CHERRY HILL TUITION OCR A CHEMISTRY A2 PAPER 29 MARK SCHEME

Similar documents
GCE. Chemistry A. Mark Scheme for June Advanced GCE Unit F325: Equilibria, Energetics and Elements. Oxford Cambridge and RSA Examinations

Wednesday 13 June 2012 Morning

Question Answer Marks Guidance 1 (a) (i)

Question Answer Marks Guidance 1 (a) (K c = ) Square brackets are essential State symbols not required. IGNORE incorrect state symbols

F325 Mark Scheme June 2011

NOTE: IF any values are omitted, DO NOT AWARD any marks. e.g. 164 may be missing

TOPIC 17 ANSWERS & MARK SCHEMES QUESTIONSHEET 1 ENTHALPY OF ATOMISATION

4.3 ANSWERS TO EXAM QUESTIONS


CHERRY HILL TUITION EDEXCEL CHEMISTRY A2 PAPER 24 MARK SCHEME

M1. (a) ph = log[h + ] 1. ph = 2.79 (penalise 1 dp or more than 2dp once in the qu) despite the addition of (small amounts of) acid/base (or dilution)

CHEM5 Energetics, Redox and Inorganic Chemistry Mark scheme

GCE Chemistry A. Mark Scheme for June Unit F325: Equilibria, Energetics and Elements. Advanced GCE PMT. Oxford Cambridge and RSA

PMT GCE. Chemistry A. Advanced GCE Unit F325: Equilibria, Energetics and Elements. Mark Scheme for January Oxford Cambridge and RSA Examinations

Atoms, Amount, Equations & Reactions (Acid-Base Redox)

because the three electron pairs on Sn repel one justification: lone pair bond pair repulsion is

1 Must be dot-and-cross circles for outer shells NOT needed IGNORE inner shells Non-bonding electrons of N do not need to be shown as a pair.

CHERRY HILL TUITION AQA CHEMISTRY A2 PAPER Section A. Answer all questions in the spaces provided.

because the three electron pairs on Sn repel one justification: lone pair bond pair repulsion is

PMT GCE MARKING SCHEME. CHEMISTRY AS/Advanced SUMMER WJEC CBAC Ltd.


TOPIC 19 ANSWERS & MARK SCHEMES QUESTIONSHEET 1. ph AND K W

Question Answer Marks Guidance 1 (a) (+)5 1 ALLOW 5+ OR V OR Cr 5+ 1 (b) For equations, IGNORE any state symbols; ALLOW multiples

Answer redox system E. Question 1 (a) Marks ALL 3 correct for 1 mark. E o Most negative. Least negative. 1 Guidance.

A.M. THURSDAY, 19 June hour 40 minutes

F321 Mark Scheme June Question Answer Marks Guidance 1 (a) (i) Mass of the isotope compared to 1/12th OR mass of the atom compared to 1/12th

Wednesday 13 June 2012 Morning

is more positive than that for Cl 2 / = (V) Must refer to data from the table for M2. 1

5.1 Module 1: Rates, Equilibrium and ph

3.5 A2 Unit F325: Equilibria, Energetics and Elements

PMT GCE. Chemistry A. Advanced GCE Unit F325: Equilibria, Energetics and Elements. Mark Scheme for January Oxford Cambridge and RSA Examinations

1. C 2. B 3. D 4. D 5. A 6. B

Practice paper - Set 1 MAXIMUM MARK 100. Final. A Level Chemistry A H432/01 Periodic table, elements and physical chemistry MARK SCHEME

2 Answer all the questions. 1 Born Haber cycles can be used to determine lattice enthalpies of ionic compounds

A-level CHEMISTRY 7405/1. Paper 1: Inorganic and Physical Chemistry. SPECIMEN MATERIAL v1.2

A-level CHEMISTRY (7405/1)

Formulae, Equations & Amount of Substance

12A Entropy. Entropy change ( S) N Goalby chemrevise.org 1. System and Surroundings

Final. Mark Scheme. Chemistry CHEM5. (Specification 2420) Unit 5: Energetics, Redox and Inorganic Chemistry

2005 Chemistry. Advanced Higher. Finalised Marking Instructions

MARK SCHEME for the October/November 2015 series 9701 CHEMISTRY

Question er Mark Guidance 1 (a) (i) proton donor 1 ALLOW H + donor

1 P a g e h t t p s : / / w w w. c i e n o t e s. c o m / Chemistry (A-level)

Unit 5. Answers Marks Examiner s tips. 1 a) ΔG = ΔH TΔS 1. b) Boiling is a spontaneous change at boiling point. 1 Accept: ΔH = TΔS

Edexcel GCE Chemistry 6244/01. June Results Mark Scheme. Chemistry 6244/01. Edexcel GCE

