GCE

Edexcel GCE Chemistry (8080/9080)

This Examiners Report relates to Mark Scheme Publication code: UA016368

Summer 2005

Examiners Report

Chemistry (8080/9080)

Edexcel GCE

Edexcel is one of the leading examining and awarding bodies in the UK and throughout the world. We provide a wide range of qualifications including academic, vocational, occupational and specific programmes for employers. Through a network of UK and overseas offices, Edexcels centres receive the support they need to help them deliver their education and training programmes to learners. For further information please call our Customer Services on 0870 240 9800, or visit our website at www.edexcel.org.uk.

Summer 2005 Publications Code UA016368 All the material in this publication is copyright Edexcel Ltd 2005

Contents

Unit Test 6241/01 Unit Test 6242/01 Unit Test 6243/01 Coursework Unit Test 6243/01A, 01B, 01C- Practical Test Unit Test 6243/02 Unit 6244/01 Unit Test 6245/01 Unit Test 6246/01 Coursework Unit Test 6246/01A, 01B, 01C - Practical Test Unit Test 6246/02 Appendix A (Candidate Record Sheets) Appendix B (Statistics) Appendix C Online Marking (ePEN)

Page 1 Page 4 Page 8 Page 12 Page 14 Page 17 Page 21 Page 25 Page 27 Page 34 Page 36 Page 38 Page 41

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6241/01
General This paper proved to be accessible to a wide range of candidates giving opportunities to show an understanding of basic work and more demanding questions requiring both a clear understanding of key concepts and an ability to construct a logical and precise argument. There were some outstanding answers to individual questions and some near flawless scripts, but at the other extreme there were candidates who had clearly not yet mastered the minimum standard required for AS Chemistry. There were no dead marks on the paper. Recurring features in answers were the careless use of basic chemical vocabulary (eg many candidates used atom, ion and molecule interchangeably) and the imprecise use of language in a more general sense. Question 1 This question tested some very basic chemistry skills but relatively few candidates were able to score full marks. In (a) there were some oxygen atoms as well as unbalanced equations from weaker candidates. In (b) single, double and dative covalent bonds were all suggested for magnesium oxide but the common errors were failure to include the inner shell electrons (as specifically required) and the charges on the ions; candidates need to show the completed structure and not merely the electrons in transit. In (c) Some candidates described metallic bonding in terms of the interaction between the sea of electrons and nuclei rather than ions but many candidates omitted any description of the bonding of magnesium altogether and focused instead on its structure; some candidates referred to clouds of electrons rather than the Fermi sea. Some candidates described the bonding of magnesium oxide rather than magnesium, although conduction was often still explained in terms the flow of delocalised electrons. Question 2 There were many excellent answers to this question with some clear explanations of redox in terms of oxidation number. For (a) the appearance and state of chlorine and bromine were well known, but there was much confusion between the appearance of iodine in the solid state and as a vapour or in aqueous solution. In (b)(i) while most candidates were able to write a correct equation for the reaction of sulphuric acid with potassium chloride, some attempted to guess products on the basis of the reaction with potassium bromide mentioned in the next section, often with potassium hydroxide appearing as a product. In (b)(ii) most candidates were able to deduce the oxidation numbers required, but many did not explain the redox processes in terms of oxidation numbers and recognise the consequent need to identify the specific species involved. The oxidising agent was frequently identified as sulphur and, conversely, candidates referred to the oxidation states of sulphuric acid, sulphate and potassium bromide. There was a frequent failure to recognise the structuring of this part of the question clearly signalled by the word hence and many candidates answered in generalisations based on gain and loss of electrons.

Question 3 This was a straightforward question most of the marks being awarded for recall and the completion of a simple calculation. Part (a) presented few problems with the filling of the 3d sub-shell being the most common error. There were many excellent definitions of first ionisation energy in (b)(i), but even here there were examples of careless identification of particles (element, molecule and species rather than atom), imprecise phrasing (moles of electrons being removed from one atom or vice versa) and stating, or implying, that the process is exothermic. In contrast (b)(ii) proved highly discriminating. Many candidates successfully identified distance of the valence electrons from the nucleus and shielding as key factors although far fewer appreciated the need to refer to the nuclear charges on the two atoms. The question explicitly required a comparison between the elements and this aspect of the question was often neglected. There was frequent confusion between nuclear charge and effective nuclear charge and, by some candidates, with ionic charge. In (c) while the vast majority of candidates were able to write accurately about isotopes and calculate a relative atomic mass from mass and abundance data, marks were needlessly lost by the failure of some candidates to notice that an answer in terms of particles was specifically required for the former and the Ar was required to a specific number of significant figures in the latter. Question 4 This was a discriminating question. While the stronger candidates had little difficulty with either the half equations or the full equation required in (a) there many poor answers to both. Half equations showing electrons being added to sodium atoms and chloride ions and unbalanced half equations were quite common while some candidates were unable to write a correct balanced equation for the formation of sodium chloride, often showing chlorine atoms and NaCl2. Virtually all candidates knew that sodium chloride is ionic and there were many excellent diagrams of its structure, including complete unit cells (a notable improvement on June 2004). However those who attempted to draw space-filling diagrams were much less likely to produce a correct representation. In (c)(i) while most candidates were aware that covalent bonding involved electron sharing, the definitions were often insufficiently precise; common errors included failure to specify the pair of electrons and that the particles involved were atoms (not ions, molecules or species). The explanation of the difference in the melting points of sodium chloride and boron trichloride required by (c)(ii) proved very challenging. There was confusion about the types of forces and bonding involved for both compounds and apart from the obvious error of describing the melting of boron trichloride in terms of breaking covalent bonds, the forces in sodium chloride were variously described as covalent or dipole-dipole interactions or as a mixture of these and those in boron trichloride as ionic. Once again different types of particle (atoms, ions and molecules) were named indiscriminately and sometimes simultaneously as being present in both compounds. A recurring misconception even from good candidates was that melting involves breaking most or even all of the bonds or intermolecular forces in a substance. Hence boron trichloride was thought to have a lower melting point because melting involved breaking fewer bonds. Even so there were some very clear, concise and correct answers to this question.

Question 5 There were many good answers to (a) although some seemed unfamiliar with the reaction, assuming that potassium oxide or superoxide was formed and a number of correct equations omitted the state symbols. Most candidates were able to give two correct observations for (b), but some duplicated (eg bubbling and effervescence) and others gave an inference rather than an observation (eg gas evolved). Most candidates tackled the calculation of the empirical formula in (b)(i) confidently and systematically. A fairly common slip was the use of atomic numbers rather than relative atomic mass; a much more serious error was to invert the mole calculation, dividing relative atomic mass by mass and these candidates compounded their problems by jumping from their incorrect answer to a correct formula. Few candidates were able to determine the oxidation number of oxygen in potassium superoxide with almost all values from +5 to -5 being offered. In (c) the comparison of the thermal stability of the two nitrates drew some good answers, showing a good appreciation of the link between ion charge and size and the consequent polarisation of the anion. The term charge density was often used without definition and, as elsewhere in the paper, the particles involved were often unspecified; weaker candidates referred to the effect of the ions on the bond between metal (ion) and nitrate or deduced that lithium nitrate would be more stable because of lithiums lower reactivity. Question 6 The mole calculations in (a) proved well within the capabilities of most of the candidates and arithmetical errors, incorrect transfers of numbers from one part of the calculation to the other and failure to quote answers to an appropriate number of significant errors rather than any fundamental misunderstandings were the most likely to cause loss of marks. In (b) most candidates could draw an adequate diagram of silicon tetrachloride and knew it to be tetrahedral, but there was rather less certainty about the value of the bond angle with 107 and 120 being common. The shape was often ascribed to repulsions between chlorine atoms or even ions and even when it was appreciated that electrons were involved candidates often neglected to mention pairs of electrons and the number of pairs. In (c) that electronegativity differences lead to bond polarity was well-understood but some candidates simply offered a description of a polar bond. It was common to suggest that the lack of a permanent dipole was due to the movement of electrons so focusing on the word permanent. Again there were frequent imprecise explanations; describing cancellation of the bonds was quite common. Hints for Revision Have a clear understanding of the different types of particles involved in chemical systems (atoms, ions and molecules) and their distinctive characteristics. Be aware that melting involves breaking a small proportion of bonds or intermolecular forces. Understand that both ionic and covalent bonds are very strong in comparison with intermolecular forces. Be aware that certain words in questions require particular types of response. For example compare requires a comparison in the answer. Be able to draw the common molecular shapes and some ionic and giant covalent structures; it would be useful to practise these. Show working in calculations.

