Raffles Junior College JC2 H2 Chemistry 2007/8 Suggested Answers to Nov 2007 Chemistry 9746 Paper 1

Suggested Solutions to Nov 2007 Chemistry 9746 Paper 2 Question 1 (a) Alkanes (b) (c) 2 C14H30 + 43 O2 28 CO2 + 30 H2O (i) Total mass of C14H30 burnt = 10700 x 10.8 = 115560 kg = 116 tonnes (3 s.f.) (ii) Mr of C14H30 = (4 x 12.0 + 30 x 1.0) = 198 Amount of C14H30 burnt = (1.16 x 105) / 198 = 585.9 mol Amount of CO2 produced = (585.9 / 2) x 28 = 8202 mol Mass of CO2 produced = 8202 x (12 + 16.0 x 2) = 361000 kg (3 s.f.) = 361 tonnes (d) P = 6 bar = 6 x 105 Pa Using PV = nRT, the amount of air (e) T = 5oC = 278 K V = 670 cm3 = 6.7 x 10-4 m3 n = 0.165 mol Using PV = nRT, the internal pressure of the tyre = (0.165x8.314x278)/ 6.7 x 10-4 = 5.69x105 Pa (f) Difference in pressure= Pinternal Pexternal = 5.69x105 0.28x105 = 5.41x105 Pa Safe difference in pressure = (8 1.01) x105 = 6.99x105 Pa Based on the above calculation, it is still within the safety range, thus dont have to deflate! V = 670 cm3 = 6.7 x 10-4 m3 T = 293 K = (6x105x6.7x10-4)/(8.314x293) = 0.165 mol

Question 2 (a) In cold aqueous NaOH, In hot aqueous NaOH, (b) (i) Reactant Products

Cl2(g) + 2OH(aq) Cl(aq) + ClO(aq) + H2O(l) 3Cl2(g) + 6OH(aq) 5Cl(aq) + ClO3(aq) + 3H2O(l)
Species Cl Cl Oxidation number 0 -1 ClO +1 Species Oxidation number

(ii) Chlorine undergoes disproportionation in this reaction.

(c)

(i) O2 + 2H+ + 2e

H2O2

(ii) 2ClO3 + H2O2 + 2H+ 2ClO2 + O2 + 2H2O (iii) It is a reducing agent in this reaction.

Question 3 (a) (i) 6 (ii) 5[Co(H2O)6]2+ + ClO2 + 4H+ 5[Co(H2O)6]3+ + Cl + 2H2O EOcell = +1.50 (+1.82) = 0.32 V Since EOcell < 0, reaction is not energetically feasible and no reaction happens. (iii) [Co(NH3)6]2+ (iv) [Co(NH3)6]3+ is formed. 5[Co(NH3)6]2+ + ClO2 + 4H+ 5[Co(NH3)6]3+ + Cl + 2H2O EOcell = +1.50 (+0.11) = + 1.39 V. Since EOcell > 0, reaction is spontaneous.

Question 4 4(a) 2CHCl3(l) + O2(g) 2COCl2(g) + 2HCl(g) Let Hof [COCl2(g)] be x kJ mol-1 Hor = -356 = [2x + 2(-92)] - [2(-134) + 0] x = -220 kJ mol-1 (b) (c) Oxidation of chloroform probably takes place in the presence of sunlight, where the light energy results in the formation of highly reactive radicals. (i) Ho = -356 kJ mol-1

(ii) (d) (i) (ii)

120o Stage I: Nucleophilic substitution Stage II: Elimination Mechanism:

O C + Cl Cl Cl Cl
-

:OH -

O C
-

OH Cl

(e) (f)

COCl(OC2H5) or CO(OC2H5)2 (i) (ii) (i) (ii) NH3 In the presence of strong acids, the lone pair of electrons on N can be donated to form a dative co-ordinate bond with a proton, thus behaving as a proton acceptor. 4CO(NH2)2 + 6NO2 4CO2 + 7N2 + 8H2O NO2 gas is highly toxic or excess NO2 gas in the atmosphere can cause acid rain.

