GCE

Edexcel GCE Chemistry (6244/01)

January 2006
Mark Scheme (Results)

Chemistry (6244/01)

Edexcel GCE

1.

(a)

(i)

2Na + O2 Na2O2 IGNORE state symbols NOT Na2O 4P + 5O2 P4O10 OR 4P + 5O2 2P2O5 OR equations starting with P4 species (1) IGNORE state symbols balance (1) balanced equation forming phosphorus(III) oxide scores (1) only

(1 mark)

(ii)

(2 marks)

(b)

Al2O3 + 6H+ 2Al3+ + 3H2O Al2O3 + 2OH- + 3H2O 2Al(OH)4OR Al2O3 + 6OH- + 3H2O 2Al(OH)63OR Al2O3 + 2OH- 2AlO2 + H2O

(1)

(1)

H+ in one equation and OH in the other for acid and alkali on left of two equations. (1) IGNORE spurious species Non-ionic equations can score 3rd mark only. (c) (i) (ii) mol3dm9 [OH-] = 2(1.31x10-4) = 2.62x10-4 (mol dm3) (1) [H+] = 10-14 / 2.62 x 10-4 = 3.82 x 10-11 (mol dm3) OR pOH = 3.58 (1) pH = -lg(3.82x10-11) = 10.4(2) OR pH 14-3.58=10.4(2) (1) NOT just 10 If [OH] = 1.31 x 10-4 pH = 10.12 (max 2) Consequential on [H+] pH for 3rd mark only if pH > 7

(3 marks) (1 mark)

(3 marks)

(d)

(i)

Mg(OH)2(s) + H2SO4(aq) MgSO4(aq) + 2H2O (l) equation (1) state symbols (1) only if species correct OR Mg(OH)2(s) + 2H+(aq) Mg2+(aq) + 2H2O(l)

(2 marks)

(ii)

barium sulphate is insoluble OR less soluble than magnesium sulphate / solubility of sulphates decreases down group (1) NOT just it is insoluble and is therefore a barrier (to further reaction) OR coats solid (1)

(2 marks)

Total for Question: 14 marks

(a)

(i)

yellow / orange/red and precipitate / crystals / solid NOT solution C=N bond (1) Rest of molecule (1)

(1 mark)

(ii)

H C6H5CH CH

H C N N NO2
(2 marks)

NO2

IGNORE position of NO2 groups (iii) (warm with) Fehlings/Benedicts solution (1) red ppt (1) mention of copper(II) oxide negates 2nd mark OR (warm with alkaline) ammoniacal silver nitrate / Tollens reagent (1) silver mirror (1) reference to Ag2+ / Ag3+ negates 1st mark ALLOW acidified (potassium) dichromate (1) orange to green/blue (1) NOT potassium manganate(VII) (iv) ketone cannot be oxidised / not a reducing agent (b) (i) HCN (1) + KCN (1) OR HCN (1) base (1) OR HCN or KCN (1) pH5-9 (1) OR KCN (1) acid (except conc H2SO4) (1) ALLOW CN for KCN Four (1) It has geometric/cis-trans and optical isomers/C atom with four different groups/chiral carbon atom/asymmetric carbon OR it has both types of stereo-isomerism (1) stand alone

(2 marks) (1 mark)

(2 marks)

(ii)

(2 marks)

(c)

(i)

reduction OR nucleophilic addition ALLOW redox NOT hydrogenation

(1 mark)

(ii)

C6H5CH=CHCH(OH)CH2NH2 MUST show C=C OR formation of amine salt (1 mark) (1 mark)

(d)

(i) (ii)

(dry) ether / ethoxyethane Grignard reagents react with water ALLOW It reacts with water to form an alkane

(1 mark)

(iii) C6H5CH=CHCH(OH)CH2CH3 C=C bond need not be shown ALLOW C2H5 for CH2CH3 (iv) Secondary Do NOT allow if primary or tertiary drawn in (iii)

(1 mark)

(1 mark)

Total for Question: 16 marks

(a)

Kp = p2(NO2) (1) p(N2O4) NOT [ ] equilibrium moles mole fractions N2O4 = 0.2 OR 20 NO2 = 1.6 OR 160 (1) (1)

(1 mark)

(b)

xN2O4 = 0.2 = 0.111 and xNO2 = 1.6 = 0.889

partial pressures

pN2O4 = 0.2 x 6.75 = 0.75 (atm)

and pNO2 = 1.6 x 6.75 = 6 (atm) 1.8 48 (1) atm (1) IGNORE S.F.