6242/01
General Candidates were able to show the full range of knowledge and skills required by the specification. The full mark range was utilised with many excellent scripts gaining full or almost full marks. A large number of candidates would do well to read the questions more carefully. In several places answers to questions not asked were common. Question 1 In (a)(i), more able candidates understood the principle behind the use of sodium hydroxide and the property of aluminium oxide involved. Many candidates did not make it clear that a reaction was taking place, comments such as dissolved being common. Most could identify the amphoteric nature of the oxide. A significant minority of candidates thought the sodium hydroxide dissolved the impurities or precipitated aluminium hydroxide. Part (a)(ii) was well done by many, but again reactions to produce precipitates were not uncommon. Part (b)(i) was poorly done by the majority of candidates. The function of the cryolite to act as a solvent for the high melting point alumina and allow a conducting medium for electrolysis to be produced was not well understood. Far too many candidates suggested the cryolite lowered the melting point of the alumina. Parts (ii) and (iv) were well done by the majority of candidates. Part (iii), while well done by many still produced errors such as 3Al, Al3, Al3+(aq). Question 2 This question was generally well done across the whole entry and tended to be the highest scoring question for many candidates. Most demonstrated their ability to draw full structural formulae clearly and accurately. A small number of candidates should be encouraged to spend a little more care in the placing of bonds. In several instances candidates who clearly understood what was required bonded the H atom in the OH group to the C to produce C-H-O groups. Candidates should be advised to count the number of hydrogen atoms on the structure they have drawn as a quick check that the structure is complete. The most common error was to identify propan-1-ol as propanol. In (ii) a number of candidates gave an aldehyde as the product. Possibly an example of failing to read the question carefully enough and missing the reference to under reflux. Most candidates scored well on the colour change. However a full range of changes, often observed in tests at this level, were seen with the most common error being purple to colourless. The choice of reagent in (b)(i) varied. The more able candidates gave precise details. The main error among those who understood what was required but failed to score was to use dilute sulphuric acid. In (ii) some candidates tried to name the compound produced rather than the stating compound. The products of the reaction with potassium hydroxide were a challenge to the weaker candidates with the alkene sometimes showing a 5 valent carbon, but many excellent answers were also seen.

Question 3 In several parts this was the least well done question for many candidates. Few candidates found any problems with (a) the only errors being to mix up the industrial process involved and Pt/Rh or Fe were among the errors. In (b)(i) the majority of candidates quoted an acceptable temperature. Many were able to demonstrate a full understanding of the effect of temperature increase on the rate of the reaction under consideration in (b)(ii). The common error was not to link the change in rate to the activation energy barrier for the reaction. A significant number of candidates talked only of increased collision frequency leading to increased rate. While this may play a small part, this factor alone cannot account for the large change in rate seen for small changes in temperature. The use of terminology was poor in places and phrases such as molecules have the activation energy were common. It was assumed candidates meant that the collision involved molecules with enough energy between them to overcome Ea. Some suggested that all the molecules have the activation energy! Far too many talked about the effect of temperature on the position of equilibrium. Part (b)(iii) was generally well done with candidates able to link the position of equilibrium to the direction of enthalpy change in the equation. A small number seemed to be unable to distinguish between right and left hand sides of an equation. Answers to (c)(i) suggested the Contact Process uses the full range of pressures from 10 Pa to 1000 atmospheres. In (ii) many candidates did not answer the question asked which was to justify the pressure used. However, there were some excellent answers from candidates who understood that all that is needed is enough pressure to push the gas through the system and that while increase in pressure will increase yield, the extra is not worth the increased cost. Many reinterpreted the question and gave the standard answer about change in pressure on position of equilibrium. Generally very few realised that the yield is high even at low pressures and had difficulty in explaining it would not be worth the extra costs of increasing the pressure for the marginal increase in yield. One problem was a lack of understanding of what, in industry, constitutes a high pressure. Many answers seemed to suggest that a small increase from 2 atm would be dangerous while others were happy with 200 atm . Some candidates gave perfect answers on the assumption that the process was the Haber process even mentioning ammonia produced from sulphur dioxide. The question tested quality of written communication skills. Many candidates found it difficult to keep to the point and brought in explanations about the effect of pressure on rate. This may or may not be a factor in this surface catalysed reaction. There is a tendency among some candidates to state that the change is due to Le Chateliers Principle rather than using the idea to predict the effect of pressure change. The main error in (d) was to suggest that the sulphur dioxide is reacted directly with water. The best answers gave a full explanation backed up by correct equations. The equation to produce the ammonium sulphate provided a stumbling block to all but the most able candidates. This equation was balanced by many by producing hydrogen. The formulae of ammonium salts should be understood by candidates at this level. The accepted uses of sulphuric acid were many and varied, but examiners expected statements such as used in the manufacture of paints not used as paint or used as detergent!

Question 4 Part (a) of this question was well done by many candidates with correct linking of reagent, catalyst and temperature. If candidates quote actual temperatures these must be within the accepted range. A number of candidates failed to score because they failed to identify which was reaction 1 and correct reagents were quoted for reactions 2 or 3. Many candidates were able to draw the structure of the addition product; the major error was to generate the 1-bromobutane rather than the 2-bromo compound. The identification of the reagent type was well done only by the more able candidates. The reagent for the conversion of the alkene into the diol was generally correct. The majority of mistakes were due to incorrect formulae or incomplete ambiguous names such as potassium manganate. Part (d) was almost the worst answered question on the paper. Very few candidates seemed to be able to take a monomer and write the polymer that it forms. Candidates might be encouraged to draw the monomer as an H shape with the double bond as the horizontal bar and the other groups as the verticals. The double bond can then be opened out to form the continuation bonds on each side. A large variety of polymers from poly(ethene) to polyesters were seen, but very few poly(butane)s Question 5 The calculation in (a) was easy for the majority of candidates. Many of those who understood what was required got the wrong answer because they failed to read the question carefully and presumably assumed it was the same as all the others that have been set previously. It quite clearly stated in the equation that the carbon was a gas and therefore single molecules. Many errors occurred because of the addition of the bond energy of carbon to the bond breakingside. Some candidates did not understand the structure of the product and left out the C-C bond. Poor arithmetic skills let some candidates down and in many cases it was difficult to follow the calculation through with numbers scattered at random over the space. The best answers identified the bonds broken and the bonds formed and then calculated the change. This helped examiners give consequential marks where errors had occurred. In (b) most candidates did not read the equation and went into this question is always set and the answer is always average bond energies mode. In this case this was not so since the equation did not represent the standard heat of formation. Other wrong answers suggested heat loss or that the candidate probably did the experiment incorrectly. Question 6 Part (a) was very well done by many candidates. The definition in (b) was well known the main errors being to mention element or compound rather than both and to omit any reference to pressure or quoted temperature. The equation proved a challenge to many candidates. Most candidates could identify the products, but could not cope with the arithmetic needed to balance the oxygens. Surprisingly some candidates made mistakes in the simple calculation of the enthalpy change per gram for butane. The numbers in 2877 were transposed, the Mr for butane was calculated wrongly, the negative sign was omitted, or numbers were multiplied instead of divided. Answers ranged from the very tiny to the enormous (5 x 1025). In (ii) candidates were instructed to use the data in the table to compare the three hydrocarbons as potential fuels for use in motor vehicles. The table contains no

reference to renewable resource, any details of combustion products, nor any reference to greenhouse effects. It contained details of physical state, energy output per cm3 and per gram. A significant number of candidates lost marks because their answers were not comparative, words such as highest and lowest being absent. Some made comparisons of energy without specifying whether it was per gram or per cm3 and some referred to the calorific value of fuels without defining what they meant by the term. Very few realised that all the compounds listed are used as fuels and many concluded octane was the least satisfactory. A surprising number thought that ethanol was unsatisfactory as a fuel because it is flammable. Others thought ethanol was dangerous because it contains alcohol and an alarmingly large number suggested ethanol would be a good, as it does not produce carbon dioxide on combustion. Some candidates reasoned that the negative sign in front meant that this was a measure of the energy needed to be put in to burn the fuel. An interesting concept that led candidates to argue that large energy values were a disadvantage. Some produced concise, well argued discussions that showed a real understanding of the data and the points to be considered. However, the majority of answers lacked clarity and did not use the data accurately, or address the issue of application to motor vehicles. Hints for revision Check the number of hydrogens on a full structural formula Learn how to convert the formula of a monomer into that of a polymer Read all the details of the question particularly equations. Do not fall into the trap of thinking the question is one you have done before. It may be, it may not. Think about layout of calculation answers and use words to explain what the numbers mean. Look at the mark allocation for the answer and relate this to the number of points to be made. Remember this is a chemistry paper and the marks will be for chemistry not for general ecological points.

6243/01 Internal Assessment of Practical Coursework

General Now that the revised assessment scheme has been running for some years it seems reasonable to expect that all centres will know exactly how to operate it. Although many centres do so admirably, others do not. This is in spite of warnings on U9s and in Examiners Reports. The Edexcel scheme was designed to be easy to follow with clear point-by-point marking schemes and relatively straightforward administration. Centre assessors may be assured that if they use Edexcel exercises and apply the mark schemes rigorously it is unlikely that marks will be altered. A moderator may not exactly agree with an assessors award of marks but any differences are likely to be within agreed tolerances. In spite of this assurance, however, some marks were altered this year because the centres application of the scheme was so wide of the moderators expectations. Examples include marks not being scaled even though this is clearly demanded in some exercises. Many comments made in previous Examiners Reports are worth repeating and are done so below. In addition some new issues arose this year. These are also referred to. Exercises from any previous version of the Internal Assessment of Practical Coursework booklet are no longer valid and should not be used. The only published excercises that are authorised for use are from issue 2 (January 2003) of the booklet. Centre designed exercises must be approved by the Principal Moderator before they are used to assess candidates. If approval has been given than some documentary evidence to this effect must accompany the sample submitted to the moderator. At least one mark from an exercise based on organic chemistry must be included in each candidates mark profile. Record cards should no longer be used. Record sheets have replaced these. A copy of a record sheet is included as an appendix to this Examiners Report. It is vital that marks are submitted and samples of requested work despatched to moderators by the set deadline.

A full explanation of the requirements of the assessment scheme is given on pages 1-5 of the 8080 Internal Assessment of Practical Coursework booklet (Issue 2, January 2003). In particular the procedures listed in section 5 Recording Marks (page 2) must be followed rigorously (for record cards read record sheets). Pages 1 to 6 of the equivalent 9080 booklet will also clarify some points concerning the scheme.

