TOPIC 8 MS
1.          M1:    uv light/sunlight
OR
T = 450 °C to 1000 °C;
(do not credit “high temperature”)
(ignore references to pressure or catalyst)
(penalise M1 if aqueous chlorine OR chlorine water)
(credit M1 if the condition appears over the arrow of the initiation step)
1
M2:    Cl2 → 2Cl.;
(credit correct half arrows, but penalise (once in the question) the use of double headed arrows)
1
M3:    C2H6 + Cl. → CH3CH2. + HCl;
(credit CH3CH3 for ethane and C2H5- for the ethyl radical)
1
M4:    CH3CH2. + Cl2  →  C2H5Cl + Cl.;
1
M5:    CH3CH2. + CH3CH2. → C4H10;
(penalise the absence of dots once only in this question)
(penalise subsequent ionic reactions as contradictions for each reaction contradicted) 
(if neither M3 nor M4 scored, allow CH3CH2. + Cl. → C2H5Cl for one mark)
1
[5]
2.      (a)     (i)      CH4 + 3F2 → CHF3 + 3HF
1
(ii)     M1 Initiation
F2 → 2F•
M2 First propagation
F• + CHF3 → •CF3 + HF
M3 Second propagation
F2 + •CF3 → CF4 + F•
M4 Termination (must make C2F6)
2•CF3 → C2F6 or CF3CF3
Penalise absence of dot once only.
Radical dot on •CF3 can be anywhere but if the structure is drawn out, the dot must be on the carbon atom. Penalise this error once only.
Penalise once only for a line and two dots to show a bond.
Penalise each of “Fl” and lower case F, once only in this clip
4

(b)     (i)      Displayed formula
e.g.
 
All bonds must be drawn out.
Ignore bond angles. Penalise “sticks”
1

(ii)     M1 C–Cl bond OR carbon-chlorine bond
M2 chlorine atom OR chlorine (free) radical
M3 2O3 → 3O2  OR  O3 → O2  +  O  
M1 NOT carbon-halogen
Penalise incorrect spelling of chlorine once only in this clip
M2 ignore formulae
Ignore Cl2 or Cl• or ClO• balanced on both sides of the equation
Ignore other equations leading to the overall equation
3
[9]

3.    (i)      M1 Electrophilic addition
 
M1 both words required.
For the mechanism
M3 Penalise incorrect partial charges on O − H bond and penalise formal charges
Ignore partial negative charge on the double bond.
M5 Not HSO4 –
For M5, credit as shown or −:OSO3H ONLY with the negative charge anywhere on this ion
OR correctly drawn out with the negative charge placed correctly on oxygen.
M2 must show an arrow from the double bond towards the H atom of the H − O bond / HO on a compound with molecular formula for H2SO4
M2 could be to an H+ ion and M3 an independent O − H bond break on a compound with molecular formula for H2SO4
Max any 3 of 4 marks for a correct mechanism using the wrong organic reactant or wrong organic product (if shown) or a primary carbocation.
M3 must show the breaking of the O − H bond on H2SO4
Penalise once only in any part of the mechanism for a line and two dots to show a bond.
M5 must show an arrow from the lone pair of electrons on the correct oxygen of the negatively charged ion towards the positively charged carbon atom on their carbocation
Credit the correct use of “sticks”.
For M5, credit attack on a partially positively charged carbocation structure, but penalise M4
NB The arrows here are double-headed
5
(ii)     Hydrolysis
Credit “(nucleophilic) substitution” but do not accept any other prefix.
Credit phonetic spelling.
1
(iii)    Catalyst
1
[7]

4.   (a)     M1 Br2 OR bromine (water) OR bromine (in CCl4 / organic solvent)
If M1, has no reagent or an incorrect reagent, CE=0.
Ignore ‘acidified’.
M2    Isomer 1: decolourised / goes colourless / loses its colour
For M1 penalise Br (or incorrect formula of other correct reagent), but mark on.
M3  Isomer 2: remains orange / red / yellow / brown / the same OR no reaction / no (observable) change OR reference to colour going to the cyclopentane layer
For M1, it must be a whole reagent and / or correct formula.
If oxidation state given in name, it must be correct. If ‘manganate’ OR ‘manganate(IV)’ or incorrect formula, penalise M1, but mark on.
Alternatives : potassium manganate(VII)
M1 KMnO4 in acid M2 colourless M3 purple
M1 KMnO4 in alkali / neutral M2 brown solid M3 purple
Credit for the use of iodine
M1 iodine (solution / in KI) M2 colourless M3 (brown) to purple (credit no change)
Credit for the use of concentrated H2SO4
M1 concentrated H2SO4 M2 brown M3 no change / colourless
Ignore ‘goes clear’.
Ignore ‘nothing (happens)’.
Ignore ‘no observation’.
No credit for combustion observations.
3
(b)     

All bonds must be drawn.
Ignore bond angles.
1

(c)    (i)      M1    Electrophilic addition
M1 both words needed.

