ANSWER AND MARK SCHEME (Pahang 2010) QUESTION 1 1.

(a) (i) nd sum of dependent on 2 mark or reference to orders (1) powers in rate equation (1) allow reference to annotated rate equation 2 (b) (i) (H2) 1 (1) eg rate trebles as [H2] trebles not rate doubles as [H2] doubles (1) (I2) 1 (1) eg rate doubles as [I2] doubles (1) mark these points independently allow 1 mark for orders if not clear that both are first order 4 (ii) rate = k[H2][I2] (1) must be [H2] not [H] allow e.c.f from (b)(i) allow mark for correct answer for (b)(ii), even if (b)(i) wrong 1 (iii) rearrange correctly correct substitution and correct consequential answer (1) 1 3 1 correct units (mol dm s ) (1) allow e.c.f. from (b)(ii) allow e.c.f. for incorrect arrangement 2 (c) 6 4 10 (1) allow e.c.f. from (b)(ii) and (b)(iii) could be worked by ratio from values in table or from rate equation 1 [10]

QUESTION 2 2. (a) HA 1 (b) + + Ka = [H ][A ]/[HA] or Ka = [H3O ][A ]/[HA] (1) 1 (c) (i) (ii) (iii) Increases (1) Decreases (1) No change (1) 3 (d) Sodium ethanoate or sodium hydroxide (1)Buffer solution (1) 2 (e) (i) + H (aq) + A (aq) or HA + H2O + H3O + A (1)

F ir s t io n is a tio n e n e rg y

(1 ) (1 ) ( 1 ) (1)

N e

N a

M g A l E le m e n t

Si

(ii)

Explanation for neon Neons electron is in a lower (2p) shell attracted more strongly to (or less shielded from) the nucleus (1) Explanation for magnesium more protons electrons in same shell or similar shielding (1)

(Total 10 marks)

QUESTION 3 3. a. (i) Mg2+ ion: 1s22s22p6 [1] Sr2+ ion: 1s22s22p63s23p63d104s24p6 [1] (ii) Al3+ ion is smaller than Mg2+ ion. Al3+ ion and Mg2+ ion are isoelectronic. However the nuclear charge in Al3+ is higher than that in Mg2+ ion. Hence the size of Al3+ ion is smaller. (iii) An aqueous solution of beryllium salt shows acidic properties due to the dissociation of the dehydrated Be2+ ion. b. (i) MgCO3 (s) MgO(s) + CO2(g) [1] [1]

[1] [1] [1] [1]

(ii) The activation energy for the reaction is high. At room temperature the particles do not have enough energy to overcome the activation energy.

(iii) As the size of the cation increases, the charge density and the polarising [1] 2power towards the CO3 decreases. Hence the carbonates become more stable. [1] Total : [ 15 ]

QUESTION 4 4. a. (i) Concentrated nitric acid and concentrated sulphuric acid. Temperature not exceeding 550C C6H6 + HNO3 (ii) Nitronium ion, NO2+ (iii) Step 1 + NO2+ Step 2 2HSO4-- + NO2+ + H3O+ [1] [1] [1] [1]

H NO2

[1]

H NO2

NO2 + H+

[1]

(iv) Benzene is used as a solvent for oils and fats / can be converted to Cumene, used for making phenol.

[1]

b. (i) CH3CONHC6H5 (ii) OH CH3

[1] [1] [1] TOTAL : [15]

(iii) (CH3)2C(OH)CH2CH3

SECTION B 5(a) Tendency or strength or ability or power of an atom/element/nucleus to attract/withdraw electrons / e density / bonding pair / shared pair In a covalent bond (tied to M1 unless silly slip in M1) (If molecule/ion then = CE = 0) (NOT electron (singular) for M1) Mark as 2 + 2 1

Increase in size or number of shells or increased shielding or bonding electrons further from nucleus [NOT increase in number of electrons] Decreased attraction for (bonding) electrons (tied to M3) (If ion here, lose M3 and M4) (NOT attraction of covalent bond) (Ignore reference to proton number or effective nuclear charge) (b) Hydrogen bonding (full name) + Diagram shows at least one H and at least one F (If full charges shown, M2 = 0) 3 lone pairs shown on at least one fluorine atom H-bond indicated, between H and a lone pair on F
:
+ +

1 1 1

H
..

:F

:F
..

