GCE

Edexcel GCE
Chemist ry (8080, 9080)
6244/ 01

Summer 2005

Mark Scheme (Result s)

Chemist ry (8080, 9080)
Edexcel GCE
 IGNORE st at e symbols in all equat ions
1. (a) (i) (Magnesium oxide is) ionic / electrovalent (1)

(Sulphur dioxide is) covalent NOT giant / dative (1) (2 marks)

(ii) MgO + H2O → Mg(OH)2
OR
MgO + H2O → Mg2+ + 2OH− (1)

Contains/produces OH- ions (1)

Thi s mar k i s dependent on an OH i n t he pr oduct of t he equat i on

SO2+ H2O → H2SO3

OR
SO2+ 2H2O → H3O+ + HSO3−
OR
SO2+ H2O → H+ + HSO3−
OR
SO2+ H2O → 2H+ + SO32− (1)

Contains/produces H+/H3O+ (1) (4 marks)

If H2SO4 f or med i n equat i on, can scor e l ast mar k
QWC* (iii) (Silicon dioxide) giant covalent/ giant atomic/ giant molecular/ (1)
macromolecular
(1)
Strong/ covalent bonds (have to be) broken (for reaction)
Ref er ence t o Si =O or van der Waal s’ f or ces scor es (0) f or t hi s mar k

(so reactants are) kinetically stable / activation energy too high (for (1)
reaction) / not enough energy released in bond formation to overcome
energy required in bond breaking
IGNORE any r ef er ences t o r eact i on mechani sm (3 marks)

(b) (i) [Al(H2O)6]3+ + H2O → / ⇌ [Al(H2O)5OH]2+ + H3O+

ACCEPT one mor e depr ot onat i on of al umi ni um i ons i . e. [ Al (H2O) 4(OH) 2] + (1 mark)

(ii) SiCl4 + 2H2O → SiO2 + 4HCl

ACCEPT pr oduct s Si O2. xH2O / Si (OH) 4 i n a bal anced equat i on (1 mark)

(c) (i) (The trend is) increasing stability of the +2 state relative to the +4
state (or instability of +4 etc)
i . e. answer must be a compar i son of oxi dat i on st at es (1 mark)
(ii) (Tin(II) chloride will) reduce / be oxidised to Sn(IV) (1)

(Fe3+ goes) to Fe2+ (1)

Cor r ect equat i on e. g. 2Fe3++Sn2+→ 2Fe2++Sn4+ scor es bot h mar ks i . e.

speci es (1) bal anci ng (1).
Do NOT penal i se an unbal anced equat i on i f 1st t wo mar ks ar e awar ded
(1) (3 marks)
(Lead(II) chloride has) no reaction

Total 15 marks

1
2. (a) (i) (The first electron affinity) is the energy/ enthalpy/ heat change when
1 electron is added to each atom in 1 mole (1)
- must not i mpl y endot her mi c pr ocess e. g. “ ener gy r equi r ed”

of gaseous atoms (1)

OR
energy change per mole (1)
(for) A(g) + e− → A− (g) (1) (2 marks)

(ii) Correct labelling of Ca(s) to Ca2+(g) (+193, +590, +1150) (1)

Correct labelling of I2(s) to 2I-(g) (+214, 2 x EA) (1)
Correct labelling of lattice energy and ∆Hf of CaI2(s) (-2074, -534) (1)
Labelling can be done with symbols, words or numbers (3 marks)

(iii) Mar k consequent i al l y on t hei r l abel s i n (i i )

∆Hf = ∆Ha of calcium + 1st IE calcium + 2nd IE calcium + 2 x ∆Ha iodine + 2 x

EA I(g) + LE CaI2(s)
OR
-534 = +193+590+1150+2x107+ 2 × EA + (-2074) (1)
OR
EA = ½(2074-534-193-590-1150-214) (1)

= -303.5 / -304 (kJ mol-1)

Ot her possi bl e answer s:

One EA and +107on cycl e gi ves EA = -500 (2)

One EA and +214 on cycl e, but 2EA shown i n wor ki ng gi ves

EA = -303. 5 / -304 (2)

One EA and +214 on cycl e but EA shown i n wor ki ng gi ves

EA = -607 (1) (2 marks)

2
 (b) (i) Potassium ion / K+ larger than Ca2+ (1)
Must not r ef er t o at oms

QWC* K+ smaller charge than Ca2+ (1)

Must not r ef er t o at oms, but CAN say “ pot assi um” has a smal l er char ge
( t han “ cal ci um” )