Penalise one mark from their total if half-headed arrows are used.
M2 must show an arrow from the double bond towards the H atom of the H–Br molecule
M2 Ignore partial negative charge on the double bond.
M3 must show the breaking of the H–Br bond
M3 Penalise incorrect partial charges on H–Br bond and penalise formal charges.
M4 is for the structure of the tertiary carbocation
Penalise M4 if there is a bond drawn to the positive charge.
Penalise once only in any part of the mechanism for a line and two dots to show a bond.
M5 must show an arrow from the lone pair of electrons on the negatively charged bromide ion towards the positively charged carbon atom of either a secondary or a tertiary carbocation
For M5, credit attack on a partially positively charged carbocation structure but penalise M4.
Max 3 of any 4 marks in the mechanism for wrong organic reactant or wrong organic product (if shown) or secondary carbocation.
Max 2 of any 4 marks in the mechanism for use of bromine.
Do not penalise the correct use of 'sticks”.
NB The arrows here are double-headed
5

(ii)     M1 Reaction goes via intermediate carbocations / carbonium ions
M1 is a lower demand mark for knowledge that carbocations are involved.
M2 (scores both marks and depends on M1)
Tertiary carbocation / carbonium ion is more stable (than the secondary carbocation / carbonium ion)
OR
Secondary carbocation / carbonium ion is less stable (than the tertiary carbocation / carbonium ion)
M2 is of higher demand and requires the idea that the secondary carbocation is less stable or the tertiary carbocation is more stable. Reference to incorrect chemistry is penalised.
A carbocation may be defined in terms of alkyl groups / number of carbon atoms, rather than formally stated.
2
 [11]

5.       (a)     (i)      Splitting/breaking C─ X/bond(s) using/by (adding)/with water
OR
Splitting/breaking the molecule/substance/compound
using/by (adding)/with water
NOT simply the reaction of/with water
NOT simply the addition or adding of water.
NOT the “splitting of water”
Accept any halogen bond, but penalise other specified bonds
1
(ii)     M1    yellow ONLY
M2    Ag+ + I– → AgI (Ag+ I–)
For M1, penalise cream(y) OR white
Ignore pale or light or dark (yellow)
For M2, ignore state symbols
2
(iii)     M1  AgF OR silver fluoride is soluble/dissolves (in water)
M2    No result
OR no precipitate
OR no (visible) change would occur
OR colourless solution
Accept “silver flouride”
Mark independently
Ignore reference to C – F bond breakage in M1
Ignore “no reaction” and “nothing”
2

(b)     The bond that takes less energy to break/the lower bond enthalpy
(energy)/weaker bond means the precipitate/reaction/hydrolysis
occurs faster/quicker/takes less time
OR
The bond that takes more energy/the higher bond enthalpy
(energy)/stronger bond means the precipitate/reaction/hydrolysis
occurs slower/takes longer/takes more time
Insist on comparative on both bond strength and rate of reaction
1
 [6]
6.      (a)     (i)      Nucleophilic substitution
1

2
M1 must show an arrow from the lone pair of electrons on the
oxygen atom of the negatively charged hydroxide ion to the
central C atom.
M2 must show the movement of a pair of electrons from the
C-Br bond to the Br atom. Mark M2 independently.
Penalise M1 if covalent KOH is used
Penalise M2 for formal charge on C or incorrect partial charges
Penalise once only for a line and two dots to show a bond.
Max 1 mark for the mechanism for the wrong reactant and/or “sticks”
Ignore product
Award full marks for an SN1 mechanism in which M1 is the
attack of the hydroxide ion on the intermediate carbocation.
(ii)     2-bromopropane ONLY
1
(iii)     Polar C–Br OR polar carbon–bromine bond OR dipole on C–Br
OR δ+ (δ–)
C atom of carbon–bromine bond is δ+/electron deficient OR C―Br
(Credit carbon–halogen bond as an alternative to
carbon–bromine bond)
It must be clear that the discussion is about the carbon atom of the C–Br bond. NOT just reference to a polar molecule.
Ignore X for halogen
1

(b)     Elimination
Credit “base elimination” but NOT “nucleophilic elimination”
No other prefix.
1

