJ mol-1 K-1 ALLOW TE from(a)(ii) and (b) Acceptable Answers ALLOW TE from (c)(i)

Reject

Mark 1

Question Number 3 (c)(ii)

Reject

Mark 1

Question Number 3 (d)(i)

Correct Answer Kp =

Acceptable Answers (1) Capital P Use of ( ) If expression the wrong way up allow second mark if units given as atm1 Acceptable Answers If moles at eqm are given as 0.025 for PCl3(g) and for Cl2(g) then 4th column should be 3.24, 0.54 and 0.54 and gets 2 (out of 3)

Reject Use of [ ]

Mark 2

p PCl 3 p Cl 2 p PCl 5

IGNORE state symbols or lack of them unless (s) or (l) Units atm (1) Question Number 3 (d)(ii) Correct Answer
Substance Moles at start Moles at equilibrium

Reject

Mark 3

Peq /atm 0.15 x 4.32 0.25

PCl5(g) PCl3(g) Cl2(g)

0.20 (1) 0.05 0.05 0.25 All three(1)

= 2.592
0.05 x 4.32 0.25

= 0.864 0.864 Total number of moles at equilibrium

All three(1)

Allow consequential marking across columns

6254_01 0806

Question Number 3 (d)(iii)

Correct Answer (Kp = 0.864 x 0.864) (2.592) = 0.288 (atm)

Acceptable Answers ALLOW TE from 3di and from 3dii Common wrong values above gives 0.090 ALLOW 0.29

Reject 0.3 0.28

Mark 1

Question Number 3 (d)(iv)

Correct Answer A No change because Kp depends only on temperature / number of moles would change in same proportion (1) B Increase because reaction is endothermic (1) OR entropy arguments

Acceptable Answers If both changes correct but no explanations then 1 (out of 2)

Reject

Mark 2

Question Number 4 (a)(i)

Correct Answer Step 1 Reagent Fuming sulphuric acid / sulphur trioxide/sulphur(VI) oxide/oleum (1) Conditions Reflux / heat (1) Only allow heat for this mark if the reagent is reasonable (e.g. conc sulphuric acid) Step 2 Reagent Sodium hydroxide (1)

Acceptable Answers

Reject

Mark 3

SO3/H2S2O7

(Concentrated) sulphuric acid/ H2SO4

If just stated temperature must be above 75 C

sodium carbonate/ sodium hydrogencarbonate/ sodium Acceptable Answers sulphonation

sodium chloride

Question Number 4 (a)(ii)

Correct Answer Step 1 (electrophilic) substitution (1) Step 2 neutralisation or acid-base (1)

Reject Nucleophilic substitution

Mark 2

6254_01 0806

Question Number 4 (b)(i)

Correct Answer Friedel-Craft(s) Accept phonetic spelling

Acceptable Answers Alkylation

Reject

Mark 1

Question Number 4 (b)(ii)

Correct Answer Reagent C12H25Cl OR C12H25Br (1) Catalyst AlCl3 (1)

Acceptable Answers (1-)chlorododecane C12H25I

Reject

Mark 2

Al2Cl6 Aluminium chloride Acceptable Answers Surfactants

AlCl4 AlCl4 Reject Dyes Drugs Antiseptics Reject Mark 1

Question Number 4 (c)

Correct Answer (Soapless) detergent OR a specific example Correct Answer Ka = [H+] x [HCO3] (1) [CO2] mol dm-3 (1) If H2O is included as denominator then allow only the 2nd mark if no units suggested

Question Number 5 (a)(i)

Acceptable Answers

Mark 2

Question Number 5 (a)(ii) Question Number 5 (b)

Correct Answer pKa = - log Ka / - lg Ka / - log10 Ka Correct Answer A solution which does not change its pH value (significantly) (1) When some/small amount of acid or alkali is added (1)

Acceptable Answers Ka = 10_pKa Acceptable Answers May be shown using an equation

Reject

Mark 1

Reject

Mark 2

Question Number 5 (c)

Correct Answer Acting as a base because it is accepting a proton (to form H2CO3/CO2 + H2O)

Acceptable Answers

Reject

Mark 1

6254_01 0806

Question Number 5 (d)(i)

Correct Answer Before race 7.4 = 6.5 log [acid] [base] Log [acid] = 0.9 [base] (1)

Acceptable Answers

Reject

Mark 2

[acid] = 0.126 (1) [base] Question Number 5 (d)(ii) Correct Answer Before race [CO2] = 0.126 x 0.0224 = 2.82 x 10-3 OR 2.52 x 10-2 2.24 x 10-2 = 2.8 x 10-3 Correct Answer Hypothesis I would result in an increase in [CO2] / [HCO3] / [CO2 + HCO3] OR Hypothesis II would produce greater acidity without additional [CO2] / [HCO3] / [CO2 + HCO3] (1) The table shows a fall in [CO2] / [HCO3] / [CO2 + HCO3] and therefore Hypothesis II must be favoured. (1)

0.13

0.12

Acceptable Answers

Reject

Mark 1

Question Number 5 (d)(iii)

Acceptable Answers

Reject

Mark 2

6254_01 0806