Comments on assessment of the abilities Ability A Planning. Most candidates find this ability to be the most demanding of the four. Often the mark on 15 for this ability is the lowest of the five marks making up the total. There appears to be some uncertainty amongst centre assessors as to the exact conditions under which ability A must be assessed. Listed below are a number of points that may clarify the way in which planning exercises should be carried out. It is likely that candidates will only have one or two opportunities to carry out a planning exercise. The most appropriate time for a planning exercise is soon after the candidate has studied the topic on which the exercise is based. Candidates should be told in advance that they are to be assessed for ability A. They should be given details of the specification topic on which the exercise is based. For example if AS11 (Identification of Organic Compounds) is to be set then candidates may be told that they need to know and understand the relevant tests from Topic 2.2. During the assessment exercise candidates must not be allowed to consult or copy from any notes or books. They should be supervised under conditions that are very close to those in written examinations. Candidates should be given a time limit for completion of the exercise. If, in the assessors opinion, candidates need more time than is available in one session they may be allowed to continue the exercise in a following lesson. When this happens the unfinished exercises must be collected by the assessor then returned for completion at the earliest opportunity. Candidates should be reminded at the start of every assessment exercise that they will be asked to sign an authentication statement to the effect that any work submitted to Edexcel is their own and that they have received no help apart from that of their teacher. Moderators are instructed to report any suspicions they may have that candidates from the same centre may have colluded to Edexcel. There is no requirement whatsoever to word-process a plan. If a word-processed plan is submitted to a moderator the centre assessor should include a note explaining the conditions under which the word-processing was carried out. Once collected in, plans must not be returned to candidates for corrections. If, in the opinion of the assessor, a candidate has under-achieved on a planning exercise then he or she may be given another opportunity to complete a planning exercise, but using a different assessment. Manipulation

Ability B

Whether using either an Edexcel exercise or a centre-designed one it is essential that marks are awarded for accuracy. Accuracy marks should make up about one third of the total for the ability B exercise. Only quantitative exercises may be used for assessing this ability. It is vital that work submitted to the moderator is accompanied by values gained by the assessor using the same equipment and chemicals as the candidates. The two marks in the mark profile must be taken from different types of exercises. A common and acceptable combination is a titration and an enthalpy exercise.

Ability C Candidates need practice in making and recording observations so it is reasonable to set an exercise in the same format as, for example AS8, to candidates in advance of the assessment itself. The mark schemes for these exercises have been written to match the demands of the written papers so it is important that assessors are just as rigorous in their award of marks as an external examiner would be. Clear should never be awarded a mark if the mark scheme gives colourless. When a gas is evolved from a solution the observation must be recorded as bubbles or effervescence. A colour change should include both the initial and final colours so acidified dichromate (VI) is observed to change from orange to colourless. Ability D The intention of ability D assessments is that candidates should make inferences, carry out calculations or draw graphs using their own observations and results. This is exactly what happens on the Edexcel practical tests. Errors in the early parts of calculations may be allowed for by e.c.f. (error carried forward) marking. It is, of course, quite possible, for a poor set of recorded observations to lead to confusing and low scoring inferences. In these cases the action should be to allow the candidate to have a second chance to carry out a similar set of observations but on a different exercise. It is not acceptable to supply a set of teacherproduced observations or quantitative results then to allow candidates to work out inferences using these. If a centre feels that this procedure is unfair then the centre assessor should contact the Edexcel Assessment Leader for Chemistry.

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Summary The large majority of candidates were, once again, assessed fairly and rigorously. There was some evidence this year that centre assessors may not have received, or at least not read, the U9 form sent to centres at the time results are published. Edexcel regards the U9 as a vital stage in its communications with centres. If the moderator includes a criticism on a U9 it is assumed that the centre will take steps to remedy its application or administration of the scheme. Failure to do so may mean that the following years marks are not accepted without significant change. Circumstances under which this may happen include the following: Failure to include an organic mark in each candidates mark profile after being reminded to do so on a previous U9. Use of exercises that have not received written approval from Edexcel. Use of exercises from previous versions of the Edexcel Internal Assessment of Practical Coursework booklet.

Hints for Revision Read your burette to the nearest 0.05 cm3. Record your readings as, for example, 23.55 cm3 or 24.20 cm3. When carrying out a reaction in a test tube always mix the contents by gentle shaking of the tube from side-to-side. When you observe a coloured solution losing its colour in a reaction record your observation as, for example, the brown solution turns colourless or the brown solution is decolourised. Never record it as goes clear. When carrying out an acid-base titration 3 or 4 drops of indicator is normally enough to use. In a planning exercise you must not use books or your own notes. The plan must be your own. The only person allowed to help you is your teacher.

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6243/01A/01B/01C Practical Tests

General The three papers [two home and one overseas version] were presented in conventional format. However, centres are advised that this style is not set in stone and variations may be considered. The titrations dealt with phosphoric acid against sodium hydroxide with different indicators for each group. The overseas paper had both versions but excluded the thermochemistry exercise in the two home papers. The Principal Examiner would like to use this opportunity to reassure centres that all exercises are well tried before use in the practical test, and accuracy data are determined against averages obtained using the same solutions dispensed from the manufacturing chemist that supplies centres. Question 1 In all groups the range for the expected titre was given to candidates to avoid anxiety caused by the actual titres expected. The indicators performed as expected, with the colour changes observed at the end point given to the candidates. The vast majority of candidates completed the titration table correctly, although there is still a surprising number who mistakenly believe the burette scale to read from 50 cm3 rather than 0 cm3. Candidates are also expected to be able to read the scale on a 50 cm3 grade B burette to 0.05 cm3. Candidates should average concordant titres only otherwise a spread penalty will be applied. The calculations were given a structure and most candidates performed these well. However, the need to show working, even if this seems trivial, must be emphasised. Question 2 This was a standard thermochemistry exercise, but a surprising number of poor scripts were seen. Temperatures may be estimated to 0.5 oc but not to two decimal places. Integral values were also penalised. Graph plotting is an art best learnt by drawing by hand, but to some candidates it still poses problems. Common problems were the choice of scale, particularly for the ordinate axis. These were sometimes non-linear, or of a bizarre scale that made interpolation a real trial. Data should be plotted carefully, and the two portions of the graph treated separately. Extrapolations of smooth curves or best fit straight lines were both acceptable, but too many candidates did not carry these lines far enough to give an estimate of the instantaneous temperature change at the time of mixing. Despite the instruction to show working in the derivation of temperature change, many candidates failed to do so. The value of the enthalpy change should have been given to three significant figures, but many candidates failed to heed this request. The sign should also be given. It is also clear that many candidates fail to recognise the difference between accuracy and precision in experimentally determined data. The most common (incorrect) answers were to put a lid on the plastic cup, or to mention heat loss to the surroundings.

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Question 3 The usual qualitative exercise employed some common tests, and indeed, many good scripts were seen. It was particularly pleasing to note that fewer references to misty, cloudy and milky solutions were seen this year. A white precipitate is both unequivocal and chemical. As in previous examinations, however, there are still a significant number of candidates who copy from their analysis schemes without thinking. Thus is was not unusual, in the Group 2 paper, to see lead II quoted as a potential ion despite the instruction that the salt contained a cation from the s-block of the Periodic Table. This poor reporting will always be penalised, so candidates are advised to look carefully at the stem of the question, and to think carefully about the unknown compounds and the inferences from the tests that are carried out. Question 4 The planning exercise continues to be the biggest challenge for candidates. However it is only a plan, and candidates are not expected to carry it out. This means that refinements are not possible, but the mark scheme is written in such a way to reward a sensible first draft. The biggest error that many candidates make is to try to force the format of a previous years plan onto the current one. Although similar to a plan from a previous series, there are differences that are unique to the current one. Some complete schemes were seen that earned full marks. Candidates are reminded of the rubric that stresses the importance of clear English. If candidates want to structure their plan under a series of bullet points then this is acceptable, the requirement being to convey their meaning in the written word. Hints for Revision Learn the difference between decimal places and significant figures. Understand the difference between precision and accuracy in experimentally determined data. Avoid including extraneous ions in qualitative analysis Use chemical terminology always in favour of more vague language

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6243/02
Many candidates answered this paper well, and were clear about the practical techniques used and the chemistry behind them. There is rather too much evidence of rote learning of tests without knowledge of reactions, and too many candidates have not looked carefully at the apparatus they are using during practical work or have not spent time thinking how results should be reported. A few candidates scored poorly on the main practical questions, but were able to do well on the calculations. Questions where more extended writing was required often resulted in confusion, especially in 1(b) and 4(a); candidates did not seem to have assembled their arguments before they began to write. They would be enormously advantaged if they were to read through the whole paper before they begin to answer it; there is a lot of subconscious processing that they will then do which should help to make their answers more fluent. Question 1 The majority of candidates gave the correct flame test for K+ ions. A fully correct answer for the ammonium ion test was much less common, usually because heating with sodium hydroxide was omitted or it was not clear that the gas evolved was being tested with red litmus paper rather than the solution. A large proportion knew that the barium sulphate precipitate indicated sulphate (or hydrogen sulphate) as the anion in D. The account of halide analysis in (b) was rarely written clearly. Candidates were surprisingly often confused with the test for halogen in halogenoalkanes and heated their initial sample with sodium hydroxide solution. This was ignored if the solution was then neutralised with nitric acid. Yet others thought that three samples were necessary, each one being tested separately for chloride, bromide, and iodide. Addition of silver nitrate was common, and many then added concentrated ammonia and came up with the correct observations. Some did not specify concentrated ammonia. Answers that used oxidation of the halide ion followed by use of an organic solvent could receive full credit, but coherent accounts via this route were rare. In general, candidates should confine themselves to one type of test; those who used both silver nitrate and an oxidising agent became hopelessly confused. In answering questions of this type, many candidates seem not to imagine themselves actually doing the experiment; certainly the considerable confusion shown by numerous answers would suggest that this is so.