(g)

O C OH + Cl -

Question 5 (a) Reagent Compound A, B, C or D

Structural Formula of Organic Product

3HCO 3H C C O O

Reagent

Compound A, B, C or D

Structural Formula of Organic Product

CH3COCl

Dilute HNO3

Na

Tollens reagent

(b)

(i)

OH Br OCH3 Br

OH OCH3

CH2CH CH2 Br
COOH

CH2CH CH2
OR

Br

OH Br

O C CH3
(ii) (c)(i)

OCH3

AND

HO

(ii)

Stage I Sage II

Reagent(s): LiAlH4 (Note: H2/ Ni not accepted) Conditions: in dry ether Reagent(s): CH3COOH Conditions: catalytic amount of conc H2SO4, heat (or: CH3COCl, room temperature) 6

O CH C HC O

HC H C2 HC

HCO

aN O

H C H C2 H C

HCO

HO

ON

H C H C 2H C
HO2HC HC HC

Suggested Solutions to Nov 2007 Chemistry 9746 Paper 3 Question 1 (a) (b) Kp = pCH3CH2 CH2 CHO/ pCH3CH=CH2 x pCO x pH2 atm-2 (i) Equilibrium partial pressures of C3H6, CO and H2 are 0.4 atm C3H6 40 -39.6 0.4 Kp = 39.6 / 0.43 = 618.8 atm-2 Higher pressure favours the formation of butanal, By LCP the forward reaction is favoured to reduce the numbers of moles of gases. S is negative as the number of gas particle decreases and the system becomes more orderly. G= H-T S Given that G is negative, then H must be at least as negative as T S. By considering the bonds broken and the bonds formed, the value of H for reaction I could be calculated as follows; Bonds broken (endothermic) 1 C-C 1 C=C 6 C-H 1 CO 1 H-H H= = (c) (i) (+350) (+610) 6x(+410) (+1077) (+436) Bonds formed (exothermic) 3 C-C 1 C=O 8 C-H 3x(-350) (-740) 8x(-410) + CO 40 -39.6 0.4 + H2 40 -39.6 0.4 CH3CH2 CH2 CHO 0 +39.6 39.6

Initial/atm Change/atm Final/atm (ii) (iii) (iv)

(v) (vi)

(+350)+(+610)+6(+410)+(+1077)+(+436)+3(-350)+(-740)-8(-410) -137 kJmol-1

Reaction II : K2Cr2O7(aq), dilute H2SO4, heat or KMnO4(aq), dilute H2SO4, heat Reaction III : H2 + Ni catalyst and heat or NaBH4(aq) or LiAlH4 in dry ether To 1bromobutane : HBr, heat (must use heating) or PBr3 or PBr5 or SOBr2 (the last three reagents do not require heating) To 2bromobutane : Step 1 : conc. H2SO4 at 180 C or pass butan1ol vapour through heated Al2O3 ; Step 2 : HBr (g) 2Iodobutane reacted faster than 2bromobutane. Bond energies of CBr and CI bonds are 280 and 240 kJ mol1 respectively. The reaction involves breaking the weaker CI bond in 2iodobutane vs a stronger CBr bond in 2bromobutane.
H3C CH CN CH2CH3
H3C CH CH2NH2 CH2CH3

(ii)

(d)

(i)

(ii)

intermediate

; product

H3C

CH OH

CHCH3 OH

intermediate H3C

CH

CH2CH3 ; product

(e)

Ratio of 1bromobutane : 2bromobutane is 3: 2 since there are 6 primary H atoms but only 4 secondary H atoms in butane.

