(a)(i sulfuric acid / fuming H SO 4 / oleum / H S O 7 Conc. (for fuming) Fuming dilute sulfuric acid Just sulfuric acid Just H SO 4 (a)(ii) Sulfur is δ+ and on at least one oxygen δ- Full + or charge(s) Oxygen is (much) more electronegative than sulfur Oxygen is very electronegative / on each oxygen (a)(iii) The sulfur trioxide can accept a pair of electrons An electron (Three oxygen atoms so) sulfur has a large δ or partial / slight positive charge bonds allow S O bonds to be polarized more easily Electron-deficient sulfur
Marks for (b)(i) and (b)(ii) can be awarded from either of the two annotated diagrams on item (b)(i) First curly arrow as shown to start inside the hexagon to the S atom Second curly arrow from bond to O (i.e. not from the S atom itself) Second curly arrow to any of the three O atoms in SO IGNE A full + charge on S
(b)(ii) Curly arrow as shown from the C-H bond to reform the ring in first line, not from the H atom in this bond Intermediate anion formed in first line (H + does not have to be shown) Last line with curly arrow and correct structure of benzenesulfonic acid Use of H O for H + Use of H SO 4 for H + with HSO 4 as other product in final step The marks for (b)(ii) may be awarded from annotations on the right hand structure given in question in (b)(i) If contradictory arrows drawn on structure in question (b)(ii), then penalise any such inconsistency The three marks for the two steps in (b)(ii) can be shown in one step / diagram / structure -SO H undisplayed -HSO
(c)(i) C 6 H 5 SO H + NaOH C 6 H 5 ONa + Na SO + H O Charges on C 6 H 5 O - Na + Charges on C 6 H 5 SO H C 6 H 5 ONa + HCl C 6 H 5 OH + NaCl C 6 H 5 O - + HCl C 6 H 5 OH + Cl - C 6 H 5 O - + H + C 6 H 5 OH (c)(ii) Any two from: Cheaper (Both) products useful / both are useful / propanone is useful So less waste / high(er) atom economy Fewer steps / one step / does not require many steps (in Hock synthesis) Continuous rather than a batch process () IGNE Only one waste product in Hock Comments relating to hazardousness of reactants / safety / energy requirements References to yield References to efficiency References to rate
(a),6-dimethylhept-5-enal () Either part scores e.,6-dimethyl hept-5-enal IGNE missing/misplaced/misused hyphens or commas ene for en methy or methly for methyl (b)(i) CH C(CH )=CHCH CH CH(CH )CH OH C 9 H 8 O CH C(CH )CHCH CH CH(CH )CH OH CH C(CH )=CHCH CH C (CH ) HCH OH displayed or skeletal formulae K Cr O 7 /Na Cr O 7 /name (oxidation state must be correct if given (VI)) This is a stand alone mark H SO 4 /name (ignore any references to concentration) KMnO 4 (0) for last marks HCl (0) for rd mark H + and Cr O 7 - () Acidified dichromate (b)(ii) (Steam) distil off melonal (as it forms) Allow add a limited amount of oxidizing agent/excess alcohol/excess X To prevent further oxidation/to prevent carboxylic acid forming Stand alone marks
(c) Wavenumber range / cm - Bond Functio group present in melonal 740 70 900 80 / 775 700 669 645 095-00 C=O C- C=C C- (saturated) Aldehyde/CHO Alkene carbon to carbon double bond Just carbonyl Just C=C in rd column any single value or range within the ranges above one mark if both wavenumber ranges and bond columns are correct but neither bond identified (d) C H 5 O + /CH CHCHO + + C 4 H 9 + C 6 H [ Structural, skeletal or displayed formulae] C 5 H 7 O + Penalise omission of + charge once only any order of atoms if correct totals. (e)(i) Circle around any other additional atoms
(e)(ii) Circle around any other additional atoms (f)(i) Arrow from anywhere on the cyanide ion to the carbon of the carbonyl. Arrow to the O must come from the carbonyl bond Formula of intermediate Arrow from oxygen to H and from H-CN bond to CN arrow from O to H + or to H O Starting from HCN/ CN - Single headed arrows
(f)(ii) These marks are stand alone EITHER No First mark: Reaction site/carbonyl/aldehyde/molecule is planar Second mark: Attack (equally likely) from both sides Attack (equally likely) from above and below attack on a (planar) carbocation attack on a (planar) intermediate S N S N planar product Any/either direction or any/either angle Third mark: (gives) racemic mixture/(gives) equal amounts of each isomer/(gives) equal amounts of each enantiomer Yes Melonal has a chiral carbon atom Correct identification of chiral centre This chiral centre unaffected by reaction
(a)(i) (a)(ii) Addition Nucleophilic Either order SN SN Hydrogen cyanide / HCN Potassium cyanide / KCN/ sodium cyanide/ NaCN Just CN - Potassium cyanide / KCN With hydrochloric acid / sulfuric acid (to generate HCN) Just CN - Just acid/ H + any weak acid Ignore concentration of acids Mark for HCl etc is consequential on KCN Hydrogen cyanide / HCN With sodium hydroxide / other base (to make cyanide ions) Mark for NaOH etc is consequential on HCN Just OH -
(a)(iii) Both arrows in first step of mechanism above correctly drawn Correct intermediate with charge Both arrows in second step with correct organic product (CN - is not required) Use of HCN for first step max marks Allow omission of lone pair on CN - and O - Allow curly arrow from negative charge or elsewhere on cyanide ion C=O breaking before attack by CN - Arrows from atoms when they should be from bonds and vice versa Allow arrow from O - in nd step to H + (no other product or only one product) or H O ( with OH - formed)
*(a) (iv) Attack (by nucleophile on the C) is from both sides (equally)/ above and below (at the planar reaction site in the aldehyde group) Attack on intermediate in reaction mechanism is from both sides Attack from both ends/two angles So a mixture of two enantiomers/(optical)isomers in equal proportions forms racemic mixture forms Just both enantiomers form First and second marks are independent (b) Any named (aqueous) strong acid or its formula. Water H + Allow (aqueous) sodium hydroxide followed by named acid or formula Potassium dichromate + sulfuric acid Carboxylic acids Ignore references to concentration (c)(i) -hydroxypropanoic acid - hydroxylpropanoic acid - hydroxopropanoic acid -hydroxypropan- -oic acid
(c)(ii) CH CH C C O C C O A dimer H O H O Missing H atoms CH CH Missing bonds at ends O C C O C C H O H O All bonds in ester link must be shown More than units may be shown but structure shown should be a repeat unit Ignore brackets/n (c)(iii) (c)(iv) Ester (link/bond) in PLA can be hydrolysed/broken down (by enzymes) Ester (link/bond) in PLA can be broken down Just it can be hydrolysed Ethene is (from crude oil so) non-renewable/ milk is from a renewable source/ energy required to make ethene is high/ high temperatures needed to make ethene/ energy requirements for process from sour milk less/ process from milk doesn t use toxic chemicals / process from milk doesn t use cyanide Milk is more readily available Greater atom economy No other chemicals needed in process from milk Allow process from ethene requires many steps so expensive/so loss of material occurs at each step /so more reagents needed Just process from ethene requires many steps Ignore references to cost, unless answer gives a reason for lower cost. Just cheaper