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Question 2 Many candidates gave sound answers to much of (a) where the temperature/time graph had to be plotted. Some inevitably did not plot the points accurately, and some joined the points as dot-to-dot. A common error, even among better answers, was to take the temperature change at 3 or 4 minutes rather than at the 3.5 minutes which was the purpose of the extrapolation. In the last part many candidates said that a series of temperature readings gave a more accurate result; this in itself is not a reason, since it is not clear what the candidate means. In (b) numerous candidates used 5 or 55 as their mass in mcT, and some ignored the injunction to give the answer in Joules. Many knew the assumption that had been made, and virtually all could state the amount of copper(II) sulphate that had been used. In the last part many failed to include a negative sign for H. In (c) many candidates produced two useful improvements to the experimental method, with the use of a pipette and of a lid on the calorimeter being the most popular. In such questions the suggestion that the experiment should be repeated will never score; candidates do not seem to realise that if a method is fundamentally poor then the results will also be poor no matter how often the experiment is performed. Question 3 The first part of this question distinguished clearly between those who had done this sort of experiment, or one very similar, and knew the reasons for each of the steps performed and the remainder who had not thought about the procedures in terms of the underlying chemistry. The former knew that there were two layers and that the halogenoalkane was the product; the latter thought that there would be three layers, and often identified the alcohol as the product. Most knew that carbon dioxide is evolved when the product mixture is shaken with sodium hydrogencarbonate, and many that hydrogen or hydroxonium ions were the ions that reacted. An astonishing number of candidates gave other ions, including many that were bizarre such as carbocations. Some did not give the formula, and some gave an equation. If this showed H+ or H3O+ reacting with HCO3 then credit was given. The three errors in the apparatus shown in (c) were usually picked up only on rare occasions, though many candidates could suggest two. Nearly all mentioned the direction of flow of water in the condenser, and a high proportion offered either the need for a vent or for the use of an alternative method of heating. A number suggested the need for anti-bumping granules, and this was credited. Some suggested that the thermometer should be in the liquid examiners wondered where they might have seen such an experiment. A surprising number opted for trivial suggestions, such as the necessity for clamps and stands or for lighting the Bunsen burner, thereby showing that they could not see what was truly significant or what the point of such a diagram is. A number of candidates gave four or more improvements, but there is no advantage in doing this. The calculation of yield and percentage yield in (d) was done well by virtually everyone in some cases including those who had not scored well on other parts of the paper.

15

The test for an alcohol using phosphorus pentachloride was widely understood, though some candidates wanted to use an aqueous solution of this reagent and could not therefore score since they had not appreciated the reaction of PCl5 with water. A significant minority suggested the use of dichromate/acid, not having realised that the alcohol is tertiary and therefore gives no reaction. Some candidates gave two tests, which seldom advantaged them. This was particularly true if a false positive was suggested for dichromate and acid, followed by a correct version of the test with PCl5. Question 4 Many candidates recognised the need for a constant flame from the Bunsen burner, or the need to keep the distance between the burner and the tube the same in each case. Fewer recognised the need for both. Some suggested the use of a water bath with all the tubes immersed simultaneously, but this was not allowed for credit since candidates ought to know that the temperature would be far too low for any decomposition to be seen. The calculation in (b) concerning the amount of barium carbonate required was largely done correctly, though a few candidates resorted to some pretty savage rounding of their figures. Many could also calculate the volume of CO2 evolved from MgCO3, though in some cases there was confusion between cm3 and dm3. However only a minority was able to calculate the percentage error in the mass of magnesium carbonate; many candidates forgot that two weighings were involved, each with its own error. Many candidates reacted to the experiment where an empty tube is heated by answering that it is a control but said nothing more. This is not a sufficient answer since it gives no idea of what the candidate means. The best answers mentioned expansion of the air and the necessity of subtracting this value from the other readings to find the amount of CO2 produced. The test for CO2 proved an easy question for almost all. However the perceived trend in thermal stability of the carbonates was not always related to the results in the table; some candidates talked about the size of the cation and its polarising power, therefore answering some other question that perhaps they had seen before, but not the one that was before them. Hints for Revision: Learn the chemistry that lies behind the practical questions; the results do not exist independently of chemistry, but come from it. Learn the reasons for each of the manipulations (distillation, washing etc in preparative organic chemistry. Look carefully at any apparatus that you assemble in the laboratory, and practise drawing it in section. Learn the reasons for the apparatus being as it is. If asked for a test or for three modifications, do not give more. It will not advantage you if two tests are contradictory. In answers that require some more extended prose, such as 1(b), you should assemble your ideas before you begin to write. It is useful to learn such material as a list of things to do. Read through the entire paper before you begin to write.

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6244/01
General This paper seemed to be accessible to most candidates and there was no evidence of any time pressure. The paper contained some relatively straightforward questions, along with a number of more challenging ones. Several questions elicited responses with a considerable lack of precision, so that words such as atom, ion and molecule were used almost interchangeably. Writing balanced equations for straightforward reactions proved difficult for a sizeable number of candidates. Some excellent scripts were seen, nonetheless, with the answers to calculation questions laid out clearly and logically. Question 1 Part (a)(i) provided a good start for many candidates. The equations in (a)(ii) proved somewhat more problematic than expected for a sizeable number of A2 candidates. The formula for magnesium hydroxide was inaccurately recalled and many thought that hydrogen gas would be formed in the reaction between magnesium oxide and water. A significant number of candidates thought that sulphuric acid, rather than sulphurous acid, would be produced in the reaction between sulphur dioxide and water. Any ensuing equation, not surprisingly, proved difficult to balance in such cases. Marks were often recovered, however, if candidates realised that hydroxide ions and hydrogen ions were the cause of the alkalinity and acidity, respectively. In (a)(iii), the full three marks were rarely achieved. The giant molecular structure of silicon dioxide was well known, but a significant number of candidates then went on to write that silicon dioxide contained Si=O double bonds, presumably by confusing the bonding with that in carbon dioxide. Some candidates remained unclear as to whether covalent bonds or van der Waals forces would have to be broken in silicon dioxide if it were to react with water. The prohibitively high activation energy for the reaction was rarely mentioned. Of the two equations in (b), the second one was known far better by candidates than the first. In (c)(i), the increasing stability of the +2 oxidation state down Group 4 was known, but no mark was awarded unless a comparison was made with the +4 oxidation state. In (c)(ii), the final oxidation states were often well known, but a significant number of candidates could not balance the equation between tin(II) ions and iron(III) ions. Full marks could be obtained, however, for a correct description of the reaction in words without writing an equation.

17

Question 2 In (a)(i), first electron affinity was often defined correctly. Common errors that were seen included omitting a reference to the gaseous state or starting with one mole of an element instead of one mole of gaseous atoms. A significant number of candidates defined this process as an endothermic one. In (a)(ii), most candidates scored two out of three marks for labelling the Born-Haber cycle. The requirement to double both the enthalpy of atomisation of iodine and the first electron affinity of iodine was frequently overlooked. Consequential marking allowed credit to be earned in (a)(iii), based on the labels that had been annotated in (a)(ii). Many candidates were unable to construct an appropriate expression to calculate the first electron affinity in (a)(iii). For example, negative signs appeared in the final answer, or the final answer was divided by two, without any explanation. In (b)(i), most candidates knew that the size and charge of the ions would affect the lattice energy. A substantial number referred to charge density, but if this term is used it should always be followed by an explanation. Many candidates thought that the potassium ion and calcium ion were of the same size. The third mark available, for consideration of the relative forces of attraction between the cation and anion in the two compounds, was frequently missed. Instead, a vague reference to stronger bonds was made or a discussion of covalent character followed. The latter was then repeated in the answer to (b)(ii). Here, the importance of clear English was evident as many contradictory answers were seen. The words atom, ion and molecule appeared to be used interchangeably, as often happened in (b)(i). Many candidates realised that calcium iodide had significant covalent character, but some candidates could not explain polarisation correctly. They thought that calcium iodide was polarised or that the iodide ion polarised the calcium ion. Other answers did not make it clear that the bonding in potassium iodide was (almost) 100% ionic. Question 3 This question provided candidates, who had thoroughly learnt and understood the organic section of the Unit, with an opportunity to score very high marks and question totals of 17+ were frequently awarded. In (a), Grignard reagent was often quoted as an answer, without a specific compound being identified. Also, for the conditions, a mixture of dry ether and dilute acid together were often proposed, instead of candidates making it clear that the intermediate compound was subsequently hydrolysed. In (b)(i), the equation for the reaction between propanoic acid and sodium carbonate was often written incorrectly. The main reasons were either NaCO3 being given as the formula of sodium carbonate or a failure to balance the equation, even though the formulae of the reactants and products were correct.