3
M1 must show an arrow from the lone pair on oxygen of a negatively
charged hydroxide ion to the correct H atom
M2 must show an arrow from the correct C-H bond to the C-C bond
and should only be awarded if an attempt has been made at M1
M3 is independent.
Mechanism
Penalise M1 if covalent KOH
Penalise M3 for formal charge on C or incorrect partial charges
Penalise once only for a line and two dots to show a bond.
Max 2 marks for the mechanism for wrong reactant and/or “sticks”
Ignore product
Award full marks for an E1 mechanism in which M2 is on the
correct carbocation.
(c)     Any one condition from this list to favour elimination;
Apply the list principle
•        alcohol(ic)/ethanol(ic) (solvent)
•        high concentration of KOH/alkali/hydroxide OR concentrated
KOH/hydroxide
Ignore “aqueous”
•        high temperature or hot or heat under reflux or T = 78 to 100°C
Ignore “excess”
1
(d)     (i)      Addition (polymerisation) ONLY
Penalise “additional”
1
(ii)     But-2-ene ONLY (hyphens not essential)
Ignore references to cis and trans or
E/Z
Ignore butane
1
[12]
 
7.	(a)    
 	M1    C6H12O6    	2CH3CH2OH
(2C2H5OH)	+ 2CO2	

Penalise C2H6O for ethanol in M1.
M2 and M3
Mark M2 and M3 independently.
Any two conditions in any order for M2 and M3 from
•        (enzymes from) yeast or zymase
•        25 °C ≤ T ≤ 42 °C    OR    298 K ≤ T ≤ 315 K
•        anaerobic / no oxygen / no air OR neutral pH
A lack of oxygen can mean either without oxygen or not having enough oxygen and does not ensure no oxygen, therefore only credit “lack of oxygen” if it is qualified.
Penalise ‘bacteria’, ‘phosphoric acid’, ‘high pressure’ using the list principle.
M4 (fractional) distillation or GLC
Ignore reference to ‘aqueous’ or ‘water’ (ie not part of the list principle).
M5 Carbon-neutral in this context means
There is no net / overall (annual) carbon dioxide / CO2 emission to the atmosphere
OR
There is no change in the total amount / level of carbon dioxide / CO2 present in the atmosphere
For M5 – must be about CO2 and the atmosphere.
The idea that the carbon dioxide / CO2 given out equals the carbon dioxide / CO2 that was taken in from the atmosphere.
5
 [5]

8.             (i)      M1 pentan-3-one only
1
M2 CH3CH2CH2COCH3
(insist on C=O being drawn out)
(penalise use of C3H7)
1
(ii)     aldehyde         (CH3)2CHCH2CHO
1
ketone             (CH3)2CHCOCH3
1
(insist on a clear structure for the C=O of the functional groups, but do not be too harsh on the vertical bonds between carbon atom son this occasion)
(If both structures correct, but wrong way around, award one mark)
(ignore names)
 [4]

 

 9.     (a)     M1:    CH3CH2CH2CH2OH;
1
M2:    CH3CH(OH)CH2CH3;
(penalise incorrect alcohols in part (a), but mark consequentially in part (b) and in part (c), if relevant)
(if three alcohols drawn, award MAX. 1 mark)
1
(b)     M1, M2 and M3:   Correct structures for butanal, butanone
and butanoic acid;
(award these structure marks wherever the structures appear, but insist that the C=O is shown in each structure and additionally, the C-O in the carboxylic acid
3
M4:                       balanced equation for the reaction of butan-1-ol
with [O] to produce butanal and water;
1
M5:                       balanced equation for the reaction of butan-1-ol
with [O] to produce butanoic acid and water
OR
balanced equation for the reaction of butanal with [O] to
produce butanoic acid;
1
M6: balanced equation for the reaction of butan-2-ol with [O] to
produce butanone and water;
(Credit condensed structures or molecular formulas in each equation, provided it is obvious to which reaction the equation refers) (Insist that whatever formula is used in each equation that it is a conventional representation of the compound; for example penalise CH3CH2CH2COH for butanal)
1
(c)     M1:    Correct structure for 2-methylpropan-2-ol;
M2:    2-methylpropan-2-ol
1
OR
methylpropan-2-ol;
(penalise on every occasion in parts (a) and (c), structures for the alcohols that are presented with the alcohol functional group as C-H-O)
1
[10]

10.   (a)     To prevent vigorous boiling / uneven boiling / bubbling vigorously
Reference to an effect on ‘reaction’ here loses this mark.
1
(b)     Condenser
Accept ‘condensation chamber’ or ‘condensation tube’.
1
Should show effective water jacket and central tube
If a flask is also drawn then the condenser must be at an appropriate angle.
Apparatus must clearly work.
Ignore direction of water flow.
Diagram must have a clear flow of vapour and water eg unblocked central tube or flow indicated by arrows.
1
[3]

11.	Figure 2
1
Further oxidation will occur / ethanoic acid formed
Do not accept ‘poor yield’ without qualification
Can gain this mark if logic correct but has chosen wrong Figure
1
[2]

12.	B
[1]
13.	B
[1]
14.	A
[1]
15.	A
[1]
16.	A
[1]
17.	C
[1]