1.8 Thermodynamics. N Goalby chemrevise.org. Definitions of enthalpy changes

Chemistry 12. Resource Exam B. Exam Booklet

Level 3 Chemistry Demonstrate understanding of thermochemical principles and the properties of particles and substances

CHEM5. (JAN13CHEM501) WMP/Jan13/CHEM5. General Certificate of Education Advanced Level Examination January 2013

12. Acid Base Equilibria

2 Answer all the questions. 1 Born Haber cycles can be used to calculate enthalpy changes indirectly.

Correct Answer Reject Mark. Correct Answer Reject Mark [ (2 x 110.5) + (2 x 285.8)] (1)

PMT. Version 1.2. General Certificate of Education June Energetics, Redox and Inorganic Chemistry. Mark Scheme

5.2 Energy. N Goalby chemrevise.org Lattice Enthalpy. Definitions of enthalpy changes

Question Answer Marks Guidance 1 (a) (i) Al (ii) 2 ALLOW multiples

Question Answer Marks Guidance 1 (a) The (weighted) mean mass of an atom (of an element) OR The (weighted) average mass of an atom (of an element)

Assessment Schedule 2015 Chemistry: Demonstrate understanding of chemical reactivity (91166)

9.1 Introduction to Oxidation and Reduction

Assessment Schedule 2016 Chemistry: Demonstrate understanding of chemical reactivity (91166)

Chemical Equilibrium

F321 Mark Scheme January 2013 Question Answer Marks Guidance 1 (b) (ii) FIRST CHECK THE ANSWER ON ANSWER LINE IF answer = 3.6(0) (dm 3 ) award 3 marks

CHEMISTRY 2815/01. Trends and Patterns. OXFORD CAMBRIDGE AND RSA EXAMINATIONS Advanced GCE

M08/4/CHEMI/SP2/ENG/TZ2/XX CHEMISTRY. Thursday 8 May 2008 (afternoon) Candidate session number. 1 hour 15 minutes INSTRUCTIONS TO CANDIDATES

Thermodynamics. Standard enthalpy change, H

PMT. GCE Chemistry A. Unit F325: Equilibria, Energetics and Elements. Advanced GCE. Mark Scheme for June Oxford Cambridge and RSA Examinations

(02) Section A. Answer all questions in the spaces provided.

2 Bonding and structure Answers to Exam practice questions

Question Answer Mark Guidance 1 (a) Method 1: 100% OR (only) one product OR no waste 2 product OR addition (reaction)

2 Answer all the questions. CO, in the presence of aqueous hydrochloric acid, HCl(aq).

CHERRY HILL TUITION AQA CHEMISTRY A2 PAPER Section A (2 marks) (1 mark) (Extra space) Property

M1. (a) Yellow (solution) 1. Orange solution 1 SO 4. Yellow / purple (solution) Allow orange / brown (solution) 1. Brown precipitate / solid 1 + 3H 2

GCE. Chemistry A. Mark Scheme for June Advanced Subsidiary GCE. Unit F321: Atoms, Bonds and Groups. Oxford Cambridge and RSA Examinations

A-level CHEMISTRY (7405/1)

14-Jul-12 Chemsheets A

A. 2.5 B. 5.0 C. 10. D. 20 (Total 1 mark) 2. Consider the following reactions. N 2 (g) + O 2 (g) 2NO(g) 2NO 2 (g) 2NO(g) + O 2 (g)

F321 Mark Scheme June 2012

A Level Chemistry A H432/01 Periodic table, elements and physical chemistry. Practice paper - Set 1 Time allowed: 2 hours 15 minutes

Explain why the bond enthalpy of a Cl Cl bond is greater than that of a Br Br bond

IB Chemistry ABS Introduction An acid was initially considered a substance that would produce H + ions in water.

Subject: Chemistry Foundation Code: Session: January Year: Final Mark Scheme

Quantitative chemistry Atomic structure Periodicity

Part of the practical procedure is given below.

Revision of Important Concepts. 1. Types of Bonding

CHEM J-14 June 2014

Cambridge Assessment International Education Cambridge International Advanced Subsidiary and Advanced Level. Published

Types of chemical reactions

B410U10-1 S16-B410U10-1. CHEMISTRY Component 1 The Language of Chemistry, Structure of Matter and Simple Reactions

(c) (i) Chlorinated hydrocarbons are carcinogens OR toxic OR Chlorine is toxic OR poisonous. PhysicsAndMathsTutor.com

Question Expected Answers Marks Additional Guidance 1 (a) (i) the energy required to remove one electron from each atom in one mole of gaseous atoms

CHEMISTRY Midterm #2 October 26, Pb(NO 3 ) 2 + Na 2 SO 4 PbSO 4 + 2NaNO 3

voltmeter salt bridge

Chapter 4 Electrolytes Acid-Base (Neutralization) Oxidation-Reduction (Redox) Reactions. Dr. Sapna Gupta