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The answers to (b)(ii) were altogether more impressive. In (c), the vast majority of candidates gave acidified potassium dichromate(VI) as the oxidising agent. Those that gave Fehlings or Tollens reagent almost invariably did not include an acidification step at the end. In (d)(i), the reaction was very well known and even the weaker candidates were usually able to state that the reaction was nucleophilic addition. Various reducing agents were quoted in (d)(ii), with lithium aluminium hydride in dry ethoxyethane being the most popular. If the reaction had not been recognised as a reduction, candidates often suggested a substitution reaction with ammonia or a Hofmann degradation reaction instead. In (e)(i), often only one of the two functional groups in the 1-aminobutan-2-ol molecule was shown to have reacted with ethanoyl chloride, despite the fact that two marks had been allocated to this part of the question. In (e)(ii), the common errors were either to substitute the OH group for a Cl atom or to draw out the bonds of the -NH3+ ion and to then place the + charge on one of the hydrogen atoms. In (f), the vast majority of candidates recognised that the isomerism was optical, but some found it difficult to draw suitable three-dimensional representations of the isomers. Question 4 Part (a) was very well answered, with the vast majority of candidates omitting the partial pressures of the solid components from their Kp expression. In (b)(i), far fewer candidates included square brackets in their Kp expression than in previous examinations, which is pleasing to note. Examiners saw many excellent answers to the calculation in (b)(ii). The steps were well laid out and easy to follow. However, a significant number of candidates were unable to deduce the molar amounts of each substance present at equilibrium. Consequential marking allowed the remaining available marks to be awarded in such cases. Surprisingly, a small proportion of candidates introduced their own units to the calculation such as Pa or mol dm-3. In (b)(iii), the fact that the reaction was endothermic, and hence Kp increases, was often omitted from candidates answers. The endothermic nature of the reaction, however, was often credited from their answer to (b)(iv). Many candidates realised that the equilibrium position would shift to the right when the temperature was increased, but did not realise that the position of equilibrium adjusted because the value of Kp had increased rather than the converse argument. Question 5 Good candidates had no difficulty in identifying the two conjugate acid-base pairs in (a). A sizeable number of candidates, however, identified which species were acids and which were bases, but did not then link the conjugate pairs. In (b)(i), the spelling of phenolphthalein proved beyond many, although some latitude was given in the range of responses allowed. Part (b)(ii) was found to be challenging by candidates of all abilities and several misconceptions were highlighted. Many candidates thought that fewer H+ ions in total would undergo neutralisation in the ethanoic acid solution and so the enthalpy of neutralisation was less exothermic for this reason.

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A significant proportion of candidates knew that the ionisation of ethanoic acid was an endothermic process, however, and that all the ethanoic acid did get neutralised. Some candidates were not able to focus on the similarity, rather than the difference, between the values of the enthalpy of neutralisation for a strong and for a weak acid. Examiners saw many very good answers to (b)(iii) and (iv). In (b)(iii), the pH was often calculated correctly, except where candidates omitted to take the square root in order to calculate the value of [H+] from their expression containing [H+]2 = . The assumptions made, however, were not always clearly stated or, on occasions, were contradictory (eg the weak acid is assumed to fully dissociate). Weaker candidates used either the Ka value or the 0.140 mol dm-3 as the hydrogen ion concentration. Candidates of average ability often knew one assumption, ie [H+] = [CH3COO-], but struggled to find a second. In (b)(iv), two out of three marks were often awarded. It was extremely rare for a candidate to appreciate that the initial concentrations of the solutions of ethanoic acid and potassium ethanoate would be halved on mixing equal volumes. Hints for revision Read the question carefully. For more complex explanations, such as the reasons for the difference in lattice energies between two compounds, write out the important points as bullet points when revising. Learn all the reagents and conditions for the organic reactions in this Unit (and in Unit 2). Practise drawing 3-D representations of optical isomers. Always make sure that you understand all the assumptions that are made in any chemical calculations that you perform during the course.

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6245/01
General This A2 paper had many straightforward questions that all candidates could acces, but it was also challenging for the most able students and gave them the opportunity to show the extent of their knowledge and understanding of the course. Some candidates lost marks by not reading the questions carefully and by just quoting standard text book answers without thinking how they should have applied them to the specific questions. Many examiners noted the lack of precision in candidates answers and not completing their arguments when trying to explain a concept. Question 1 Many candidates could draw the correct structure of poly(pent-1-ene), However there were some who showed five carbon atoms in a chain in the repeat unit and others who left the double bond in the polymer. Candidates should be advised to take care over the use of C3H7 as this is ambiguous and could be a straight or branched chain. Some of those who did give the correct type of structure lost a mark by imprecise bonds from the C in the repeat unit to the CH3 or middle CH2 of the side chain. Many candidates knew the initiating step in the mechanism of polymerisation and could use a single headed arrow to represent the movement of an electron. However only the best candidates could show the two propagating steps. Terminating steps were not asked for and some candidates wasted time by including these in their mechanism. There were a lot of excellent electrophilic addition mechanisms, although some candidates need to understand what curly arrows represent so that they draw them with more precision. Many candidates were able to consider the relative stability of the intermediate primary and secondary carbocations to explain the major product. Some candidates referred to the stability of the two products and others just stated that the hydrogen joins the carbon with the most hydrogens, without attempting to explain why. Some candidates just stated that a secondary carbocation is more stable but omitted to state what it is relative to. The test for optical activity was usually answered well but the question asked how would you test for it and many candidates omitted to describe how they would carry it out using a polarimeter or simply by passing plane polarised monochromatic light through the sample. Some candidates shone the light at or on the solution and a small number of candidates thought that the light rotated the molecules. There were some excellent answers explaining how a racemic mixture is produced, although the majority of candidates omitted the essential part played by the planar intermediate cation.

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Question 2 Many candidates found this to be the most challenging question on the paper. The electronic structures of iron and Fe2+ were usually answered correctly, although some candidates ignored the [Ar] and included the 1s22s2 etc. The octahedral shape of the complex ion was known by nearly all candidates, but there were some very poor diagrams and these were not credited. Candidates should be familiar with a wedge representing a bond in front of the paper and a dotted line representing a bond going behind the plane of the paper. A flat diagram with the word octahedral written by it is not acceptable. A significant number of candidates did not balance the equation in (a)(ii) and a lot did not realise that the green precipitate turns brown when left to stand in air and suggested that it rusted. The majority of candidates realised that iron is used as a catalyst in the Haber process, but not all of them could write the balanced equation for the reaction. It was very disappointing to see A2 students using 2N to represent nitrogen gas. The definition for standard electrode potential frequently scored one mark as candidates wrote a general text book definition comparing a half cell with a standard hydrogen electrode. They did not read the question and refer to the electrode specified. Some did realise that a specific half cell was needed and wrote about a piece of platinum wire dipping into a solution of Fe3+ and Fe2+ ions. There were some excellent answers to (b)(ii) in which candidates wrote the equation for the reaction, worked out Eocell and stated that as it was positive the reaction was feasible. Candidates who chose to write generally about the electrode potential values and reversing the iron equation so that it becomes positive usually did not include enough information to score full marks. Some candidates did not realise that the standard electrode potential for hydrogen is 0.0 volts. The answers to (b)(iii) were often disappointing with many candidates just giving a general answer of high activation energy or kinetic stability without explaining the effect of these. There were a number of candidates who thought that the reaction was kinetically stable. Answers in terms of non-standard conditions did not receive any credit. The candidates who worked out Eocell for the formation of iron(III) iodide and showed that it was negative and not feasible or showed that its change into Fe2+ and iodine was feasible scored full marks for (c). Those who just worked out an Eocell from Erhs-Elhs and did not refer to a particular reaction could not receive credit. Some candidates chose to compare the Eo values but they must be careful to refer to couples and not just individual species, eg Fe3+/Fe2+ has a more positive electrode potential than I2/I-.

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Question 3 Almost all candidates knew the catalyst in Step 1 of the reaction scheme and a large number of candidates could suggest the correct synthetic route for the formation of ethanoyl chloride from ethanol. The most common error was to add HCl to ethanoic acid to produce the acid chloride. The reagent and condition for Step 2 were wellknown but a lot of candidates struggled with Step 3. There were many suggestions of heating with aqueous sodium hydroxide because they did not realise that a carbon atom had been lost. There were some excellent answers to the infra red spectroscopy questions, but candidates should be encouraged to look at the actual spectra and not just quote the possible range of wavenumbers for a particular bond. Many candidates knew that the optical isomers had identical functional groups, but they did not indicate that infra red spectra depend on the bonds present in the molecules. A lot of candidates could not suggest a correct oxidising agent in the iodoform reaction and it was not uncommon to see acidified potassium dichromate or other similar oxidising agents, even though these reagents were not given in the stem of the question. Only the best candidates could give a fully correct equation for the iodoform reaction. It was disappointing to see CH3I given as the formula for triiodomethane quite regularly. A significant number of candidates thought that triiodomethane contains elemental iodine and tested for it with starch or titrated it with sodium thiosulphate. Others thought that the iodine was already present as iodide ions and just described the silver nitrate test. Those candidates who did realise that hydrolysis was necessary often went on to score 4 marks, although some did not realise that excess nitric acid is needed to ensure that the sodium hydroxide is neutralised. Question 4 Although a lot of candidates probably know the meaning of overall order of a reaction, not all of them could define it. The sum of the partial orders is not sufficient, unless partial order is explained. Candidates may find it helpful to illustrate their answers with a general example. The term rate constant was often explained well, but again, an example may have been useful for those candidates who find it difficult to express what they mean in words. The majority of candidates could deduce the two orders of reaction, but not all of them explained how they deduced them very well. Some candidates used the data from experiments 2 and 3 and deduced the reaction to be zero order with respect to hydroxide ions. It is important for candidates to realise and state that while doubling the concentration of one reactant the other must remain constant. The majority of rate equations were correct although some candidates omitted the rate constant. The values of the rate constant were usually correct, but many candidates omitted the unit or worked it out incorrectly. The SN2 mechanism was often correct, with only a small number of candidates giving the SN1 mechanism. The most common errors were not showing the breaking of the