Char ge densi t y of K+ i s l ess t han char ge densi t y f or Ca2+ wi t hout expl anat i on
i s wor t h (1) out of t hese 1st t wo mar ks
(1)
+ −
Less attraction between (K and I ) ions
NOT j ust “weaker bonds”

ACCEPT r ever se ar gument (3 marks)

IGNORE r ef er ences t o ext ent of coval ency

(ii) Potassium ion / K+ less polarising (than Ca2+) (1)

KI (close to) 100 % ionic / no covalent character (1)

CaI2 partially/ significantly covalent

OR
Correct description of anion polarisation in CaI2 (1) (3 marks)
NOT j ust ‘ di st or t i on’ of ani on

Total 13 marks

3
3. (a) Ethylmagnesium bromide or formula, or any other halide NOT C2H5BrMg, (1)
Dry ether/ ethoxyethane
Followed by hydrolysis/ acid/ water (1)

Gr i gnar d r eagent / named r eagent wi t h i ncor r ect al kyl gr oup scor es (0) f or (1)
r eagent but can scor e bot h condi t i on mar ks.
If hal ogenoal kane gi ven as r eagent , can scor e 1st mar k i f Mg i ncl uded under
condi t i ons. (3 marks)

(b) (i) Obser vat i on

ef f er vescence/ bubbl es/ f i zzi ng (1)
NOT gas evol ved

2C2H5COOH + Na2CO3 → 2C2H5COONa + CO2 + H2O (1) (2 marks)

(ii) Observation
steamy/ misty/ white fumes (1)
NOT smoke
C2H5COOH + PCl5 → C2H5COCl + POCl3 + HCl (1) (2 marks)

(c) Reagents potassium dichromate ((VI)) / K2Cr2O7, (1)

sulphuric acid/ H2SO4/ hydrochloric acid/ HCl but conseq. on an oxidising agent (1)
ALLOW acidified potassium dichromate / H+ and Cr2O72- (2)
ALLOW acidified dichromate ions (2)
Aci di f i ed di chr omat e (wi t hout i on) scor es j ust (1)
ACCEPT
Potassium manganate(VII) / potassium permanganate/ KMnO4 / Tollens’ * /
Fehling’s* (1)
Acidified /alkaline*/neutral (1)
* need to acidify to liberate free acid for 2nd mark (2 marks)

(d) (i) Reagent Condi t i on

(any one of ) (t o mat ch)
HCN and KCN
HCN or KCN (buffered between) pH between 6 and 9
KCN + acid /H+ NOT excess
HCN + base / OH− NOT excess (2)

Type of reaction
Nucleophilic addition - bot h wor ds needed (1) (3 marks)
(ii) Reagent Condi t i on
(any one of ) (t o mat ch)
Hydrogen Pt / Ni / Pd (catalyst) – IGNORE r ef t o t emp.
Sodium (in) ethanol
Lithium aluminium hydride dry ether/ ethoxyethane
Sodium borohydride (in) aqueous/ water/ ethanol/ methanol
(2)
Type of reaction
Reduction
ACCEPT redox / hydrogenation (not addition)
ACCEPT nucleophilic addition if metal hydrides used (1) (3 marks)

4
(e) (i)
H H O
C C N C CH3 (1)
H
O
C
O CH3 (1)

O
ALLOW NHCH3

If C O represented as CO, penalise once only

(2 marks)

(ii) H H H H
+ -
H C C C C NH3Cl + -
H H OH H OR NH3 Cl

OR

H H H H
H C C C C NH3Cl
H H OH H

OR

H H H H
+
H C C C C NH3
+
H H OH H OR NH3

NOT

H H H H
H C C C C NH3 Cl
H H OH H

+
If show all bonds in NH3, + charge must be shown on N atom
ie H
+
N H
H (1 mark)

5
(f) Optical
NOT st er eo (1)

CH2NH2 H2NH2C

C C CH2NH2
CH2CH3 CH3CH2 OH OR
HO H C
H

ALLOW -C2H5 for -CH2CH3

MUST show the two as object and mirror image

e.g. (2)
OR are acceptable
C C

but NOT

C must not be bonded t o H i n OH gr oup

Near -mi ss mol ecul e pl us mi r r or i mage (1)
The t wo sol i d l i nes i n 3D st r uct ur e must not be at 180° (3 marks)

Total 21 marks

6
4. (a) (i) Kp = p(CO2) al l ow wi t hout br acket s, IGNORE p[ ] (1 mark)
(ii) 1.48 (atm)

