2008 PJC H2 Chemistry Prelim Paper 3 (Suggested Answers) 1 (a) (i) Using pV = nRT (38.9 x 101000)(2.

0 x 10-3) = ntotal x 8.31 x (273 + 30) [] Total no. of moles at equilibrium, ntotal = 3.12 mol [] SO2Cl2(g) 2 -x 2x SO2(g) + Cl2(g) 0 0 +x +x x x

Initial no of mol Change in no of mol Eqm no of mol

At equilibrium, ntotal = 2 x + x + x = (2 + x) mol x = 1.12 mol no. of mol of SO2Cl2 = 2 1.12 = 0.88 mol [1] no. of mol of SO2 = no. of mol of Cl2 = 1.12 mol [1] (ii) [SO2Cl2] = (0.88) = 0.44 mol dm-3 [] [SO2] = [Cl2] = (1.12) = 0.56 mol dm-3 [] Kc =

[1] for table

[ SO2 ][Cl2 ] [] = (0.56 )2 (0.44 ) [ SO2Cl2 ]

Similar approach to MJC MYE 09 Paper 3 Q2.

= 0.713 mol dm-3 []

(iii) If a system at dynamic equilibrium is subjected to a change in which disturbs the equilibrium [], the system will respond in such a way as to counteract the effect of the change. [] (iv) SO2Cl2(g) SO2(g) + Cl2(g) H negative

By Le Chateliers principle, the equilibrium position shifts to the left [] towards the endothermic [] reaction where heat is absorbed []. Thus, the value of Kc will decrease. [] (b) NaCl has a high melting point [] whereas SiCl4 has a low melting point []. NaCl is a giant ionic compound [] with strong electrostatic forces of attraction between Na+ and Cl- ions, [] hence large amount of energy [] is required to break the bonds during melting. SiCl4 has simple molecular structure [] with weak intermolecular Van der waals forces []. Lesser energy [] is required to overcome these intermolecular forces of attractions during melting. Another possible physical property: electrical conductivity.

2 NaCl gives Na+ and Cl- on dissolution in water and both do not undergo hydrolysis [] thus a solution of sodium chloride is neutral. However, SiCl4 undergoes hydrolysis [] to give an acidic solution. Na+(aq) + Cl-(aq) [] NaCl(s) + aq SiCl4(l) + 2H2O(l) SiO2(s) + 4HCl(aq) [] (c) (i)
CH3CH2OH I CH3CH2Cl [] II CH3CH2CN [] III CH3CH2CH2NH2 []

Step I: PCl5 [] Step II: KCN in ethanol, heat [] Step III: LiAlH4, dry ether []

(ii)
CH3CH=CH2 Step I: Br2(aq) I CH3CH(OH)CH2Br II CH3COCH2Br III CH3COCH2OH

[] []
Step II: KMnO4(aq), H2SO4(aq), heat [] Step III: NaOH(aq), heat []

[]

[]

3 2 (a) (i) Standard enthalpy change of neutralisation (Hn) is the energy released when an acid and a base react [] to form one mole of water at 298K and 1 atm. [] Ethanoic acid is weak acid which undergoes partial dissociation []. Some of the energy liberated from the neutralisation is used for the dissociation of the weak acid [] unlike HCl and HNO3 which dissociate completely. CH3CH2NH2 + HCl CH3CH2NH3+Cl-

(ii)

(iii)

Heat evolved, Q = mCT = (35.0 + 45.0) x 4.2 x 5.2 [] = 1747 J = 1.747 kJ [] No of moles of salt produced = 35.0/1000 x 1.0 = 0.0350 [] Hreaction = Q / n = -1.747.2/0.035 = - 49.9 kJ mol-1 [] (b) (i) Initial [ ] Change in [ ] [ ]eqm / mol dm-3
+

CH3CH2NH2 + H2O 0.10 -x 0.10 x

CH3CH2NH3+ + OH0 0 x x x x [] for table

Kb =

[CH 3 CH 2NH3 ][OH ] [] [CH 3 CH 2NH 2 ]