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C-Br bond in the first step, omitting the charge on the transition state and imprecise curly arrows. The majority of candidates could show the relative energies of reactants and products on the reaction profile, but a significant number drew a double hump and showed that they did not appreciate the difference between a transition state and an intermediate. Question 5 A large number of candidates could draw the correct structural formulae for the organic products for the reactions of phenol, with (iii) being the most difficult. Many candidates knew how to convert phenylamine into benzenediazonium chloride. However, some used sodium nitrate, some just quoted nitrous acid and not how to make it and some quoted a temperature of less than 5 oc but not how much less, an actual temperature or a small range of temperatures is much more clear. Candidates should realise that HCl represents hydrogen chloride and if they mean hydrochloric acid they should say so or use the state symbol (aq). Many candidates knew the formula for benzenediazonium ions, but those who drew the triple bond sometimes put the positive charge on the wrong nitrogen atom. Many candidates could also draw the correct azo dye, but unfortunately they did not balance their equation so could not score full marks. A significant number of candidates did not know that alkaline conditions are needed to form an azo dye.

Hints for Revision Learn definitions carefully and apply them to a specific example if requested. You may use a general example if it helps to explain your answer. Practise writing complete balanced equations do no omit some of the products. Learn the mechanism for the formation of addition polymers. Understand the difference between iodine as an element, an ion and joined to another element by a covalent bond and how to identify it in each of these situations. Understand the difference between an intermediate and a transition state.

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6246/01 Internal Assessment of Practical Coursework

General Most of the remarks in the AS report apply equally here. The great majority of candidates gain a mark of between 40 and 50. Most candidates gain their highest mark for ability B. Annotation of work is usually acceptable and often excellent. The moderators wish to encourage the use of numbered ticks since these make the task of tracking the award of marks straightforward. Word-processing of work, especially ability A plans, is becoming more common. Although the moderators have no objection to this practice it is not necessary and does raise the question of the conditions under which the exercise was carried out. The point made in the AS report is re-emphasised here. Planning exercises must be carried out under the direct supervision of the centre assessor. This includes the word-processing of a plan. If a plan has been word-processed under supervision a note explaining the circumstances should be included with the sample of work sent to the moderator. There is clear evidence from moderators that those candidates who are given multiple opportunities to carry out assessment exercises score an overall higher mark than those who complete the minimum four exercises.

Exercises The great majority of centres used exclusively exercises from the Edexcel Internal Assessment of Practical Coursework (Issue 2). This edition was issued to centres in August 2003. It is a puzzle to the moderators that a few centres continue to use the exercises from the previous edition. Centre assessors should note that these latter exercises are no longer valid. If they use them in 2006 after being clearly told not to do so in a 2005 U9 then it is quite likely that marks awarded will be moderated downwards. If a centre assessor wishes to use one of the older exercises he or she should submit a request to this effect to the Edexcel Assessment Leader. Centres are perfectly welcome, indeed encouraged, to design their own assessment exercises. Centre assessors are, however, reminded, that these must be submitted to the Principal Moderator for approval before they are used with candidates. This is done via the Edexcel Assessment Leader. It is vital that a centre-designed exercise is accompanied by a detailed mark scheme. Every one of the 15 marks must have a clear description of what is required from the candidate for that mark to be awarded. Marks for using the apparatus safely, for example, are no longer acceptable.

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Summary The large majority of candidates were, once again, assessed fairly and rigorously. There was some evidence this year that centre assessors may not have received, or at least not read, the U9 form sent to centres at the time results are published. Edexcel regards the U9 as a vital communication with centres. If the moderator includes a criticism on a U9 it is assumed that the centre will take steps to remedy its application or administration of the scheme. Failure to do so may mean that the following years marks are not accepted without significant change. Circumstances under which this may happen include the following: Failure to include an organic mark in each candidates mark profile after being reminded to do so on a previous U9. Use of exercises that have not received approval from the Principal Moderator. Use of exercises from any previous version of the Edexcel Internal Assessment of Practical Coursework booklet.

Hints for Revision When adding one solution to another in a test tube it is important to mix the contents of the tube by gentle shaking during the addition. If a precipitate forms this may dissolve in excess of the reagent being added. Use accepted chemical language in your observations in ability C exercises. Describe reagents such as aqueous sodium hydroxide as solutions rather than liquids. If a coloured solution loses its colour it is decolourised. Do not record that it goes clear. Phosphorus pentachloride, PCl5, is used to test for the hydroxyl, OH, group. The observation for a positive test should be that steamy, white fumes are given off. These turn damp blue litmus red. The inference is that hydrogen chloride, HCl, gas is formed and the OH group is present. If you have no other evidence about the compound being tested then infer that it is an alcohol or carboxylic acid. If, however, the compound is known to be neutral then it can only be an alcohol. When you are given a mass spectrum to interpret the line having the highest value of m/e is due to the molecular ion. Normally the molar mass of the compound will be numerically equal to the m/e value.

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6246/01A/01B/01C Practical Tests

General The papers were set to continue the format established in recent years. At least some candidates in every centre succeeded in making the expected observations and measurements. Indeed, from some centres, almost all candidates recorded complete and accurate observations. A failure to gain a very high mark was usually due to a lack of detail and accuracy in the inferences, evaluations and the planning exercise rather than being due to a lack of practical skills. Some candidates continue to be penalised by the fact that they are allowed the use of textbooks and their own class notes during the practical test. They fail to modify the general inferences listed alongside tests to fit the particular compound being investigated. For example, once a compound had given a positive 2,4-dinitrophenylhydrazine reaction in Q2(a) then further tests on the same compound should not have led to the inference that the compound could be an alcohol. In the Q4 planning exercise some candidates presumably based their answers on notes for a similar exercise to that being asked in this question. Very many, however, failed to modify their knowledge and understanding of similar chemistry to fit the exact demands of the question. Group 1 Compound A was manganese(II) sulphate. Compound B was zinc nitrate. (a) Some candidates failed to record the fact that the off-white precipitate of manganese(II) hydroxide darkened on standing then went to a darker brown colour on the addition of hydrogen peroxide. To gain both inference marks some reference had to be made to the oxidation of manganese(II) to manganese(IV). Candidates need to understand that the purpose of using hydrochloric acid as part of the test for the sulphate ion is to ensure that any white precipitate is barium sulphate and not any other insoluble barium compound such as the carbonate or sulphite. In this test the acid was added after the barium chloride, but it could equally well be added before the barium chloride solution. There is no need to include charges on ions as part of the formula of a compound unless they are specifically asked for. All that was required was MnSO4. Sometimes, from the same centre, most candidates recorded that the precipitate of zinc hydroxide dissolved in excess ammonia, but others stated that it did not. Presumably this is because of a failure of the latter group of candidates to either add enough ammonia or to shake the test tube adequately. Candidates may assume that if ammonia is given off following the addition of alkali and aluminium foil, a nitrate is present. If the examiners wished the candidates to detect the ammonium ion the test set would be to heat the unknown compound with aqueous sodium hydroxide alone. Most candidates correctly suggested the formula of zinc nitrate.

(b)

(c) (d)

(e)

(f)

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Question 2 Compound C was propanone. Compound D was propan-2-ol. (a) (b) The great majority of candidates observed the expected yellow or orange precipitate. A carbonyl group was also almost entirely correctly inferred. Candidates should be made aware that the inclusion of a negative test in the practical test is always a possibility. Surprisingly some candidates did record an orange to green colour change, but this seems most unlikely with a ketone. Possibly these candidates confused the two unknowns or perhaps they just assumed that there would be a reaction so copied the expected observation when using acidified dichromate(VI) from their notes or book. If a ketone had been inferred in (b) then the inference in this part should have included that compound D was an alcohol only. D could not be a carboxylic acid since this could not be made from or converted into a ketone by oxidation. Following on from the inference of an alcohol in (c) the only valid inference here was that the formation of a yellow precipitate of iodoform showed D to be a methyl secondary alcohol. At this point D could not be ethanol since this would not convert to C by oxidation. A full structure of propanone was drawn by most candidates although, since the question simply asked for a structure, the examiners were prepared to allow CH3 groups. C=O had to be shown. A correct structure of propan-2-ol was drawn by most candidates.

(c)

(d)

(e)

(f)

Question 3 Solid E was phenyl benzoate. (a) Most candidates correctly recorded two temperatures to one decimal place in Table 1. If the candidates mean temperature agreed with that of the examiner to within 3 oC then all three marks for accuracy were awarded.

(b)(i) The assumption in this part was that the melting temperature had been determined accurately so reasons concerned with problems arising from use of the apparatus were not allowed. In fact, many candidates did follow the intention of the question by suggesting that E may have been damp or impure and that other compounds will have the same melting temperature. (ii) It was assumed that since two marks were available candidates would suggest two modifications to the experiment. Although most gave the use of oil rather than water fewer suggested replacing the thermometer with one having a higher range.