IGCSE Chemistry 4437 / 5H Mark Scheme (Final) November 2007

13 Energetics II. Eg. Na (g) Na + (g) + e - ΔH = +550 kj mol -1

Chapter 4. Reactions in Aqueous Solution


M1.C [1] M2.B [1] M3.D [1] M4.B [1] M5.D [1] M6.D [1] M7.A [1] M8.A [1] M9.C [1] M10.D [1] M11.C [1] M12. B [1] M13. C [1]

Name:. Correct Questions = Wrong Questions =.. Unattempt Questions = Marks =

The Periodic Table consists of blocks of elements

THE BRIDGING COURSE TO SIXTH FORM CHEMISTRY Birchwood High School

Transcription:

1 (a) (The enthalpy change that accompanies) the formation of one mole of a(n ionic) compound IGNE 'Energy needed' energy required from its gaseous ions (under standard conditions) ALLOW as alternative for compound: lattice, crystal, substance, solid, product Note: 1st mark requires 1 mole nd mark requires gaseous ions IF candidate response has 1 mole of gaseous ions, award nd mark but NOT 1st mark IGNE reference to constituent elements IGNE: Li + (g) + F (g) LiF(s) Question asks for a definition, not an equation 1

1 (b) (i) 1. Mark Line 1 first as below (right or wrong). Mark Line 4 as below (right or wrong) ANNOTATIONS MUST BE USED 3. Mark difference in species on Line 1 and Line MUST match one of the enthalpy changes in the table: atomisation of Li(s) atomisation of ½F (g) first ionisation energy of Li(g) --------------------------------------------------- ALLOW marks by ECF as follows: Follow order at top of Answer column 4. Repeat for differences on Line and Line 3 4 Li + (g) + F(g) + e ALLOW atomisation of ½F (g) before atomisation of Li(s): ALLOW ionisation of Li(g) before atomisation of ½F (g): 3 1 Li(g) + F(g) Li(g) + 1 / F (g) Li(s) + 1 / F (g) Correct species and state symbols required for all marks IF an electron has formed, it MUST be shown as e e 4 4 3 1 Li + (g) + F(g) + e Li(g) + F(g) Li(s) + 1 / F (g) Li(s) + F(g) Li(g) Li + (g) + F(g) + e e required for marks involving Line 3 AND Line 4 Common errors Line 4: Missing e and rest correct 3 marks Line 1: IF ½F (g) is NOT shown max [Line 4 and Li(s) Li(g) ] e.g., for F(g), F(s), F(l), F(aq), F (g) DO NOT ALLOW Fl when first seen but credit subsequently 4 3 1 Li + (g) + e + 1 / F (g) + 1 / F (g) Li(s) + 1 / F (g)

1 (b) (ii) FIRST, CHECK THE ANSWER ON ANSWER LINE IF answer = 1046 (kj mol 1 ) award marks -------------------------------------------------------------------- ( 616) = (+159) + (+79) + (+50) + ( 38) + H LE (LiF) IF there is an alternative answer, check the list below for marking of answers from common errors ------------------------------------------------------------- ALLOW for 1 mark: +1046 wrong sign H LE (LiF) = ( 616) [ (+159) + (+79) + (+50) + ( 38) ] 186 +186 +430 instead of 430 +616 instead of 616 1006.5 (+79) H at (F) halved to +39.5 = 616 430 170 wrong sign for 38 = 1046 (kj mol 1 ) Any other number: CHECK for ECF from 1st marking point for expressions with ONE error only e.g. one transcription error: e.g. +195 instead of +159 (c) ANNOTATIONS MUST BE USED H < T S H T S < 0 H is more negative than T S Negative value of H is more significant than negative value of T S NOTE IGNE comments about G 1 ALLOW exothermic for negative ALLOW a negative lattice energy value ALLOW H is negative AND magnitude of H > magnitude of T S IGNE ONLY magnitude of H > magnitude of T S 3