Note: If moles NO2 = 0.8, Kp = 21.6 atm If moles NO2 = 0.2 and moles N2O4 = 0.8, Kp = 0.338 atm (c) (i) Reaction is endothermic (1) Kp increases (1) Therefore equilibrium position shifts to the right / forward direction (1) 3rd mark can only be awarded if it follows a change in Kp (ii) equilibrium mixture gets darker / more brown Consequential on answer to (c)(i)

(5 marks)

(3 marks)

(1 mark)

Total for Question: 10 marks

(a)

enthalpy /heat change for production of one mole of gaseous atoms (1) ALLOW energy change NOT awarded if exothermic process stated or implied Gaseous can be awarded from RHS of equation from an element in its standard state (1) ALLOW element under standard conditions I2(s) I(g) (1) State symbols required NOT multiples

(3 marks)

(b)

(i)

state symbols of Li species i.e. LiI(s), Li(s), Li(g), Li+(g) (1) species (1) IGNORE stoichiometry (2 marks)

(ii)

Either LE = 270 (+159) (+107) (+520) (295) OR -270 = (+159) + (+107) + (+520) + (-295) + (LE) (1) -761 (kJ mol-1) (1) If units stated these must be correct Consequential on numbers and signs

(2 marks)

(c)

magnesium ion is small and highly/2+ charged OR magnesium ion has high charge density (1) leading to polarisation of the (large) iodide ion (1) ALLOW distortion of electron cloud of (large) iodide ion and (causing) covalency (into the lattice) OR theoretical value assumes magnesium iodide is 100 % ionic OR magnesium iodide is not 100 % ionic (1) If atoms or molecules mentioned, only the 3rd mark is available. (3 marks)

Total for Question: 10 marks

5.

(a)

(i)

NH3+CH(CH2OH)COO If all bonds drawn, + must be shown on N high energy needed to overcome (strong) ionic attractions/strong ionic bonds (1) between (different) zwitterions OR between molecules [if ions have been mentioned] (1)

(1 mark)

(ii)

(2 marks) Max (1) if intermolecular forces mentioned out of context (b) (i)

O C OH H C CH2OH NH3+
ALLOW COOH / CO2H and IGNORE position of charge on NH3+ unless drawn in full (ii)

(1 mark)

O C OH C CH2OH NH2
ALLOW COO OR CO2 (1 mark)

(iii)

O HO C H C H O C O C CH3

NH2 H
or esterified zwitterion ALLOW COOH on acid but ester group must be drawn ALLOW substituted amide as alternative to, or in addition to, ester (1 mark)

(c)

(i) (ii)

HOCH2CH2OH

(1 mark)

O OR

H H H H

OCH2CH2 O CC6H4C
brackets optional
CO ]

C C O C C6H4C O

ALLOW

at right hand side

ester link (1) ALLOW OCO / OOC (as link was required in (b)(iii)) rest of repeat unit, including continuation bonds (1) (d) (i) (ii) hydrolysis / nucleophilic substitution/saponification only goes one way / goes to completion / irreversible with NaOH/not an equilibrium (1) reaction with acid is reversible/is an equilibrium (1) (so yield is improved with alkali) OR both reagents catalyse the reaction (1) hydroxide ions react with product to prevent reverse reaction (1) (so yield is improved with alkali) (2 marks) (1 mark)

(2 marks)

Total for Question: 12 marks

6.

(a)

starts at 2.2 (1) vertical section at 40cm3 of sodium hydroxide (1) vertical section centred between pH 8-9 and between 2 to 3 squares high (1) shape to include initial jump and finish between pH = 12-13 (1) If curve drawn back to front, only 2nd and 3rd marks available (4 marks)

(b)

(i) (ii)

maintains nearly constant pH / resists change in pH (1) on adding small amounts of acid or alkali (1) [H+] =
Ka[ acid ] [ salt ]

(2 marks)

OR

pH = pKa lg

[acid] [salt]

(1)

[H+] = 1.78 x104 x 0.25 (1) 0.125 [H+] = 3.56 x 104 (mol dm-3) pH = 3.4(5) (1) IGNORE no. of decimal places but penalise pH = 3 (iii) acid partially ionised and salt fully ionised OR equations (1) HA + OH A + H2O (1) ALLOW H+ + OH H2O followed by more dissociation of HA A + H+ HA (1) [HA] and [A] are large (relative to H+ and OH added)/ large reserves of undissociated acid and salt (and so the values of [HA] and [A] do not change significantly) (1)
NOTE: If no equations given for effect of adding OH- and H+, correct explanation can score (1) out of these two marks.

(3 marks)

(4 marks)

Total for Question: 13 marks

TOTAL FOR PAPER: 75 MARKS