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Question 4 Since it is not feasible to ask candidates to carry out an organic preparation and purification, this question was set in an attempt to test their understanding of the procedures and chemistry involved. It was not expected that candidates would have carried out this particular experiment rather that they would be familiar with the types of compounds involved and be able to adapt laboratory procedures for this exercise. It was vital for candidates to realise that methyl propanoate is a liquid. Those who described purifying it by recrystallisation thinking it to be a solid inevitably lost marks. It was not necessary to use fractional distillation at any point in the purification. Simple distillation should have been described at the end of the purification, as the method to separate the ester from any remaining traces of other liquids. Candidates should be taught that a liquid is not collected at its precise boiling temperature. Rather it should be collected in a temperature range of about three degrees spanning its boiling temperature. Group 2 Question 1 Compound F was chromium(III) sulphate (aqueous chromium(III) potassium sulphate was supplied, but no tests were carried out for the potassium ion). Compound G was lead(II) nitrate. (a) Most candidates recorded that the precipitate of chromium(III) hydroxide dissolved in excess sodium hydroxide solution although fewer included the formula or name of the [Cr(OH)6]3- as an inference. There was some understandable confusion with iron(II) ion as an inference, but iron(II) hydroxide would not have dissolved in excess alkali. Candidates need to understand that the purpose of using hydrochloric acid as part of the test for the sulphate ion is to ensure that any white precipitate is barium sulphate and not any other insoluble barium compound such as the carbonate or sulphite. In this test the acid was added after the barium chloride but it could equally well be added before the barium chloride solution. Only the formula of chromium(III) sulphate was accepted. Presumably those candidates who failed to record that the yellow precipitate dissolved in hot water failed to heat the mixture for long enough. Although it did not readily dissolve in excess sodium hydroxide solution the precipitate of lead(II) hydroxide did so for many candidates. It was necessary to add quite a large excess of alkali and to shake the boiling tube during the addition. Although a number of suggestions were made for the identity of G only the formula of lead(II) nitrate was accepted.

(b)

(c) (d) (e)

(f)

29

Question 2 Compound H was butanone. Compound I was butan-2-ol. (a) (b) The great majority of candidates observed the expected yellow or orange precipitate. A carbonyl group was also almost entirely correctly inferred. Candidates should be made aware that the inclusion of a negative test in the practical test is always a possibility. Surprisingly some candidates did record an orange to green colour change, but this seems most unlikely with a ketone. Possibly these candidates confused the two unknowns or perhaps they just assumed that there would be a reaction so copied the expected observation when using acidified dichromate(VI) from their notes or book. If a ketone had been inferred in (b) then the inference in this part should have included that compound I was an alcohol only. I could not be a carboxylic acid since this could not be made from or converted into a ketone by oxidation. Following on from the inference of an alcohol in (c) the only valid inference here was that the formation of a yellow precipitate of iodoform showed I to be a methyl secondary alcohol. At this point I could not be ethanol since this would not convert to H by oxidation. A full structure of butanone was drawn by most candidates although, since the question simply asked for a structure, the examiners were prepared to allow CH3 and CH2 groups. C=O had to be shown. A correct structure of butan-2-ol was drawn by most candidates.

(c)

(d)

(e)

(f)

Question 3 Solid J was phenyl benzoate. (a) Most candidates correctly recorded two temperatures to one decimal place in Table 1. If the candidates mean temperature agreed with that of the examiner to within 3 oC then all three marks for accuracy were awarded.

(b)(i) The assumption in this part was that the melting temperature had been determined accurately so reasons concerned with problems arising from use of the apparatus were not allowed. In fact, many candidates did follow the intention of the question by suggesting that J may have been damp or impure and that other compounds will have the same melting temperature. (ii) It was assumed that since two marks were available candidates would suggest two modifications to the experiment. Although most gave the use of oil rather than water fewer suggested replacing the thermometer with one having a higher range.

30

Question 4 Since it is not feasible to ask candidates to carry out an organic preparation and purification, this question was set in an attempt to test their understanding of the procedures and chemistry involved. It was not expected that candidates would have carried out this particular experiment rather that they would be familiar with the types of compounds involved and be able to adapt laboratory procedures for this exercise. It was vital for candidates to realise that 1-bromopentane is a liquid. Those who described purifying it by recrystallisation thinking it to be a solid inevitably lost marks. It was not necessary to use fractional distillation at any point in the purification. Simple distillation should have been described at the end of the purification as the method to separate the halogenoalkane from any remaining traces of other liquids. Candidates should be taught that a liquid is not collected at its precise boiling temperature. Rather it should be collected in a temperature range of about three degrees spanning its boiling temperature. Group 3 Question 1 Compound P was copper(II) sulphate. (a) Solid element Q was iron. It was expected that candidates would record the colour of the solution of P before ammonia was added. The expected inference to account for the solubility of the pale blue precipitate in excess ammonia solution was that the copper complex, [Cu(NH3)4(H2O)2]2+, was formed. Candidates need to understand that the purpose of using hydrochloric acid as part of the test for the sulphate ion is to ensure that any white precipitate is barium sulphate and not any other insoluble barium compound such as the carbonate or sulphite. In this test the acid was added after the barium chloride, but it could equally well be added before the barium chloride solution. Although many candidates recorded that a red solid was formed and that the blue solution became colourless fewer accurately inferred that copper metal was being displaced from solution or that copper(II) was being reduced to copper.

(b)

(c)

(d)(i) Most candidates correctly observed that the purple manganate(VII) solution became decolourised. A number of inferences were acceptable including that the manganate(VII) ion was being reduced to manganese(II). (ii) The essential point to be made in this part was that the green precipitate of iron(II) hydroxide turned brown as it was oxidised to iron(III). (e)(i) Most candidates correctly suggested the formula CuSO4. (ii) Many candidates failed to gain a mark here by writing iron(II) when Q was, in fact, the element iron or Fe.

31

Question 2 Compound R was propanone. (a) (b) Compound S was propanoic acid. The great majority of candidates observed the expected yellow or orange precipitate. A carbonyl group was also almost entirely correctly inferred. Following on from the inference of a carbonyl group in (a) the only valid inference here was that the formation of a yellow precipitate of iodoform showed R to have a methyl carbonyl group. At this point an alternative correct inference was that R was a methyl ketone or ethanal. The expected effervescence was recorded by almost all candidates as was the inference of a carboxylic acid. A range of descriptions of the smell of an ester was given credit.

(c) (d)

(e)(i) The only acceptable structure given credit was that of propanone. (ii) It was only possible to infer that R was propanone from a knowledge of its molar mass. One of the essential reasons to be given here was that the molecular ion of R had an m/e value of 58. (f) Some candidates had, by this stage of the question, become confused about the identity of S so failed to identify it by drawing the structure of propanoic acid.

Question 3 Compound T was phenyl benzoate. (a) Most candidates correctly recorded two temperatures to one decimal place in Table 1. If the candidates mean temperature agreed with that of the centre supervisor to within 3 oC then all three marks for accuracy were awarded.

(b)(i) The assumption in this part was that the melting temperature had been determined accurately so reasons concerned with problems arising from use of the apparatus were not allowed. In fact, many candidates did follow the intention of the question by suggesting that T may have been damp or impure and that other compounds will have the same melting temperature. (ii) It was assumed that since two marks were available candidates would suggest two modifications to the experiment. Although most gave the use of oil rather than water fewer suggested replacing the thermometer with one having a higher range.

32

Question 4 Some candidates wrote concise, accurate plans in which each solution was identified in turn and in a logical order. Hydrochloric acid was first added to each solution when just one, silver nitrate, would form a white precipitate. Now identified, silver nitrate may be added to the three remaining unknowns. Two would form white precipitates with one, ammonia, giving a brown precipitate. Many missed this last point. The solution now known to be ammonia was added to the two remaining solutions. Both formed white precipitates with one, zinc hydroxide, being soluble in excess ammonia. Many other candidates, however, missed the point of the exercise by assuming the identity of at least one solution from the start. Plans which started by stating, the ammonia is added. inevitably failed to score a high mark. Another error was to introduce reagents not allowed by the question. A surprisingly large number of candidates suggested that when hydrochloric acid is added to the zinc and aluminium chlorides, hydrogen gas is evolved. Hints for Revision When adding one reagent to another in a test tube shake the test tube gently to ensure mixing of the reagents. When the suggested identity of a compound is asked for read the question carefully. Sometimes a formula is required but, at other times, the name will be asked for. Take care when identifying structures from a mass spectrum. The highest value of m/e is given by the molecular ion. Normally the m/e value will be the same as the molar mass of the compound. The molecular ion has a positive change. All fragments also have positive charges. When referring to books or notes in the practical tests it is often not appropriate to simply copy inferences. You need to modify them to fit a particular question. If an organic compound is a liquid then it cannot be purified by recrystallisation. This method of purification only applies to solids. If you are required to carry out tests on a coloured solution then begin by describing its colour. When ammonia solution is added to a blue solution of a copper(II) salt a pale blue precipitate is formed. This dissolves in excess ammonia to give a deep blue solution containing the complex ion, [Cu(NH3)4(H2O)2]2+.