1 (d) For FIRST TWO marking points, assume that the following refer to ions, Mg +, etc. For ions, ALLOW atoms For Mg +, Na +, Cl and F, ALLOW symbols: Mg, Na, Cl and F ALLOW names: magnesium, sodium, chlorine, chloride, fluorine, fluoride i.e. ALLOW Mg has a smaller (atomic) radius DO NOT ALLOW molecules ALLOW Fl for F For THIRD marking point, IONS must be used Comparison of size of anions Chloride ion Cl is larger (than F ) Cl has smaller charge density (than F ) Comparison of size AND charge of cations Mg + is smaller (than Na + ) AND Mg + has a greater charge (than Na + ) Comparison of attraction between ions F has greater attraction for Na + / + ions AND Mg + has greater attraction for F / ions Quality of Written Communication: --------------------------------------------------------------------------- Third mark needs to link ionic size and ionic charge with the attraction that results in lattice enthalpy 3 Total 1 ANNOTATIONS MUST BE USED -------------------------------------------------------------------------------- A F is smaller F has a larger charge density IGNE just Cl is large comparison required A: Na + is larger AND Na + has a smaller charge IGNE just Mg + is small comparison required ALLOW greater charge density for greater charge but NOT for smaller size + AND IONS must be used for this mark IGNE greater attraction between ions in NaF AND MgF + AND ions oppositely charged ions are required ASSUME attraction to be electrostatic unless stated otherwise: e.g. DO NOT ALLOW nuclear attraction ALLOW pull for attraction ALLOW attracts with more force for greater attraction IGNE just greater force (could be repulsion) IGNE comparison of bond strength/energy to break bonds IGNE comparisons of numbers of ions IGNE responses in terms of packing 4

(a) (i) (K c = ) [CO ] [N ] [CO] [NO] 1 Square brackets required for ALL four concentrations (ii) dm 3 mol 1 1 ALLOW mol 1 dm 3 5

(a) (iii) FIRST, CHECK THE ANSWER ON ANSWER LINE IF answer = 0.95 award 4 marks -------------------------------------------------------------------- Equilibrium amounts: n(co) = 0.46 0.0 = 0.6 mol n(co ) = 0.(0) mol n(n ) = 0.1(0) mol K c calculation Must use calculated equilibrium amounts AND 0.5 0.0 0.10 3 1 (K c = ) = 0.95 (dm mol ) 0.6 0.5 4 ANNOTATIONS MUST BE USED IF there is an alternative answer, apply ECF by checking working for intermediate marks ---------------------------------------------------------------------------- APPLY ECF from incorrect starting n(co) By ECF, n(n ) = n(co )/ For all parts, ALLOW numerical answers from significant figures up to the calculator value Correct numerical answer with no working scores 4 marks ALLOW calculator value: 0.94674556 down to 0.95 (SF), correctly rounded, e.g. 0.947 IGNE units, even if incorrect --------------------------------------------------------------- Common errors 1.89 3 marks use of n(n ) = 0.(0) mol (K c = ) 0.0 0.0 3 1 0.6 = 1.89349114 (dm mol ) 0.5 1.9 3 marks 0.45 and 0.46 swapped over n(co) = 0.45 0.1 = 0.4 mol n(co ) = 0.1 mol n(n ) = 0.105 mol (K c = ) 0.1 0.105 3 1 0.4 = 1.865 (dm mol ) 0.5 1.043 marks 0.45 used twice n(co) = 0.45 0.0 = 0.5 mol n(co ) = 0.(0) mol n(n ) = 0.1(0) mol (K c = ) 0.0 0.10 3 1 0.5 = 1.04 (dm mol ) 0.5 1.1853 marks 0.46 used twice n(co) = 0.46 0.1 = 0.5 mol n(co ) = 0.1 mol n(n ) = 0.105 mol (K c = ) 0.1 0.105 3 1 0.5 = 1.185408 (dm mol ) 0.5 6

(a) (iv) Mark ECF from (iii) IF K c from (iii) < 1 equilibrium to left/towards reactants IF K c from (iii) > 1 equilibrium to right/towards products 1 First look at K c value for (iii) at bottom of cut ------------------------------------------------- ALLOW favours reverse reaction For correct K c value in (iii) of 0.95, ALSO ALLOW equilibrium position near to centre (b) (i) K c has decreased AND H is negative (forward) reaction is exothermic 1 Statement AND reason required for mark ALLOW for reason: reverse reaction is endothermic (ii) Effect of T and P on equilibrium (increased) temperature shifts equilibrium to left AND (increased) pressure shifts equilibrium to right AND fewer (gaseous) moles on right-hand side Reason ONLY required for pressure Temperature and H had been required in (i) ALLOW ratio of (gas) moles is 4:3 Overall effect on equilibrium Difficult to predict relative contributions of two opposing factors Total 10 ALLOW opposing effects may not be the same size ALLOW effects could cancel each other out ALLOW effects oppose one another DO NOT ALLOW just it is difficult to predict equilibrium position (in question) For the nd mark, we are assessing the idea that we don t know which factor is dominant 7

