1.

i From the Data Booklet: Fe Fe+ + e 6 2 [Ar]3d 4s [Ar]3d64s1 Cu [Ar]3d104s1 Cu+ + e [Ar]3d10 1st IE : +762 kJ mol-1 1st IE: +745 kJ mol-1

- 1st IE of Cu < 1st IE of Fe - Cu has a greater shielding effect since it has 10 3d electrons thus less
energy is required to remove the 4s electron.

Alternative:

- Removal of one electron from Cu result in stable electronic configuration/stable

d10 configuration/fully filled d sub-shell.

- Less energy is required to remove the first electron from Cu than from Fe
ii.

Blue or violet or indigo The d orbitals in copper ion are split into two groups due to the ability of the ligands
to split them into the energy levels as shown.

The d electron undergoes d-d electron transition and is promoted to a higher

energy d orbital.

During the transition, the d electron absorbs the red light (longer wavelength of light)
from the visible region of the electromagnetic spectrum and transmits the blue light (shorter wavelength of light) which appears as the colour observed. iii. NH3(aq) + H2O (l) > NH4+(aq) + OH-(aq) [Cu(H2O)6]2+ (aq) + 2OH- (aq) Cu(OH)2 (s)
2+

Cu(OH)2 (s) + 6H2O (l)

-

Cu (aq) + 2OH (aq) ----- (1)

When NH3(aq) is added gradually, [OH-] will increase Equilibrium position in (1) shifts right. Ionic product of Cu(OH)2 > Ksp of Cu(OH)2 Pale blue ppt, Cu(OH)2 is formed

[Cu(H2O)6]2+(aq) + 4NH3(aq) When NH3 is added in excess,

[Cu(NH3)4(H2O)2]2+(aq) + 4H2O(l) -----(2) Stronger NH3 ligands replaces the H2O ligands, forming a

deep blue [Cu(NH3)4(H2O)2]2+ complex

 complex

[Cu2+(aq)] decreases as it is being used to form the equilibrium position in (1) shifts left to increase [Cu2+(aq)] Pale blue ppt dissolves.

OR Ionic product of Cu(OH)2 < Ksp of Cu(OH)2

2.i.

ii.

3 alkyl halide (2-bromo-2-methylpropane) reacted fastest in the AgNO3 test while it hardly showed any reaction in NaI test. 1 alkyl halide (1-bromobutane) reacted slowest in AgNO3 test while it reacted the fastest in NaI test. 3 alkyl halides form stable carbocations and tend to react via SN1 mechanism, which can be seen from its fast reaction in the AgNO3 test. On the other hand, there is a great amount of steric hindrance caused by the 3 R groups in 3 alkyl halides, hence causing reaction via SN2 mechanism to be very slow.

CH2CH3 CH3
.

CH2CH3

Br

slow

CH3

C + H
CH2CH3

Br

H
CH2CH3 CH3 C H

HOC 2H5

fast

CH3

C H

OC 2H5

iii. Resulting compound does not rotate plane polarized light. Nucleophile attacks the planar carbocation from either sides, forming equimolar amounts of enantiomers. Hence a racemic mixture is formed. iv.

Energy / kJ mol-1

Ea1
CH3CHBrCH2 CH3 CH3C+HCH2C H3

Ea2

CH3CH(OC2H5)C H2CH3

Reaction pathway
v. For 1-chlorobutane:

Time take for ppt to appear > 1 min. C-Cl bond is shorter and stronger than C-Br bond, hence less easily hydrolysed Ppt formed immediately Positive dipole on C is increased due to the highly electronwithdrawing C=O group, hence more susceptible to nucleophilic attack.

For ethanoyl bromide:

(3) (i)

AgCl (s) + e Ag + Cl Ag+ + e Ag Overall equation: Ag+ (aq) + Cl (aq) AgCl (s) E cell = 0.80 0.22 = +0.58 V At equilibrium, E = 0 V 0 = E cell (RT/nF)ln(1/[Ag+][Cl]) (Note: [AgCl (s)] is a constant) Therefore, 0 = +0.58 (8.31)(298)/(1)(96500) ln (1/Ksp ) Ksp = 1.53 x 1010 mol2 dm6

(ii)

4(a)(i) O T CH3 W CH3 X C CH(OH)C(CH3)2OH O C O CH(OH)CH(CH3)2

CH3
O CH3 C

CH3
O O C CH3

CH(OH)C(CH3)2O O C

CH3 Z OR

CHC(CH3)2OH O C O C O O C CH3 CH3

O CH3 OR O C O C O C CHC(CH3)2O

O C CH3

4(a)(ii) Step I: Cl2(g) Step II: aqueous NaOH, warm Step III: KMnO4/H+, warm 4(b)(i) Secondary alcohol and ketone 4 (b)(ii) E.g. use Br2(aq), PCl5 etc 4(c) CH CH CO 3 2 C 5.i. C H CH3CH2CO C C CH3

H H H CH Comparing Expt 1 and 2,3when [CH3CH=CHCH2Cl] doubles, rate doubles. Hence order of reaction with respect to CH3CH=CHCH2Cl is 1. Comparing Expt 1 and 3, when [CH3CH=CHCH2Cl] is tripled, rate should triple. When [OH] is tripled, there is no further change to the rate. Hence order of reaction with respect to OH is 0. Hence, mechanism is nucleophilic substitution (SN1)

(ii)

to show exothermicity and for showing that the first activation energy higher than second activation energy (iii) The p-orbital of chlorine overlaps with the pi-electron cloud of the double bond or there is partial double character between C and Cl (a) oxidation state of Fe in super-iron battery is +6, which is much higher than the common oxidation state of +2/+3 in Fe compounds.

(b)

Anode: Zn(s)+2OH (aq) Zn(OH)2(s) + 2e

Cathode: FeO42 (aq) + 4H2O (l) + 3e Fe(OH)3 (s) + 5OH (aq) (c) Amount of FeO42 =

10.0 = 0.0505 mol 2(39.1) + 55.8 + 4(16)

Amount of e = 3(0.0505) mol Q = 3(0.0505) 96500 = 1.46 104 C 7 (i) (ii) (iii) 8 (i) The pH value of 2.2 represents the maximum buffer capacity. pH = 1.65 NaH2PO4. Mg2+ has a higher charge over ionic radius ratio than Cu2+ Hhydration of Mg2+ is more exo than Hhydration of Cu2+ L.E is approximately constant in both compounds Hsolution of Mg(OH)2 is more exo than Hsolution of Cu(OH)2 Hence Mg(OH)2 is more soluble than Cu(OH)2. 7.2 10 20 mol dm 2 Higher due to the absence of common ion effect.

(ii) (iii)