Question 2 (a)
1 Ionisation Energy x x x x x x x
st

Na

Mg

Al

Si

Cl

Ar

Across the period, Nuclear charge increases Shielding effect remains approximately constant since electrons are added to the same outermost principal quantum shell Effective nuclear charge increases Electrons are attracted closer to the nucleus Hence, the general trend of 1st IE increases across period 3. (b) MgO being ionic is a basic oxide (reacts with acid) Al2O3 is ionic with covalent character, hence it is amphoteric (reacts with both acid and base) SiO2 being covalent is an acidic oxide (reacts only with concentrated base)

Thus, the 3 oxides can be distinguished based on their reactions with acid/ base. Compounds Observation upon addition of water Does not dissolve Does not dissolve Observation upon addition of dilute HCl Dissolves in HCl Equation: MgO + 2H+ Mg2+ +H2O Dissolves in HCl Equation: Al2O3 + 6H+ 2Al3+ + 3H2O Does not dissolve in HCl since it does not react with HCl Observation upon addition of dilute NaOH Does not dissolve in NaOH since it does not react with NaOH Dissolves in NaOH Equation: Al2O3 + 2OH + 3H2O 2Al(OH)4 Does not dissolve in dilute NaOH. (although it does dissolve in conc NaOH)

MgO

Al2O3

SiO2

Does not dissolve

(c) NaCl has a giant ionic lattice, it dissolves in water to form the aquated ions, Na+ (aq) and Cl-(aq). NaCl (s) + aq Na+ (aq) + Cl-(aq) Since Na+ has a low charge density, and hence low polarizing power, it does not weaken the O-H bond in water significantly enough to cause hydrolysis. no additional H+ ions are formed Thus, pH remains at 7 (solution is neutral) PCl5 is a simple covalent molecule When added to water, PCl5 reacts with water to form HCl and H3PO4. PCl5 + 4H2O H3PO4 + 5HCl Although H3PO4 is a weaker acid, HCl is a strong acid which dissociates completely in water to form H+ ions. 9

 (d)

Thus, the resulting solution is strongly acidic and has a low pH of 1. (i) (ii) (iii) The reaction should be done in the fume cupboard since a poisonous gas, SO2, and HCl which is corrosive (or acidic) will be produced in the reaction. SOCl2 + H2O SO2 + 2HCl White ppt of formed. Ag+(aq) + Cl(aq) AgCl(s) Orange solution turns green. Cr2O72 +2H+ + 3SO2 2Cr3+ + 3SO42 + H2O
COOH COCl

(e)

(i) (ii) (iii)

A:

COOH

B:

COCl

I : acidbase reaction (or neutralization) ; II : nucleophilic substitution; III : hydrolysis dilute HCl (aq) , heat or dilute NaOH(aq), heat

10

Question 3 (a)(i)
energy Ca2+(g) + 2e + 2F(g) BE(F F) Ca (g) + 2e + F2(g) IE2 of Ca
2+

Note: IE1 = first ionisation energy IE2 = second ionisation energy EA = electron affinity BE = bond energy

2 EA of F Ca (g) + 2F (g)
2+

Ca (g) + e + F2(g) IE1 of Ca Ca(g) + F2(g) Hatom [Ca(s)]

Lattice energy of CaF2

Ca(s) + F2(g) Hf [CaF2(s)] CaF2(s)

By Hess law, lattice energy of CaF2(s) = Hf[CaF2(s)] Hatom[Ca(s)] IE1[Ca(g)] IE2[Ca(g)] BE(FF) 2EA of F = 1220 178 590 1150 158 (2)(328) = 2640 kJ mol-1 (a)(ii)
+

Since the ionic radius of F is smaller than that of Cl-, the magnitude of the lattice energy of CaF2 is greater than that of CaCl2. Though the ionic radius of F- is smaller than that of O2-, its charge is only half that of O2-. The smaller charge of F- results in the magnitude of the lattice energy of CaF2 being smaller than that of CaO. (b)(i) Ksp of CaF2 = [Ca2+(aq)][F-(aq)]2 In the given saturated solution of CaF2, [Ca2+] = 2.3 x 10-4 mol dm-3 [F-] = (2)(2.3 x 10-4) = 4.6 x 10-3 mol dm-3 Ksp of CaF2 = (2.3 x 10-4)(4.6 x 10-4)2 = 4.87 x 10-11 mol3 dm-9

ygrene ecittal

11

(b)(ii)

Hsolution [CaF2(s)]

Ca(s) + F2(g)
By Hess law, Hsolution[CaF2(s)]