3 (a) (i) (K a =) [H+ ][CH 3 (CH ) COO ] ALLOW CH 3 CH CH COOH C 3 H 7 COOH in expression 1 [CH 3 (CH ) COOH] DO NOT ALLOW use of HA and A in this part. DO NOT ALLOW: [H + ][CH 3 (CH ) COO ] [H + ] = [CH 3 (CH ) COOH] [CH 3 (CH ) COOH] : CON (ii) pk a = logk a = 4.8 1 ALLOW 4.8 up to calculator value of 4.8103053 DO NOT ALLOW 4.8 (iii) FIRST, CHECK THE ANSWER ON ANSWER LINE IF answer =.71 award 3 marks -------------------------------------------------------------------- [H + ] = [K a ][CH 3 (CH ) COOH] 1.51 10 5 0.50 [H + ] = 1.94 x 10 3 (mol dm 3 ) IF alternative answer to more or fewer decimal places, check calculator value and working for 1st and nd marks ------------------------------------------------------------ ALLOW use of HA and A in this part Calculator: 1.9493593 x 10 3 ALLOW use of calculated K a value, either calculator value or rounded on script. ph must be to decimal places ph = log[h + ] =.71 3 ALLOW ECF from incorrectly calculated [H + ] and ph ONLY when values for both K a AND [CH 3 CH CH COOH] have been used, i.e. 1.5 x 10 5 AND 0.50. e.g.: ph = 5.4 marks ph =.11 marks log(1.51 x 10 5 x 0.50) No 1.5110 5 log( ) 0.50 1.51 105 ph = 4. 1 mark log( ) No 0.50 DO NOT ALLOW just log(1.51 x 10 5 ) = 4.8 NO MARKS 8

3 (b) (i) Mg + H + Mg + + H 1 IGNE state symbols ALLOW Mg + CH 3 (CH ) COOH CH 3 (CH ) COO + Mg + + H DO NOT ALLOW on RHS: (CH 3 (CH ) COO ) Mg + Ions must be shown separately (ii) CO 3 + H + H O + CO 1 IGNE state symbols ALLOW CO 3 + CH 3 (CH ) COOH CH 3 (CH ) COO + H O + CO ALLOW as product H CO 3 (c) (i) CH 3 (CH ) COONa CH 3 (CH ) COO forms CH 3 (CH ) COOH + OH CH 3 (CH ) COO + H O CH 3 (CH ) COOH is in excess acid is in excess some acid remains ALLOW names throughout ALLOW sodium salt of butanoic acid ALLOW CH 3 (CH ) COOH + NaOH CH 3 (CH ) COONa + H O DO NOT ALLOW just forms a salt/conjugate base i.e. identity of product is required 9

3 (c) (ii) Moles ( marks) ANNOTATIONS MUST BE USED amount CH 3 (CH ) COOH = 0.0100 (mol) -------------------------------------------------------------------------------- ALLOW HA and A throughout amount CH 3 (CH ) COO = 0.005 (mol) Concentration (1 mark) [CH 3 (CH ) COOH] = 0.100 mol dm 3 AND [CH 3 (CH ) COO ] = 0.05 mol dm 3 [H + ] and ph ( marks) [H + ] = 1.5110 5 0.100 0.05 = 6.04 x 10-5 (mol dm 3 ) 1 Mark by ECF throughout ONLY award final marks via a correct ph calculation via K a [CH (CH ) COOH] 3 using data derived from that in the [CH 3 (CH ) COO ] question (i.e. not just made up values) ph = log 6.04 x 10-5 = 4. ph to DP ALLOW alternative approach based on Henderson Hasselbalch equation for final marks 0.05 ph = pk a + log pk a log 0.100 0.100 0.05 ph = 4.8 0.60 = 4. ALLOW logk a for pk a TAKE CARE with awarding marks for ph = 4. There is a mark for the concentration stage. If this has been omitted, the ratio for the last marks will be 0.0100 and 0.005. 4 marks max. Common errors ph = 5.4 As above for 4. but with acid/base ratio inverted. Award 4 3 marks Award zero marks for: 4.1 from no working or random values ph value from K a square root approach (weak acid ph) ph value from K w /10 14 approach (strong base ph) Common errors ph = 4.1 use of initial concentrations: 0.50 and 0.050 given in question. Award last 3 marks for: 0.50/ AND 0.050/ = 0.15 AND 0.05 1.5110 5 0.15 0.05 = 7.55 x 10-5 (mol dm 3 ) ph = log[h + ] = 4.1 Award last marks for: 1.5110 5 0.50 0.050 = 7.55 x 10-5 (mol dm 3 ) ph = log[h + ] = 4.1 ph = 5.5 As above for 4.1 but with acid/base ratio inverted. Award 1 marks as outlined for 4.1 above 10

3 (d) HCOOH + CH 3 (CH ) COOH State symbols NOT required HCOO + + CH 3 (CH ) COOH ALLOW 1 and labels the other way around. ALLOW just acid and base labels throughout if linked by lines so that it is clear what the acid-base pairs are acid 1 base base 1 acid CARE: Both + and charges are required for the products in the equilibrium DO NOT AWARD the nd mark from an equilibrium expression that omits either charge Total 16 For 1st mark, DO NOT ALLOW COOH (i.e. H at end rather than start) but within nd mark ALLOW COOH by ECF IF proton transfer is wrong way around then ALLOW nd mark for idea of acid base pairs, i.e. HCOOH + CH 3 (CH ) COOH HCOOH + + CH 3 (CH ) COO base acid 1 acid base 1 For H COOH + shown with wrong proton transfer, DO NOT ALLOW an ECF mark for acid base pairs 11