4.5 x 10-4 =

x2 0.10 x

Since CH3CH2NH2 is a weak base, it undergoes partial dissociation. Hence, 0.10 >> x. Thus, 0.10 x 0.10 x = [OH-] = 6.71 x 10-3 mol dm-3 [] pH = 14 pOH = 14 - [-lg(6.71 x 10-3)] = 11.8 [] (ii) A solution that is equally effective in resisting changes in pH is a buffer at its maximum buffer capacity [], which occurs at Ve in this case. Volume of HCl required for complete neutralisation = 20.00 cm3 Volume of HCl required to neutralise half the amount of CH3CH2NH2 = 10.00 cm3. [] At the maximum buffer capacity, pOH = pKb pOH = -lg(4.5 x 10-4) = 3.35 [] pH = 14 3.35 = 10.7 []

4 (iii)

pH
Max. Buffer capacity (10, 10.7)

11.8 10.7

<7

Equivalence point

10

20

Vol of HCl / cm3

[4] for graph, -[] for each missing/wrong labels (c) phenylamine < 4-methylphenylamine < ethylamine [1] Both the phenylamines are weaker bases than ethylamine due to the delocalisation of the lone pair of electrons on their N atoms into their benzene rings. [] Hence, the lone pair on their N atoms are less available to accept a proton. [] 4-methylphenylamine is a stronger base than phenylamine due to its electron-donating CH3 group which increases the electron density [] on the lone pair of N atom. Hence, the lone pair on N atom is more available to accept a proton. [] (d) (i) (ii) CH3COCl [], r.t.p. [] Phenol is not a good nucleophile [1] to react with ethanoyl chloride to form the ester. [Note: To form the ester, phenol is usually treated with NaOH(aq) to form sodium phenoxide. Phenoxide ion is a better nucleophile.] (iii) NaOH(aq) at r.t.p. [] Product:
CH3COHN O Na
+

[]

NaOH(aq), heat [] Products:

H2 N

O Na

[1]

CH3CO2-Na+ []

5 3 (a) (i) The order of reaction with respect to a reactant is the power to which the concentration of that reactant is raised in the experimentally determined rate equation. [1] Half-life, t, is the time taken for the reactant concentration to decrease to half of its original value. [1] (ii) Let rate= k[H2O2(aq)]m[ I-(aq)]n Compare experiments 1 & 2, keeping [H2O2(aq)] constant 1.2x10 4 k(0.020 )m (0.040 )n (or use inspection method) = 1.5 x10 4 k(0.020 )m (0.050 )n n=1 Rate of reaction is 1st order [1] with respect to (or rate [I-(aq)]). Compare experiments 1 & 3, keeping [I-(aq)] constant 1.2x10 4 k(0.020 )m (0.040 )n (or use comparing method) = 3.0 x10 4 k(0.050 )m (0.040 )n m=1 Rate of reaction is 1st order [1] with respect to H2O2(aq) (or rate [H2O2]) Rate= k[H2O2(aq)][ I-(aq)] [1] (iii) Using experiment 1, Rate= k[H2O2(aq)][I-(aq)] 1.2 x 10-4 = k(0.020)(0.040) k = 0.150 mol-1 dm3 min-1 [1] (iv) For experiments 4 and 5, since [I-(aq)] >> [H2O2(aq)], [I-(aq)] is approximately constant. Thus, rate = k[H2O2(aq)] (a pseudo first order reaction) where k = k[I-(aq)] ln 2 ln 2 t1/2 = = = k' k[I ] t1/2 of H2O2 in experiment 4 = 9.2 min (for [I-(aq)] = 0.500 mol dm-3) t1/2 of H2O2 in experiment 5 = 4.6 min [1] (for [I-(aq)] = 1.00 mol dm-3) (b) (i)
The reaction can be quenched by: adding NaOH/NaHCO3/Na2CO3 to remove the H+(aq) sudden cooling of the reaction mixture sudden dilution through the addition of large volume of water any of the above method [1]

I-(aq)

(ii)

I2(aq) + 2S2O32-(aq) 2I-(aq) + S4O62-(aq) [1]