33

6246/02
General Comments This paper was fairly challenging, as expected at this level. There were some straightforward parts, but also a number of discriminating sections. The optional questions were selected in roughly equal proportions, and were of similar demand. A considerable number of candidates achieved marks above forty, and very few were awarded single figures. Question 1 (a)(i) The vast majority of candidates scored both marks here. (a)(ii) Again, it was common to award full marks here. Sometimes the tangent was drawn at the wrong place, and the values for x and y carelessly read. (b)(i) It was very common to award the slope mark here. Better candidates then had little difficulty in explaining that the reaction was second order. Weaker candidates often proposed a fourth order reaction, due to the 4:1 ratio. (b)(ii) This part was marked consequentially on the candidates order given in (b)(i), and it was common to award both rate equation marks. Sometimes the rate constant was capitalised, or missing, as was rate or even =. Many candidates were able to explain how to adapt the experiment, but some failed to address the idea of distinguishing between their rate equations. Question 2 (a)(i) (a)(ii) These reagents were generally well known, but very few candidates appreciated the need to add acid, after adding alkali, in step two. Virtually every candidate could draw the required structures, but only a minority explained the need for greater energy to break the double bond.

(b) and (c)(i) These structures were generally well known. (c)(ii) Many candidates referred to the partial ionisation of the weak acid. Fewer stated that the salt would be fully ionised. Candidates were generally aware how the buffer mixture responded to the addition of alkali, but it was less common to see reference to a large amount of HX. This calculation was straightforward for the stronger candidates. With consequential marking, the vast majority of candidates achieved some success here. The Mr of the salt was often carelessly miscalculated, or that of the acid was used.

(c)(iii)

34

Question 3 (a) Good candidates were often able to secure all the marks in this part. The most common error was to ignore the volume, divide by 90 or not to address the issue of units. Consequential marking gave credit where it was due. Many candidates omitted water from their Kc expression, but were still able to score six of the seven marks, for due process. A well answered question, but sometimes the mass ratio was used to compute a yield. This part was very well answered. The most common error was to draw the structure of a simple compound, with just one ester linkage.

(b) (c)(i)

(c)(ii) Many candidates understood that acid may hydrolyse ester linkages. (d) Very good candidates could score all five marks here, for a careful explanation. The majority, however, struggled to put across their ideas clearly, or omitted key points. The reasons why carboxylic acids form hydrogen bonds were often absent, and the idea of intermolecular forces was often missing. Weak candidates sometimes referred to breaking covalent bonds, even at this level.

Question 4
(a)(i) It was relatively uncommon to see a totally correct cycle here. Often state symbols were missing, or only one hydroxide ion was shown. The calculation was more often correct, and some degree of consequentiality was allowed. (a)(ii) This part was generally well attempted, and many candidates were able to clearly discuss the relevant factors. The most common error was a failure to mention the fact that the enthalpy of solution becomes more exothermic down the group. (b)(i) very many candidates were able to score two of the three marks here, but it was extremely rare to see any meaningful reference to the change in the value of the equilibrium constant. (b)(ii) This proved to be a fairly easy question for most. The common error was to not refer to the increased concentration of hydroxide ions. (c) The three gases were quite well known, sulphur dioxide proving the most elusive. Hydrogen, hydrogen sulphide and various calcium-containing compounds were the common errors. The reason for only HCl being produced with calcium chloride was beyond the knowledge, or the ability to explain, of most candidates.

Hints for Revision Learn carefully how buffer solutions respond to the addition of acid and alkali. Practise Ka and Kc calculations: they can be worth many marks. Revise the concepts of intermolecular forces very carefully. Practise explaining how and why equilibrium mixtures respond to changes in conditions. Memorise all the required reagents and conditions, to ensure you can pick up the more straightforward marks.

35

Appendix A
Candidate Record Sheet (Assessment of Practical Skills) GCE Advanced Subsidiary Chemistry - Unit 6243/01
Centre Number Centre Name Candidate Name Duration of course: September 20 to January / May 20.
Note: each ability mark and the final scaled mark out of 50 should be rounded up or down to the nearest whole number.

AS

Candidate Number

ASSESSMENT Title of experiment and topic number

Date of Assessment

Abilities B C

A Ability mark Max marks 15

Summary B

Total

30

15

15

75

Final scaled mark out of 50 For office use only MODERATED MARK .. Declaration of Authentication I declare that the work submitted for assessment has been carried out without assistance other than that which is acceptable under the scheme of assessment. Signed (candidate) Date Signed (teacher) Date .. .. ... ..

/50

36

Candidate Record Sheet (Assessment of Practical Skills) GCE Advanced Level Chemistry - Unit 6246/01
Centre Number Centre Name Candidate Name Duration of course: September 20 to January / May 20.
Note: each ability mark and the final scaled mark out of 50 should be rounded up or down to the nearest whole number.

A2

Candidate Number

ASSESSMENT Title of experiment and topic number

Date of Assessment

Abilities B C

A Ability mark Max marks 15

Summary B

Total

15

30

15

75

Final scaled mark out of 50 For office use only MODERATED MARK ..

/50

Declaration of Authentication I declare that the work submitted for assessment has been carried out without assistance other than that which is acceptable under the scheme of assessment.
Signed (candidate) Date Signed (teacher) Date .. .. .. .

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Appendix B Statistics
6241/01 Grade Raw boundary mark Uniform boundary mark 6242/01 Grade Raw boundary mark Uniform boundary mark 6243/01 cwk + 3B Grade Raw boundary mark Uniform boundary mark 6243/01A + 3B Grade Raw boundary mark Uniform boundary mark 6243/01B + 3B Grade Raw boundary mark Uniform boundary mark 6243/01C + 3B Grade Raw boundary mark Uniform boundary mark Max. Mark 100 120 A 71 96 B 63 84 C 56 72 D 49 60 E 42 48 Max. Mark 100 120 A 70 96 B 63 84 C 56 72 D 49 60 E 42 48 Max. Mark 100 120 A 70 96 B 63 84 C 56 72 D 49 60 E 42 48 Max. Mark 100 120 A 79 96 B 71 84 C 64 72 D 57 60 E 50 48 Max. Mark 60 90 A 43 72 B 37 63 C 31 54 D 26 45 E 21 36 Max. Mark 60 90 A 46 72 B 40 63 C 34 54 D 29 45 E 24 36

38

6243/01T tcwk + 3B Grade Raw boundary mark Uniform boundary mark 6244/01 Grade Raw boundary mark Uniform boundary mark 6245/01 Grade Raw boundary mark Uniform boundary mark 6246/01 cwk + 6B Grade Raw boundary mark Uniform boundary mark 6246/01A + 6B Grade Raw boundary mark Uniform boundary mark 6246/01B + 6B Grade Raw boundary mark Uniform boundary mark Max. Mark 100 120 A 73 96 B 65 84 C 57 72 D 49 60 E 42 48 Max. Mark 100 120 A 73 96 B 65 84 C 57 72 D 49 60 E 42 48 Max. Mark 100 120 A 82 96 B 75 84 C 68 72 D 61 60 E 55 48 Max. Mark 75 90 A 52 72 B 45 63 C 38 54 D 32 45 E 26 36 Max. Mark 75 90 A 56 72 B 49 63 C 43 54 D 37 45 E 31 36 Max. Mark 100 120 A 79 96 B 71 84 C 64 72 D 57 60 E 50 48

39

6246/01C + 6B Grade Raw boundary mark Uniform boundary mark 6246/01T tcwk + 6B Grade Raw boundary mark Uniform boundary mark Notes Maximum Mark (Raw): the mark corresponding to the sum total of the marks shown on the mark scheme. Boundary mark: the minimum mark required by a candidate to qualify for a given grade. Max. Mark 100 120 A 82 96 B 75 84 C 68 72 D 61 60 E 55 48 Max. Mark 100 120 A 73 96 B 65 84 C 57 72 D 50 60 E 43 48

40

APPENDIX C online marking (ePEN) From January 2006 onwards, it is likely that most of the chemistry papers will be marked online by ePEN (electronic Performance Evaluation Network). ePEN is an image based marking system available online. ePEN allows the user to mark sections of papers, known as items. Scripts are scanned into the system and divided (electronically) into individual responses which correspond to each item. The responses are displayed on the examiners PC. Candidates and centres should be assured that the ePEN marking system results in more accurate marking. The following is offered as a guide to teachers preparing candidates for the exam. 1. Candidates should write their answers in the spaces provided on the question paper. They should be reminded that the mark allocation is more likely to be the best guide as to how much to write, not the number of lines or the space provided. If a candidate has more to write than the space allows s/he can: - extend the answer beyond the borders or - use space on a blank page or - use space after other questions An additional answer sheet (or booklet) is only necessary where there is a significant amount of additional writing needed. The candidate must alert the examiner to the fact that there is more of an answer written elsewhere on the script by writing, for example, see page # or see below or using an arrow to point to the rest of the answer. This will enable the examiner to refer the matter to the Team Leader who can see the whole paper. 2. As per normal candidates must write their answers in dark blue or black ink. Pencil is permitted for graphs and diagrams (and is visible when the script is scanned). Candidates are not permitted to use coloured inks (red is still frequently seen). Coloured inks may not scan very clearly. Candidates should be informed that there is no benefit in using coloured inks to highlight different features on their answer - these colours may not scan clearly and the script is scanned in monochrome and hence any differentiation is lost.

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Further copies of this publication are available from Edexcel Publications, Adamsway, Mansfield, Notts, NG18 4FN Telephone 01623 467467 Fax 01623 450481 Email publications@linneydirect.com Order Code UA016368 Summer 2005 For more information on Edexcel qualifications, please visit www.edexcel.org.uk/qualifications Alternatively, you can contact Customer Services at www.edexcel.org.uk/ask or on 0870 240 9800 Edexcel Limited. Registered in England and Wales no.4496750 Registered Office: One90 High Holborn, London, WC1V 7BH