4 (a) (i) initial rates data: From Experiment 1 to Experiment AND [NO ] x 1.5, rate x 1.5 ANNOTATIONS MUST BE USED Quality of Written Communication: -------------------------------------------------------------------------------- Changes MUST be linked to Experiment numbers in writing (Could be described unambiguously) IGNE annotations in the table -------------------------------------------------------------------------------- For nd condition, ALLOW when [NO ] increases by half, rate increases by half 1st order with respect to NO NOTE: Orders may be identified within a rate equation From Experiment to Experiment 3 AND [O 3 ] is doubled, rate x 1st order with respect to O 3 rate equation and rate constant: rate = k[no ] [O 3 ] rate k = [NO ][O 3 ] 4.80 10 8 0.00150 0.0050 = 0.018 dm 3 mol 1 s 1 8 ALLOW: working from any of the Experiments : All give the same calculated answer 0.018 subsumes previous rearrangement mark ALLOW: mol 1 dm 3 s 1 DO NOT ALLOW 0.013 over-rounding ----------------------------------------------------------------------------- [NO ALLOW ECF from inverted k expression: k = ][O ] 3 : rate k = 78.15 ALLOW 3 SF or more NOTE units must be from rate equation 1

4 (a) (ii) step 1: NO + O 3 LHS of step one NO 3 + O State symbols NOT required For rest of equations, ALLOW other combinations that step : NO + NO 3 N O 5 together give the overall equation, rest of equations for step 1 AND step e.g.: NO 5 NO + NO 5 N O 5 + O CHECK that each equation is balanced CARE: Step 1 AND Step must add up to give overall equation In Step, IGNE extra species shown on both sides, e.g. NO + NO 3 + O N O 5 + O Step can only gain a mark when Step 1 is correct e.g.: NO + O NO + NO + O N O 5 DO NOT ALLOW use of algebraic species, e.g. X (b) (i) 3 gaseous moles gaseous moles Less randomness becomes more ordered ALLOW products have fewer gaseous moles A ALLOW molecules instead of moles ALLOW fewer ways of distributing energy fewer degrees of freedom fewer ways to arrange (ii) FIRST, CHECK THE ANSWER ON ANSWER LINE IF answer = 148 award 3 marks -------------------------------------------------------------------- G = H T S = 198 (98 x 168/1000) = 148 (kj mol 1 ) 3 IF there is an alternative answer, check calculator value and working for intermediate marks by ECF ------------------------------------------------------------ nd mark subsumes 1st mark for G = H T S ALLOW 148 to calculator value of 147.936 ALLOW for marks: 49866 (kj mol 1 ): not converting S from J to kj (no 1000) 193.8 (kj mol 1 ) use of 5 instead of 98 13

4 (b) (iii) CARE: responses involve changes of negative values -------------------------------------------------------------------------- ANNOTATIONS MUST BE USED Feasibility with increasing temperature Reaction becomes less feasible/not feasible AND G increases G becomes less negative G = 0 G > 0 G is positive G approaches zero ***IF a candidate makes a correct statement about the link between G and feasibility, IGNE an incorrect H and T S relationship IF there is no G statement, then mark any H and T S relationship in line with the mark scheme --------------------- Effect on T S T S becomes more negative T S decreases T S increases magnitude of T S increases -------------------------------------------------------------------------------- As alternative for not feasible ALLOW not spontaneous a comment that implies reaction does not take place ALLOW for G increases H = T S H > T S H T S is positive T S becomes more significant than H T S becomes the same as H T S becomes more negative than H NOTE Last statement will also score nd mark ------------------- DO NOT ALLOW T S increases --------------------------------------------------------------------------------- Total 17 ---------------------------------------------------------------------- APPROACH BASED ON TOTAL ENTROPY: Feasibility with increasing temperature Reaction becomes less feasible/not feasible AND S H/T S total decreases/ less positive S outweighs/ is less significant than H/T Effect on H/T H/T is less negative H/T increases H/T decreases magnitude of H/T decreases 14