Penal i se wr ong uni t

Answer i s consequent i al on (a)(i ) e. g. 1 must have atm-1 (1 mark)
1.48
(b) (i) Kp = p(Cl2) x p(NO)2 al l ow wi t hout br acket s, penal i se [ ] (1 mark)
2
(p(NOCl))
(ii) 2NOCl ⇌ 2NO + Cl2
Start 1 0 0
∆ -0.22 +0.22 +0.11
eq moles 0.78 0.22 0.11 (1)

total moles of gas 1.11

mole fractions above values ÷ 1.11 (1)
0.7027 0.1982 0.09910

partial pressure / atm above values x 5.00 (1)

3.51 0.991 0.495

Kp = 0.495 atm x (0.991 atm)2 (1)

2
(3.51 atm)

= 0.0395/ 0.0394 atm (1)

r ange of answer s 0. 0408/ 0. 041 Æ 0. 039/ 0. 0392 NOT 0. 04
ACCEPT ≥2 S.F
Cor r ect answer pl us some r ecogni sabl e wor ki ng (5)

Mar ks ar e f or pr ocesses
• Equi l i br i um mol es
• Di vi di ng by t ot al mol es
• Mul t i pl yi ng by t ot al pr essur e
• Subst i t ut i ng equilibrium val ues i nt o expr essi on f or Kp (5 marks)
Cal cul at i ng t he val ue of Kp wi t h cor r ect consequent i al uni t .
(iii) As the reaction is endothermic – st and al one (1)

the value of Kp will increase (as the temperature is increased) – (1)

consequent i al on 1st answer (i f exot her mi c (0) t hen Kp decr eases (1) )
For ef f ect on Kp mar k, must have addr essed whet her r eact i on i s
endot her mi c or exot her mi c (2 marks)

(iv) Because (as the value of Kp goes up), the value of

pCl2 x (pNO)2/(pNOCl)2 (the quotient) must also go up (1)

and so the position of equilibrium moves to the right – st and al one (1)

But mar k consequent i al l y on change i n K i n (i i i )

If “ posi t i on of equi l i br i um moves t o r i ght so Kp i ncr eases” (max 1) (2 marks)
IGNORE r ef er ences t o Le Chat el i er ’ s Pr i nci pl e
Total 12 marks

7
5. (a) CH3COOH labelled as base and linked to CH3COOH2+ labelled (conjugate) acid (1)
H2SO4 labelled acid and linked to HSO4- labelled (conjugate) base (1)
If aci ds and bases cor r ect but not cl ear l y or cor r ect l y l i nked 1 (out of 2)
Just l i nk but no i dent i f i cat i on of aci ds and bases (0) (2 marks)

(b) (i) (pH) more than 7/ 8-9 (1)

Indicator: phenolphthalein ALLOW thymolphthalein OR thymol blue

(mar k consequent i al l y on pH) (1)
Mar k consequent i al l y on pH but i f pH7 do not al l ow ei t her met hyl (2 marks)
or ange or phenol pht hal ei n
QWC* (ii) As OH- / base removes H+ ions / ∆Hneut is per mole of H2O produced / (1)
H+ + OH- = H2O
the equilibrium shifts to the right (1)
and so all the ethanoic acid reacts (not just 1% of it) (1)
OR
Endothermic (OH) bond breaking (1)
is compensated for (1)
by exothermic hydration of ions (1)
OR
∆H for CH3COOH + H2O → CH3COO- + H3O+ = +2 kJ mol-1 / almost zero /
very small (1)
∴ ∆Hneut [CH3COOH] = +2 + ∆Hneut [HCl] (1)
≈ the same (for both acids) (1)
OR
∆Hneut is per mole of H2O produced (1)
(heat) energy required for full dissociation (of weak acid) (1)
so ∆Hneut slightly less exothermic (for weak acid) (1) (3 marks)

(iii) [H+]2 = Ka [CH3COOH] = 1.74x10-5 x 0.140 = 2.44x10-6

[H+] = 0.00156 (mol dm-3) (1)

pH = 2.81 consequent i al on [ H+] but not pH>7 (1)

ACCEPT 2.80/2.8 (answers to 1 or 2 dp)

The assumptions are two from:

[H+] = [CH3COO-] - t hi s mar k can be ear ned f r om wor ki ng /
negligible [H+] from ionisation of water (1)

[CH3COOH] = 0.140 – [H+] ≈ 0.140 (mol dm-3) / ionisation of acid

negligible (1) max
solution at 25 oC (1) (2) (4 marks)

(iv) 1.74 x 10-5 = [H+] [salt]

[acid] (1)

[H+] = 1.74 x 10-5 x 0.070 = 1.22 x 10-5 (1)

0.100
pH = 4.91 / 4.9 / 4.92 NOT 5
Max 2 i f 0. 140 / 0. 200 i s used (1) (3 marks)
Total 14 marks
TOTAL FOR PAPER: 75 MARKS