Marking Scheme - GERAK GEMPUR CHEMISTRY 2 ( 2012 ) SECTION A ( STRUCTURE ) ester No.

. of moles of oil = mass of oil = formula mass No. of moles of CH3OH = SCORE 1 mk 1013.0 = 1.144 885.6 1 mk REMARKS

a b

200.0 = 6.25 32.0

From equation, 1 mole oil 3 moles CH3OH 1.144 moles oil 3(1.144) = 3.432 moles CH3OH Excess CH3OH = 6.25 3.432 = 2.818 = 2.82 moles ( 3 sf ) c (i) Dynamic equilibrium a condition in a reversible reaction when the rate of forward reaction = rate of reverse reaction Kc = [glycerol] [biodiesel]3 [vegetable oil] [methanol]3 1 mk 1 mk

(ii)

1 mk

(iii)

-so that equilibrium shifts to the right according to Le Chateliers Principle OR -to increase the yield of biodiesel - Catalyst NaOH has no effect on the position of equilibrium i.e. it has no effect on the yield of biodiesel - as a catalyst increase the rate of both the forward and reverse reactions to the same extent 3.432 moles CH3OH 3.432 moles biodiesel = 3.432 x formula mass = 3.432 x 296.0 = 1015.9 g ( theory) % yield of biodiesel = 811.0 g x 100 = 79.83 % 1015.9 g ( 4sf )

1 mk

either answer

(iv)

1 mk 1 mk

1 mk

1 mk Total = 10 mk 1 mk

Minimum energy required to remove 1 mole electron from 1 mole atom of the element in gaseous state - IE1 increases across Period 3 from Na to Ar - Effective nuclear charge increases due to increase in no. of protons but screening effect is constant P : 1s2 2s2 2p6 3s2 3p3 S : 1s2 2s2 2p6 3s2 3p4 P has extra stability due to half-filled p orbitals - Repulsion between e- pair in 3p of S enables the first mole of e- to be easily removed - Hence IE1 of P > IE1 of S -1-

1 mk 1 mk

1 mk 1 mk 1 mk

SECTION A ( STRUCTURE ) d (i) F B 120o H F F trigonal planar (ii) xx xx F xx xx xo xx F xo B S x H xx xo x xx F xx H xx - B atom is e- deficient, having an empty orbital while S has an e- pair to donate A coordinate / dative bond forms between BF3 and H2S 3 a Rate2 = 5.05 x 10 6 = ( 0.200 ) n Rate1 2.53 x 10 6 ( 0.100 ) n 2 = 2n , n=1 first order w.r.t. H2 Rate3 = 10.10 x 10 6 = ( 0.200 ) n Rate1 2.53 x 10 6 ( 0.100 ) n 2 n 3.99 4 = 2 = 2 , n=2 second order w.r.t. NO b c Rate = k[NO]2 [H2] Using expt 1 : k = Rate1 = 2.53 x 10 6 mol dm3s-1 [NO]2 [H2] (0.100)2(0.100)( mol dm3)3 = 2.53 x 10 3 mol 2 dm6 s 1 ( 3 sf ) d - At equilibrium for step 1 K = [X]___ [NO][H2] - For step 2, slow or rate determining step , - Rate = k [X][NO] = kK[NO] [H2] [NO] = kK[NO]2[H2] - Mechanism agrees with experimental rate expression. Rate of formation of H2O(g) = 2 x rate of formation of N2(g) = 2 (2.53 x 10 6 ) mol dm3s-1 = 5.06 x 10 6 mol dm3s-1 (3sf) sp2 hybridisation Side-by-side / sideways overlapping of 2 unhybridised 2p orbitals -2105 H
o

SCORE 1 mk S 1 mk

REMARKS

V-shaped / bent

1 mk

1 mk Total = 10 mk 1 mk 1 mk 1 mk 1 mk 1 mk 1 mk Max 3 mk

1 mk 1 mk 1 mk 1 mk 1 mk 1 mk 1 mk 1 mk 1 mk

Max 3 mk

a (i) (ii)

SECTION A ( STRUCTURE ) 4 b(i) Any one H2C=CHCH2CH3 1 butene H2C=C(CH3)2 methylpropene cyclobutane

SCORE 1 mk

REMARKS

methylcyclopropane CH3 (ii) CH3 CH3 C=C H H cis 2 butene CH3 H C=C H CH3 trans 2 butene 2 mk

c or
( both are saturated hydrocarbons )

1 mk CH3

d (i)

- plastics have a wide range and versatile uses - cheap - chemically inert products CH3 CH3 CH3 CH3 CH3 CH3 C H C H C H C H C H C H

1 mk 1 mk

Any 2

(ii)

1 mk

(iii)

- Monomers are small monomers with with weak intermolecular forces of attraction e.g. VDW or H-bonds

1 mk

-3-

a(i)

(ii)