5 (a) (A transition element) has (at least) one ion with a partially filled d sub-shell/ d orbital ALLOW incomplete for partially filled DO NOT ALLOW d shell Fe AND 1s s p 6 3s 3p 6 3d 6 4s Fe(II) / Fe + AND 1s s p 6 3s 3p 6 3d 6 Fe(III) / Fe 3+ AND 1s s p 6 3s 3p 6 3d 5 4 ALLOW 4s before 3d, i.e. 1s s p 6 3s 3p 6 4s 3d 6 IF candidate has used subscripts caps [Ar], DO NOT ALLOW when first seen but credit subsequently, i.e. 1s s p 6 3s 3p 6 3d 6 4s 1s s p 6 3s 3p 6 4s 3D 6 [Ar]4s 3d 6 For Fe + and Fe 3+, ALLOW 4s 0 in electron configuration IGNE electron configurations of elements other than Fe (b) EXAMPLES MUST REFER TO Cu + F ALL MARKS PRECIPITATION Reagent NaOH(aq) KOH(aq) States not required ANNOTATIONS MUST BE USED -------------------------------------------------------------------------------- ALLOW NaOH in equation if reagent not given in description ALLOW a small amount of NH 3 /ammonia DO NOT ALLOW concentrated NH 3 DO NOT ALLOW just OH Transition metal product AND observation Cu(OH) AND blue precipitate/solid Correct balanced equation Cu + (aq) + OH (aq) Cu(OH) (s) state symbols not required IF more than one example shown, mark example giving lower mark 3 ALLOW Cu(OH) (H O) 4 ALLOW any shade of blue ALLOW (s) as state symbol for ppt (may be in equation) ALLOW [Cu(H O) 6 ] + + OH Cu(OH) (H O) 4 + H O For NH 3, also ALLOW: + [Cu(H O) 6 ] + + NH 3 Cu(OH) (H O) 4 + NH 4 ALLOW full equation, e.g. CuSO 4 + NaOH Cu(OH) + Na SO 4 CuCl + NaOH Cu(OH) + NaCl 15

5 (b) LIGAND SUBSTITUTION likely Reagent NH 3 (aq)/ammonia State not required IF more than one example shown, mark example giving lower mark ALLOW NH 3 in equation if reagent not given in description Transition metal product AND observation [Cu(NH 3 ) 4 (H O) ] + AND deeper/darker blue (solution) Correct balanced equation [Cu(H O) 6 ] + + 4NH 3 [Cu(NH 3 ) 4 (H O) ] + + 4H O ------------------------------------------------------- Reagent Concentrated HCl (dilute) HCl(aq) NaCl(aq) State not required Transition metal product AND observation [ CuCl 4] AND yellow (solution) Correct balanced equation [Cu(H O) ] + + 4Cl [CuCl ] + 6H O 6 4 3 DO NOT ALLOW precipitate ALLOW royal blue, ultramarine blue or any blue colour that is clearly darker than for [Cu(H O) 6 ] + ----------------------------------------------- ALLOW CuCl 4 i.e. no brackets ALLOW any shades of yellow, e.g. yellow green DO NOT ALLOW precipitate ALLOW other correct ligand substitutions using same principles for marking as in two examples given (c) (i) Pt oxidised from 0 +4 N reduced from +5 to +4 ALLOW 1 mark for Pt from 0 to +4 AND N from +5 to +4 i.e. oxidation and reduction not identified or wrong way round DO NOT ALLOW Pt is oxidised and N reduced with no evidence DO NOT ALLOW responses using other incorrect oxidation numbers (CON) 16

5 (c) (ii) Pt + 6HCl + 4HNO 3 H PtCl 6 + 4NO + 4H O 1st mark for ALL species correct and no extras: i.e: Pt + HCl + HNO 3 H PtCl 6 + NO + H O DO NOT ALLOW charge on Pt, e.g. Pt + nd mark for correct balancing ALLOW correct multiples (d) Cl Cl Cl Pt Cl Cl Cl Must contain out wedges, in wedges and lines in plane of paper 4 lines, 1 out wedge and 1 in wedge For bond into paper, ALLOW: IGNE charges on Pt and Cl for this mark The marks for charge AND bond angle are ONLY available from a diagram showing Pt bonded to 6 Cl ONLY 3-D Shape 1 mark Correct 3-D diagram of Pt surrounded by 6Cl ONLY Bond angle 1 mark bond angle of 90º on diagram or stated 3 ALLOW ONLY if diagram has Pt surrounded by 6Cl ONLY BUT 3-D shape may not be correct DO NOT ALLOW if ANY charges shown on Pt or Cl within brackets Charge 1 mark charge shown outside of brackets 17

5 (e) (i) Donates two electron pairs to a metal (ion) ALLOW lone pairs for electron pairs forms two coordinate bonds ALLOW dative (covalent) bond for coordinate bond ALLOW 1 mark for a full definition of a ligand (without reference to : i.e. Donates an electron pair to a metal (ion) forming a coordinate bond (ii) NH O O ALLOW displayed formulae charges essential in (COO ) structure DO NOT ALLOW H N NH O O Total 1 18