(If atoms not identified, zero for diag) (Fl for fluorine - mark to Max 2) (Max 1 if only one HF molecule shown, or HCl shown) Dipole results from electronegativity difference or values quoted 1

(difference may be inferred) (Allow explanation e.g. F attracts bonding electrons more strongly than H) Fluorine more/very electronegative or iodine less electronegative or electronegativity difference too small in HI Comparison required, may be implied. HI dipole weaker or bonding e more equally shared - wtte NaCl is ionic (lattice) (Treat atoms/molecules as a contradiction) (Accept cubic lattice) Diamond is macromolecular/giant covalent/giant atomic/giant molecular (NOT molecular or tetrahedral) (Ionic/van der Waals = CE = 0) (Many) covalent/C-C bonds need to be broken / overcome (NOT just weakened etc.) (Covalent may be inferred from diagram) (Treat diagram of graphite (without one of diamond) as a contradiction lose M2 but allow M3/M4]) Which takes much energy or covalent bonds are strong 1

(c)

1 1

1 [15]

QUESTION 6 (a) (i) enthalpy change when 1 mol of a substance (or compound) 1 is (completely) burned in oxygen (or reacted in excess oxygen) 1 at 298 K and 100 kPa (or under standard conditions) 1 (ii) heat produced = mass of water Sp heat capacity x T (or mcT) = 1504.1864 (note if mass = 2.12 lose first 2 marks then conseq) = 40100 J or = 40.1 kJ (allow 39.9-40.2 must have correct units) moles methanol = mass/Mr = 2.12/32 (1) = 0.0663 1 H = 40.1/0.0663 = 605 kJ (mol ) (allow 602 to 608 or answer in J) (note allow conseq marking after all mistakes but note use of 2.12 g loses 2 marks 1 1 1 1

(b)

(i)

equilibrium shifts to left at high pressure 1 because position of equilibrium moves to favour fewer moles (of gas) 1

(ii)

at high temperature reaction yield is low (or at low T yield is high) 1 at low temperature reaction is slow (or at high T reaction is fast) 1 therefore use a balance (or compromise) between rate and yield 1

(c)

H = Hc (reactants) Hc (products) (or correct cycle) 1 Hc (CH3OH) = Hc (CO) + 2 Hc (H2) H 1 = (283) + (2 286) (91) (mark for previous equation or this) 1 = 764 (kJ mol ) ( units not essential but lose mark if units wrong) 1 (note + 764 scores 1/3) [15]

7. (a) During the electrolysis of aqueous sodium chloride, hydrogen is liberated at the cathode (1) While chlorine is liberated at the anode. (1) At the cathode, 4OH2H2O + O2 + 4e Hence for every mole of electron that passes through the electrolyte, one mole of NaOH will be produced. (1) NaOH + HCl NaCl + H2O 0.25 x 15.50 No of moles of HCl used in titration = ------------------- = 3.88 x 10-3 mol (1) 1000 No of moles of NaOH produced = 3.88 x 10-3 mol (1) Quantity of charge required , Q = 3.88 x 10-3 mol x 96500 C = 374.4 C

Using Q = It, 374.4 = I x 25 x 60 I = 0.25 A/ (1) (b) (i) The partition law states that a solute, s distributes itself between the two Immiscible solvents, ether and water in such a way that the ration of the concentrations in the two solvent is constant. (1) Concentration of S in ether --------------------------------- = 12.50 Concentration of S in water (1) (ii) (iii) The partition law only holds when the temperature is constant and the molecular condition in both solvents. (2) single extraction Let a be the amount of S left in the aqueous layer, 8.00 a ---------- = 12.50 a a = 0.59 g (1) 1st portion in 2 extractions, Let b be the amount of S left in the aqueous layer, (8.00 b)/12.50 -------------------- = 12.50 b/25.0 b = 4.00 g 2nd portion in 2 extractions, Let b be the amount of S left in the aqueous layer, (8.00 1.10 - c)/12.50 ----------------------------- = 12.50 c/25.0 c = 2.00 g total extraction = 4 + 2 = 6.00 g

(1)

[1] [1] ______ [ 15 ] [1] [1] [1]

8. a. In aqueous solution, the Al3+ ion which has the empty valence orbitals forms coordinate bond with water molecules producing [Al(H2O)6]3+ complex ions. The Al3+ ion has a small ionic radius and a high charge density. In the coordinated H2O molecule, the O-H bond is weakened as the electrons of the oxygen atom are strongly attracted towards the Al3+ ion. The complex ion acts as a Bronsted- Lowry acid by donating a proton to an uncoordinated H2O molecule forming the H3O+ ion which makes the solution acidic.