= Hf [CaF2(s)] + Hf [Ca2+(aq)] + 2Hf [F-(aq)] = (1220) 543 (2)(333) = +11 kJ mol-1

(b)(iii) CaF2(s) Ca2+(aq) + 2F-(aq) Hsolution[CaF2(s)] > 0

Consider the above equilibrium reaction in which Hsolution[CaF2(s)] is endothermic. When temperature is increased, the equilibrium position shifts right, favouring the forward reaction. This shift is in accordance to Le Chateliers principle as the system attempts to remove the added heat energy via the forward endothermic reaction. Hence CaF2 will be more soluble in hot water than in cold water. (c)(i) Be(NO3)2 has a low melting while Ca(NO3)2 has a high melting point. Thus Be(NO3)2 is a simple molecular covalent compound, whereas Ca(NO3)2 is a typical ionic compound with a giant lattice. Mg(NO3)2 MgO + 2NO2 + O2

(c)(ii)

Ca2+ has a larger ionic radius than Mg2+ but same charge. This means that Ca2+ has a lower charge density and hence a lower polarising power than Mg2+. Ca2+ distorts the electron cloud of the NO3 anion to a lower extent than Mg2+. Hence, the NO bond in Ca(NO3)2 is less easily broken resulting in Ca(NO3)2 decomposing at a higher temperature.

(d)(i)
O C H H H3C O C H H3C O C CH3 in the ratio of 1: 2 : 1

(d)(ii)

To distinguish between the aldehydes and ketone : use Tollens reagent and warm H2CO and CH3CHO : silver mirror formed. CH3COCH3 : no silver mirror formed. To distinguish between H2CO and CH3CHO : use aq I2 and aq NaOH, warm H2CO : no yellow ppt formed CH3CHO : yellow ppt formed.

2+

Hf [CaF2(s)]

.qa +

CaF2(s)

Ca2+(aq) + 2F-(aq) Hf [Ca2+(aq)] Hf [F (aq)]

-

12

Question 4 (a) (i)

H + CN - Ka = HCN ] [
HCN H+ + CN

(ii)

H + CN - Ka = [ HCN ]
[H+]2 / [HCN] = 4.9 x 1010 mol dm-3 [H+]2 / 0.100 = 4.9 x 1010 [H+] = 7 x 106 mol dm-3 Percentage dissociation of HCN = ([H+]/ [HCN]) x 100 = (7 x 106 / 0.100) x 100 = 0.007% When NaCN is added to the aqueous solution of HCN acid, it ionizes fully to give Na+ and CN ions. HCN H+ + CN The introduction of the common ion, CN will cause the equilibrium position of the above equilibrium system to shift to the left according to Le Chateliers principle. This will cause suppress the ionization of HCN and cause less HCN to dissociate, and so it will decrease the percentage of HCN molecules ionized. (b)(i) Order of reaction with respect to a reactant is the power to which the concentration of that reactant is raised to in the rate equation. The overall order of the reaction is the sum of the individual orders. By inspection method: Comparing expt 1 & 2: Initial [HCN] and [NaCN] are kept constant in both expts. When [(CH3)2CO] is increased from 0.040 to 0.050 mol dm3 (i.e. by 1.25 times), the relative initial rate increases from 1.00 to 1.25 mol dm3. Hence the order of reaction with respect to (CH3)2CO is one. Comparing expt 1 & 3: Initial [(CH3)2CO] and [HCN] are kept constant in both expts. When [NaCN] is changed from 0.008 to 0.006 mol dm3 (i.e. decreases by 1.33 times), the relative initial rate decreases from 1.00 to 0.75 mol dm3 (i.e. decreases by 1.33 times). Hence the order of reaction with respect to NaCN is one. Let y be the order of reaction with respect to HCN. Rate = k[(CH3)2CO][NaCN][HCN]y Substituting values from expt 3 into the equation, 0.75 = k(0.040)(0.006)(0.040)y Substituting values from expt 4 into the equation, 0.94 = k(0.050)(0.006)(0.050)y 13

(iii)