6 (a) (i) complete circuit with voltmeter and salt bridge linking two half-cells Salt bridge MUST be labelled Pt electrode in Fe 3+ /Fe + half-cell with same concentrations Cr electrode in 1 mol dm 3 Cr 3+ half-cell 3 ALLOW Fe + and Fe 3+ with concentrations of 1 mol dm 3 ALLOW 1 M but DO NOT ALLOW 1 mol (ii) Cr + 3Fe 3+ Cr 3+ + 3Fe + 1 ALLOW sign (iii) 1.51 V 1 IGNE sign DO NOT ALLOW if e shown uncancelled on both sides, e.g. Cr + 3Fe 3+ + 3e Cr 3+ + 3Fe + + 3e (b) Cr O 7 AND H + 1 ALLOW acidified dichromate (c) Cr O 7 (aq) + 8H + (aq) + 3HCOOH(aq) Cr 3+ (aq) + 7H O(l) + 3CO (l) State symbols not required 1st mark for ALL species correct and no extras: Cr O 7, H +, HCOOH, Cr 3+, H O AND CO NOTE: H + may be shown on both sides ALLOW sign (d) (i) E o for chromium (redox system) is more negative/lower/less (than copper redox system) A nd mark for correct balancing with H + cancelled down ALLOW E cell is +1.08 V (sign required) chromium system shifts to the left / Cr(s) Cr 3+ (aq) + 3e AND copper system shifts to the right / Cu + (aq) + e Cu(s) ALLOW Cr loses electrons more readily/more easily oxidised Cr is a stronger reducing agent Cu loses electrons less readily Cu is a weaker reducing agent 19

6 (d) (ii) Cr reacts with H + ions/acid to form H gas 1 ALLOW equation: Cr + 6H + Cr 3+ + 3H (ALLOW multiples) DO NOT ALLOW just hydrogen forms, i.e. Cr, H + /acid AND H must all be included for the mark (e) (i) 1.45 V 1 IGNE sign (ii) marks,, for two points from the following list: 1. Methanoic acid is a liquid AND easier to store/transport hydrogen is a gas AND harder to store/transport hydrogen as a liquid is stored under pressure. Hydrogen is explosive/more flammable 3. HCOOH gives a greater cell potential/voltage ASSUME it refers to HCOOH DO NOT ALLOW 'produces no CO ' IGNE comments about biomass and renewable HCOOH and H are both manufactured from natural gas 4. HCOOH has more public/political acceptance than hydrogen as a fuel Total 14 0

ALLOW e : 7 (a) MnO + 4OH MnO 4 + H O + e i.e. sign not required 3H O + ClO 3 + 6e 6OH + Cl (b) Role of CO CO reacts with H O forming an acid carbonic acid/h CO 3 forms CO is acidic Equation involving OH H CO 3 + OH H O + HCO 3 H CO 3 + OH H O + CO 3 CO + OH CO 3 + H + CO + OH HCO 3 CO + OH CO 3 + H O H + + OH H O ANNOTATIONS MUST BE USED -------------------------------------------------------------------------------- ALLOW equation: CO + H O H CO 3 CO + H O H + + HCO 3 CO + H O H + + CO 3 Effect on equilibrium with reason equilibrium shifts to right AND to restore OH 3 ALLOW for restores OH the following: makes more OH, OH has been used up DO NOT ALLOW just equilibrium shifts to right 1

F35 Mark Scheme June 01 7 (c) FOLLOW through stages to mark -------------------------------------------------------------------------- Moles in titration n(kmno 4 ) = 0.000 x 6. 1000 = 5.4 x 10 4 mol ANNOTATIONS MUST BE USED AT LEAST 3 SF for each step -------------------------------------------------------------------------------- n(so 3 ) = 1.31 x 10 3 mol Scaling n(so 3 - ) in original 100 cm 3 = 4 x 1.31 x 10 3 = 5.4 x 10 3 mol ECF.5 x answer above ECF 4 x answer above Mass Mass of Na SO 3 in sample = 16.1 x 5.4 x 10 3 g = 0.660764 g ECF 16.1 x answer above ALLOW 0.661 g up to calculator value Percentage % Na SO 3 = 0.660764 0.70 100 = 91.8% 5 ALLOW alternative approach based on theoretical content of Na SO 3 for last marks Theoretical amount, in moles, of Na SO 3 in sample 0.70 n(na SO 3 ) = 16.1 = 5.71 x 10 3 mol Percentage % Na SO 3 = 5.4 103 100 = 91.8% 3 5.7110 calculated mass above ECF 100 0.70 ALLOW 91.8% (1 DP) up to calculator value of 91.7777778 i.e. DO NOT ALLOW 9% COMMON ERRS: 36.8(1)% 4 marks no.5 factor.9(4)% 4 marks no scaling by 4 9.18% 3 marks no.5 and no x 4 Watch for random ECF %s for % from incorrect M(Na SO 3 ), e.g. use of M(SO 3 ) = 80.1 giving 58.3% Total 10 4