6 (c) (i)
Reason: Down the group, Size of electron cloud of HX increases (HI > HBr > HCl) [] Extent of distortion of the electron cloud increases [] Intermolecular Van Der Waals forces of attraction becomes more extensive [] Larger amount of energy required [] Down the group, Covalent bond length of H-X increases (HI > HBr > HCl) [] Covalent bond strength decreases [] Bond dissociation energy decreases [] Lesser amount of energy required []

(ii)

(d) Information given Deduction P, C10H11O2Br, has comparable no. of Presence of benzene ring C and H atoms, no. of C > 6. [] P, C10H11O2Br, does not undergo P does not contain a carboxylic neutralization with aq Na2CO3 acid group. P undergoes alkaline hydrolysis and P is an ester. [] nucleophilic substitution to form Q Q is salt of carboxylic acid and and R(C7H8O). [] contains OH group. R is an alcohol with aromatic ring. R undergoes oxidation benzoic acid. [] Q is optically active.
to give R Is phenylmethanol. []

Q has a chiral carbon with 4 different groups attached. []

Q undergoes nucleophilic substitution Q contains a carboxylic acid and an with PCl5 to form steamy fumes of alcohol group. [] HCl. []

Structures:

H H3C C OH C

O
OH

CH2OH

[]

R, C7H8O []

O CH2 O C CH CH3 Br

P (C10H11O2Br) []
Equations:

CH2OH + 2[O]

COOH + H2O

[]

H H3C C OH
C

O OH

H + 2 PCl5 H3C C Cl
C

O Cl + 2POCl3 + 2HCl

[]

O CH2 O C CH CH3 Br

+ 2NaOH(aq)
CH2OH
+

H H3C C C OH

O + O-Na

+ NaBr(aq)

[]

8 4 (a) (i) (ii)

3Mg(NH2)2(s) Mg3N2(s) + 4NH3(g) [1]

Ionic size of Mg2+ < Ba2+ Charge density of Mg2+ > Ba2+ [] Polarising power of Mg2+ > Ba2+ [] Extent of polarising effect on the anion charge cloud: Mg2+ > Ba2+ [] Hence, magnesium amide is less thermally stable than barium amide []

(iii) (Group II Tutorial Question)

Mg3N2(s) + 6H2O(l) NH3(aq) + HCl 3Mg(OH)2(s) + 2NH3(aq) []

NH4+ + Cl-

Amount of acid = 12/1000 x 0.50 = 0.0060 mol = amount of ammonia Amount of Mg3N2 formed = x 0.0060 = 0.0030 mol [] Mr of Mg3N2 = 100.9 Mass of Mg3N2 = 0.003 x 100.9 = 0.303 g [] Percentage of magnesium nitride = 0.303/1.00 x 100% = 30.3% []

(b) (i)

At 298K, G = H - T S = +71 298(174/1000) = +19.1 kJ mol-1 [1] The reaction is not energetically feasible as the G is positive [1].

(ii)

Yes [1] justified by reason; since S > 0, -TS < 0 hence at higher temperatures, the negative -TS term will outweigh the positive H term to make G < 0 [1]

9 (c)
Enthalpy Zn2+(g) + O2-(g)

1st + 2nd E.A. (O) Zn2+(g) + 2e + O(g)

1st + 2nd I.E. (Zn)

Hlattice (ZnO)

Zn(g) + O(g) 1/2 B.E. (O=O)

Zn(g) + 1/2O2(g) Zn(s) + 1/2O2(g) Hof (ZnO)

Hoat (Zn)

ZnO(s)

[3] correct Born Haber cycle

By Hess Law, H lattice (ZnO) = -657 908 1730 (496) - 130 + (-348) = -4021 kJmol-1 [1]