(ii)

Thus, 0.94/0.75 y = (0.050/0.040)(0.050/0.040)y = (5/4)y+1 =0

Hence the order of reaction with respect to HCN is zero. Therefore, Rate = k[(CH3)2CO][NaCN] (iii) Generation of nucleophile, CN HCN is a weak acid and hence a poor source of CN ion. The CN ion comes initially from the catalytic amount of NaCN(aq) added: NaCN(aq) Na+(aq) + CN(aq) Step 1: Nucleophilic attack by the CN ion on the carbonyl carbon
CH3 C O CN

: CNslow

CH3

O-

CH3 H

H CH3

Step 2: Protonation of the anionic intermediate to form cyanohydrin

CN CH3 C OCN

H C

N fast

CH3

OH

+ CN-

H 3 CH

H 3 CH

(iv)

The carbonyl carbon in CH3CH2CHO is less sterically hindered than that in (CH3)2CO, hence more easily attacked by the nucleophile. In addition, the carbonyl carbon in CH3CH2CHO is also more electron deficient (more +) than that of (CH3)2CO as the latter has an additional electron donating methyl group. NaCN provides the initial CN ions for the nucleophilic attack on the carbonyl carbon. HCN is used in the second step as a (Bronsted) acid. (Do NOT merely say that NaCN is the catalyst while HCN is the reagent)

(v)

14

(c)
O CH3CH2 C H
+

OH HCN CH3CH2 C D H CN

OH H C CH2CH3 CN E

propanal

equimolar mixture of two optical isomers Optical Isomerism OH CH3CH2 C D H CN OH

or

H C CH2CH3 CN E

Al2O3 heat

CH3 C C H

H
+

CH3 C C H

CN
+

CN

H2 O

Both optical isomers, D & E, can lose a H and OH through dehydration from adjacent C atoms in 2 different ways to give cis-trans isomers, F & G.

trans-isomer F

cis-isomer G

Geometric (cis-trans) Isomerism

Displayed formulae of compounds D to G. H H H C C H H O H C H C N N H O H C C H H C C H H H H C H H C C C N trans-isomer F H H H H cis-isomer G H C C C H H C N

Optical isomer D

Optical isomer E

15

Question 5 (a) (i) Hydrogen atom joined to an electronegative atom (N, O or F) in one molecule an atom with a lone pair of electrons in the other molecule
H H O

H-bond
N H H H

+
(ii)

Attractions betw RCO2H molecules consist of both van der Waals forces (betw the R-chains) and hydrogen bonding (betw the CO2H groups) Attractions betw H2O molecules and themselves, or betw H2O molecules and RCO2H molecules are mainly hydrogen bonding As the chain length increases, the van der Waals bonding betw RCO2H molecules become predominant and the long hydrophobic chains get in the way of, and interfere with, the hydrogen bonding betw H2O molecules and themselves. Thus the solution of long chain RCO2H molecules would entail (hydrogen) bond breaking, and be too endothermic a process for the positive entropy of solution to counter.

(b) (i) (ii)

N H

the sequence of the amino acids in a protein chain

H C CH2 CH2 C H O H O O C N H H H C CH2 C CH3 CH3 O C N H H C CH2 CH2 CH2 CH2 N H O C

Any 3, any sequence. Need to show displayed formula, all bonds clearly shown, especially NHCOpeptide group. Need to show 3 repeating NH-CHR-CO- sequence in the chain (with N-terminal and C-terminal) (iii) >NH group of each peptide link is hydrogen bonded to the >C=O group of the fourth following peptide link To include a sketch of the helix -CH2-SH + HS-CH2 + [O] -CH2-S-S-CH2- + H2O (note that the CH2chain is required) Total number of disulphide bridges possible = 18 (v) (vi) Ionic interactions (lys-glu) (Note: Hydrogen bonding NOT accepted) Hydrogen bonding (lys-ser or thr-glu or thr-ser) Any two of the three non-polar amino acids (leu, val or phe)

(iv)

(vii) Any three of the polar amino acids (glu, lys, thr, ser) 16