SECTION B ( ESSAY ) - 9 X : 1s 2s 2p5 Group 17, non-metal , electronegative, accepts electron - 19 Y : [Ar] 4s1 Group 1, metal, electropositive , donates electron + Y + X [ Y ] [ X ] - Involves transfer of electron from metal to non-metal. YX is an ionic compound. - 34 Z : [Ar] 3d10 4s2 4p4 Group 16, non-metal , electronegative - Both X and Z combine through sharing of electron pairs . X2Z covalent compound. X Z X
2 2

SCORE 1 mk 1 mk

REMARKS

1 mk

1 mk 1 mk 1 mk

Any 6

1 mk Max 6 mk 2 mk Any 2

b(i)

- Strong electrostatic forces of attraction exist between oppositely-charged ions, Y+ and X , difficult for solid YX to vapourise, making YX non volatile. - X2Z exists as simple covalent molecules. with weak VDW forces between them. - Thus X2Z have lower b.p. than YX , making it more volatile than YX. - In molten state or in aqueous solution, the ions in YX are mobile, making it an electrical conductor. - X2Z being neutral molecules, are unable to conduct electricity. - Activation energy - minimum energy that must be overcome by the reactant particles before a reaction can occur, forming products Energy Ea R(g)+S(g) H = positive Reaction
Ea = activation energy H = enthalpy of reaction

(ii)

1 mk 1 mk

c(i)

1 mk

(ii)

2 mk

P(g)+Q(g)

(iii)

- Catalyst increases the rate of a reaction by providing an alternative pathway, with a lower activation energy, Ea - More reactant particles have energy equal or greater than the lower activation energy,increasing the no. of effective collisions.

1 mk 1 mk

-4-

a(i)

3 mk

axes + correct units 1 mk correct plot - 1 mk balanced graph - 1 mk

a(ii)

(ii) (iii)

- straight line parallel to x-axis ( as shown ) - Gas M is a non-ideal gas, it does not obey Boyles law as pV is not constant for all pressures of p. - Non-ideal gas shows ideal behaviour under low pressure. At p = 0 kPa, pV = 6.83 x 103 kPa m3 - Assuming gas M is ideal, pV = mRT Mr Mr = mRT = ( 65.0 g ) ( 8.31 J K 1 mol 1 ) ( 298 K ) pV 6.83 x 103 N m2 m3 Mr = 23.6 ( 3sf )

1 mk 1 mk

(iv)

1 mk

1 mk 1 mk Total 8 mk

Pressure ( atm ) 3 mk correct axes - 1 mk correct curves - 1 mk correct areas - 1 mk 1 atm Temp.(oC ) -5-

solid 5.1 atm

liquid

gas

triplepoint

- Triple point for solid CO2 has a pressure above 1 atm., so when temperature of a sample of solid CO2 increases, it turns to gas without melting. c(i) - H2O H + OH Kw = [H+][OH ]
+

1 mk Total 4 mk 1 mk

(ii)

- At 25 oC, Kw = 10 14 mol2 dm 6 0.200 mol dm3 NaOH [OH ] = 0.200 mol dm3 [H+] = 1014 = 1014 = 5.00 x 10 14 mol dm3 [OH ] 0.200 - pH = - log10 [H+] = 13.3 ( 3 sf )

1 mk

1 mk 1 mk 1 mk 1 mk 1 mk 1 mk 1 mk 1 mk 1 mk 1 mk each

Total 3 mk

a(i)

- 2 Na + 2 H2O 2 NaOH + H2 (g) Sodium burns & fizzes on the surface of the water. - pH of strong alkali NaOH about 13 - Phosphorus has no reaction with water. - 4 Na + O2 2 Na2O Sodium burns in air vigorously. - Na2O + H2O 2 NaOH - 4 P + 5 O2 P4O10 OR 4 P + 3 O2 P4O6 - P4O10 + 6 H2O 4 H3PO4 OR P4O6 + 6 H2O 4 H3PO3 - pH for a weak acid, H3PO4 or H3PO3 about 3

(ii)

Total 8 mk

b(i)

- Electrolyte used is molten aluminium oxide. - Cryolite, Na3AlF6 is added to lower the melting point of Al2O3 from 2050 oC to 900 oC . - Graphites are used as electrodes. - At cathode : Al3+(l) + 3e Al (s) - At anode : 2O2 (l) O2 (g) + 4e - AlF3 is an ionic compound with covalent character, with strong electrostatic forces of attraction between its Al3+ and F ions - Cl ion bigger than F ion, polarised by Al3+ ion making - aluminium chloride exists as simple covalent dimer Al2Cl6 molecules with weak intermolecular Van der Waals forces. - 50.0 mg = 50.0 103 g = 0.0500 g 1 mole HCN = 1.0 + 12.0 + 14.0 = 27.0 g - No. of moles HCN = 0.0500/27.0 = 0.00185 ( 3 sf ) - Forward reaction is endothermic, according to Le Chateliers principle - high temperature will shift equilibrium to the right increasing the yield of HCN. - Forward reaction involves an increase in volume of gases - so high pressure will not favour production of HCN as -6-