10 (d) Information given in Qn Deduction L, C9H8O, has a high C:H ratio A benzene/aromatic ring present [] (comparable no. of C and H atoms) and number of C > 6. Compound L is insoluble in water and L does not contain a phenol group [] aqueous sodium hydroxide. L undergoes electrophilic addition L contains an alkene group [] with liquid bromine to form M, C9H8OBr2. L undergoes oxidation with Tollens L is an aromatic reagent to give a silver mirror but not benzaldehyde [] with Fehlings solution. L undergoes oxidation with acidified potassium manganate(VII) to give N, C8H6O4 with the loss of 1 C as CO2. [] Compound N undergoes acid-base reaction with aqueous sodium hydroxide to form a soluble sodium salt. [] N undergoes nucleophilic substitution with SOCl2 to form two acid chloride groups which undergoes further nucleophilic substitution with ethylamine. [] L M aldehyde /

L has the C=C is at the terminal position. N is a diacid due to the presence of 4 oxygen atoms. [] N contains carboxylic acid groups. []

The final product O is a diamide. []

[]

[]

[]

[]

11 5 (a)
surface area of artefact = 800 cm2 volume of Al2O3 deposited = surface area x thickness = 800 x (0.1/10) = 8.00 cm3 []

mass of Al2O3 deposited = 4.0 x 8.00 = 32.0 g amount of Al2O3 deposited During anodising, O2 + 4H+ + 4e [] 2H2O 4Al + 3O2 2Al2O3 Hence, 2Al2O3 3O2 12 e1Al2O3 3/2 O2 6 e= 32.0 / [2(27.0) + 3(16.0)] = 0.3137 mol []

amount of e- needed to deposit 0.3137 mole of Al2O3 = 0.3137 x 6 = 1.882 mol [] Q = nF = 1.882 x 96500 = 181613C

1.82 x 105 C [1]

(b) (i) (ii)

A complex ion contains a central metal ion bonded to ligands [1] by coordinate / dative bonds [1]. An example of a complex ion is [Fe(H2O)6]3+. The d orbitals are split into two groups due to the ability of the ligands to split them into the energy levels as shown. This effect is known as d orbital splitting. [1]

E
d orbitals in free ion d orbitals in octahedral complex

The d electrons undergoes d-d transition and is promoted to the higher d orbital [1] During the transition, the d electron absorbs a certain wavelength of light from the visible region of the electromagnetic spectrum and emits the remaining wavelength which appears as the colour of the complex observed. [1]

12 (c)
Fe3+(aq) + e
I2(aq) + 2e

Fe2+(aq) 2I- (aq)

E = + 0.77 V E = + 0.54 V = + 0.36 V

cell

[Fe(CN)6]3- + e 2Fe3+ + 2I-

[Fe(CN)6]4- E 2Fe2+ + I2 E

= +0.77 + (-0.54) = +0.23 V > 0 [] Hence, reaction is energetically feasible []. Iodide is oxidised to iodine which accounts for the reddish brown solution. 2[Fe(CN)6]3- + 2I2[Fe(CN)6]4- + I2 E
cell

The reaction is not energetically feasible [].

= +0.36 + (-0.54) = -0.18 V < 0 []

[Fe(CN)6]3- cannot be reduced by I- [], this is because CN- ligands are able to stabilise the +3 oxidation state of iron [] (relative to the +2 oxidation).

(d) Haemoglobin consists of 4 sub-units: 2 -sub-units and 2 each being non-covalently linked to a haem residue []
Iron in haem group binds reversibly to oxygen : [] Haemoglobin + O2 Oxyhaemoglobin [] Both the and -sub-units have 70 % -helical regions []

-sub-units,

There is little contact within the pairs of - and -sub-units [] There is much contact between an -sub-unit and its neighbouring -sub-unit []

(e)

(i) (ii)

Dative [] bonding in which the lone pair of electrons on the oxygen atom is donated to the vacant orbitals of iron []. The oxidation state of iron remains as +2 [1] as the reaction to form oxyhaemoglobin is a ligand exchange not a redox reaction [1]. Aspartic acid, Asp
O
H3 N
+

(f)
H2N

Glycine, Gly
O CH2 + C H3N CH 2 C OH

Lysine, Lys
O H3N CH (CH 2)4 NH 3
+ +

CH CH2

C O-

C O-

O-

[]

[]

O-

[] C Lysine []

A Aspartic acid [] ; B Glycine [] ;