[1]

[Al(H2O)6]3+ (aq) + H2O(l) (i) Al2Cl6 (s) + 12H2O(l)

[Al(H2O)5OH]2+(aq) + H3O+(l) 2[Al(H2O)6]3+ (aq) + 6Cl-

[1] [1] [1] [1]

Anhydrous aluminium chloride exists as a dimer which dissolves in water forming [Al(H2O)6]3+ and Cl- ions. (ii) 2[Al(H2O)6]3+ (aq) + 3CO32- (aq) 2[Al(H2O)3(OH)3](s) + 3 CO2 (g) + 3H2O(l)

The Al3+ ion solution contains the [Al(H2O)6]3+ complex ion which forms the solid aluminium hydroxide with a strong base such as a carbonate or a sulphide. Aluminium carbonate and aluminium sulphide are not formed in the reaction between the Al3+ (aq) solution with sodium carbonate or sodium sulphide solutions. 2[Al(H2O)6]3+ (aq) + 3S2- (aq) 2[Al(H2O)3(OH)3](s) + 3H2S (g)

[1] [1]

[1]

(iii) Aluminium chloride is a simple covalent compound. The molecules are held by weak van der Waals forces. [1] It has a low melting point and sublimes at 1800C. [1] It fumes in moist air because of hydrolysis. [1] The white fume is hydrogen chloride gas. AlCl3 (s) + 3H2O (l) Al(OH)3 ( s) + 3HCl (g) [1] _______ [ 15 ]

9. a (i) phenylamine < ammonia < ethylamine (ii) The strength of a base depends on its ability to donate its lone pair electrons for sharing with a proton. In phenylamine, the lone pair electron on N atom is delocalised into the ring. The p orbital of N atom overlaps with those of the carbon atoms in the ring. Thus it is not readily shared with protons. In ethylamine, the ethyl group has an electron donating effect. This makes the lone pair electron on N atom more available for sharing with protons.

[1] [1] [1]

[1] [1]

b. (i) Add acidified KMnO4 to methylbenzene and heat. Benzoic acid is formed. C6H5CH3 + 3[O] C6H5COOH + H2O Add PCl5 and heat, benzoyl chloride is formed C6H5COOH + PCl5 C6H5COCl + POCl3 Add concentrated ammonia C6H5COCl + NH3 C6H5CONH2 + HCl

[1] [1] [1] [1] [1]

(ii)Chlorine gas , sunlight and boiling methylbenzene Chloromethylbenzene is formed C6H5CH3 + Cl2 C6H5CH2Cl + HCl Add aqueous sodium hydroxide and reflux C6H5CH2Cl + NaOH C6H5CH2OH + NaCl To prove the presence of OH group in (ii), add PCl5 White fumes of hydrogen chloride is observed C6H5CH2OH + PCl5 C6H5CH2Cl + HCl + POCl3

[1] [1] [1] [1] [1] _____ [ 15 ]

10. a. X is an ester ( sweet smelling liquid ) Y is phenol ( formation of white precipitate with bromine water ) Reduction of X would produce two alcohols. Y is a tertiary alcohol And Z is a primary alcohol. Structure of X CH3 O CH3 C C O H Name of X : phenyl-2-methylpropanoate

[1] [1] [1]

[1] [1]

Hydrolysis of X : CH3 O C C H

CH3

+ H2O

[1]

(CH3)2CHCOOH +

OH

10

(Y)

[1]

Reaction of Y with bromine water OH + 3 Br2 Br Br OH + 3HBr Br [1]

Reduction of X : CH3 O C C H

CH3

+ 4[H]

(CH3)2CHCH2OH (Z) + OH

[1] [1]

Dehydration of Z : (CH3)2CHCH2OH (CH3)2C= CH2 + H2O [1]

b. (i) Ethyl magnesium bromide can be prepared by heating bromoethane with magnesium metal at 350C in dry ether (ii)CH3CH2MgBr + CH3COCH3 CH3CH2C(CH3)2 + MgBr+ + H2O OCH3CH2C(CH3)2 + MgBr+ OCH3CH2C(CH3)2 + Mg(OH)Br

[1] [1] [1] [1] _____ [ 15 ]

11