Total 5 mk

(ii)

Any 2

Total 2 mk 1 mk 1 mk 1 mk 1 mk 1 mk 1 mk

b(i)

(ii)

equilibrium will shift to the left. c NH3(g) + CH4(g) HCN(g) + 3H2(g) Initial/mol 0.200 0.200 0 0 Change/mol__- 0.100 - 0.100 + 0.100__ +3(0.100) Eqm/mol 0.100 0.100 0.100 0.300 Kc = [HCN][H2]3 = (0.100)(0.300)3 = 0.270 mol2 dm6 [NH3][CH4] (0.100)(0.100) d (i) - NaCN is salt of weak acid HCN, under hydrolysis in water CN + H2O HCN + OH giving an alkaline solution due to presence of OH ions - HCN + H2O H3O+ + CN HCN undergoes partial dissociation in water. NaCN Na+ + CN ( salt complete dissociates ) - Concentration of HCN and CN high in mixture. - Addition of an acid, H+ + CN HCN Addition of an alkali, OH + HCN H2O + CN - For a buffer, pH = pKa + log10 [ Salt ] [ Acid ] - pH = - log10 (4.90 1010) + log10 (1.00 x 200 /400) (0.500 x 200/400) = 9.61 ( 3 sf ) 9 a CH3 + HNO3 CH3 + H2O 1 mk NO2 Mechanism for nitration electrophilic substitution - Formation of electrophile, nitronium ion 2 H2SO4 + HNO3 2 HSO4 + NO2+ + H3O+ fast CH3 + NO2+ + NO2 CH3 + HSO4 NO2 -7+ H2SO4 fast 1 mk CH3 slow
intermediate arenium / carbonium ion

1 mk

2 mk

1 mk

(ii)

1 mk

1 mk 1 mk

(iii)

1 mk

1 mk

1 mk

1 mk

CH3 + H NO2

catalyst regenerated

b (i)

SnCl2 is a weak reducing agent, but LiAlH4, is a very strong reducing agent which can reduce - COOH group to CH2OH SnCl4
(+4)4(-1)

1 mk

(ii)

SnCl2
(+2)2(-1)

Cl2
0

1 mk

- Sn undergoes reduction, while Cl undergoes oxidation so reaction is a redox reaction (iii) Cl Sn Cl Cl Cl tetrahedral molecule

1 mk

1 mk

- White fumes and a white solid are observed - due to hydrolysis reaction. or SnCl4 + 2 H2O SnO2 (s) + 4 HCl (g) c - Sodium nitrite and dilute HCl are added to mixture. - Effervescence of a colourless gas observed. - HOOC C6H4 NH2 + O=NOH HOOC C6H4 OH + N2(g) + H2O OR

1 mk 1 mk

1 mk 1 mk 1 mk

1 mk - A little aqueous copper(II) sulphate solution is added to the mixture. - A dark blue solution is observed. - 2 H2NC6H4COOH + Cu2+ H2N C6H4 COO+ 2 H+ d (i) (ii) - Ethanol, concentrated sulphuric acid , reflux COOH + HOCH2CH3 COOCH2CH3 + H2O 1 mk Cu2+ NH2 - OOC C6H4 1 mk

1 mk

1 mk

NH2

NH2 -8-

(esterification)

10

CH3 CH3 C CH3 ,

CH3 1 mk CH3 C CH2Br 1 mk

Br H - 2-bromo-2-methylpropane is major product as its formation involves stable 3o free radical (CH3)3C
b(i)

1 mk

H X =

H H 1 mk

CH3 C = C C* CH2CH3 CH3 H2(g) H H H

Y =

CH3 C C C* CH2CH3 H H H CH3 H H

1 mk

X =

CH3 C = C C* CH2CH3 CH3 Oxidation

H

CH3COOH +

HOOC C* CH2CH3 CH3 (Z)

1 mk

- Both X and Y, each has a chiral C atom bonded to 4 different groups making it optically active. - X is an alkene with one double bond as only 1 mole of H2 can be added.

1 mk 1 mk

- X is unsaturated hydrocarbon but Y is saturated b(ii) - Bromine water OR acidified potassium manganate(VII) is added to liquid X and liquid Y in separate test tubes. - X decolourises reddish-brown bromine water OR purple colour of acidified KMnO4.

1 mk 1 mk

1 mk

-9-

- CH3CH=CHCH(CH3)CH2CH3 + Br2 CH3CH(Br)CH(Br)CH(CH3)CH2CH3 OR KMnO4/H+ - CH3CH=CHCH(CH3)CH2CH3 CH3CH(OH)CH(OH)CH(CH3)CH2CH3

H A = HOCH2 C* CH2CH3

1 mk

( reduction of RCOOH to 1o ROH )

1 mk

CH3 O H B = Cl C C* CH2CH3 CH3 H O C = CH3CH2 C C O CH3 Mg2+ 2 1 mk ( - OH Cl ) 1 mk