JC CHEMISTRY

Topical Revision
(Reaction Kinetics)
 Contents: Tables of Chemical data

1 Important values, constants and standards

2 Ionisation energies (1st, 2nd, 3rd and 4th) of selected elements in kJ mol–1
3 Bond energies
4 Standard electrode potential and redox potentials, E⦵ at 298 K (25 °C)
5 Atomic and ionic radii
6 Typical proton (1H) chemical shift values (δ) relative to TMS = 0
7 Characteristic infra-red absorption frequencies for some selected bonds
8 The orientating effect of groups in aromatic substitution reactions
9 Qualitative Analysis Notes
10 The Periodic Table of Elements

Data Booklet
for

Chemistry
(Advanced Level)

For use from 2017 in all papers, except practical

examinations, for the 9729 H2 Chemistry and H3
Chemistry syllabuses.

For use from 2018 in all papers, for the 8873 H1

Chemistry syllabuses.

39 40

2
1 Important values, constants and standards 2 Ionisation energies (1st, 2nd, 3rd and 4th) of selected elements, in kJ mol–1

molar gas constant R = 8.31 J K–1 mol–1 Proton Number First Second Third Fourth

the Faraday constant F = 9.65 × 104 C mol–1 H 1 1310 – – –

23 –1
the Avogadro constant L = 6.02 × 10 mol He 2 2370 5250 – –
–34
the Planck constant h = 6.63 × 10 Js Li 3 519 7300 11800 –

8 –1 Be 4 900 1760 14800 21000

speed of light in a vacuum c = 3.00 × 10 m s

1 –27 B 5 799 2420 3660 25000

rest mass of proton, H1 mp = 1.67 × 10 kg

1
C 6 1090 2350 4610 6220
rest mass of neutron, 0 n mn = 1.67 × 10–27 kg
N 7 1400 2860 4590 7480
0
rest mass of electron, −1 e me = 9.11 × 10–31 kg
O 8 1310 3390 5320 7450
electronic charge e = –1.60 × 10–19 C
F 9 1680 3370 6040 8410
molar volume of gas Vm = 22.7 dm3 mol–1 at s.t.p.
Ne 10 2080 3950 6150 9290
Vm = 24 dm3 mol–1 at r.t.p.
(where s.t.p. is expressed as 105 Pa [1 bar] and 273 K [0 °C], Na 11 494 4560 6940 9540
r.t.p. is expressed as 101325 Pa [1 atm] and 293 K [20 °C])
Mg 12 736 1450 7740 10500
Kw = 1.00 × 10–14 mol2 dm–6
ionic product of water
(at 298 K [25 °C]) Al 13 577 1820 2740 11600

= 4.18 kJ kg–1 K–1 Si 14 786 1580 3230 4360

specific heat capacity of water
(= 4.18 J g–1 K–1)
P 15 1060 1900 2920 4960

S 16 1000 2260 3390 4540

Cl 17 1260 2300 3850 5150

Ar 18 1520 2660 3950 5770

K 19 418 3070 4600 5860

Ca 20 590 1150 4940 6480

Sc 21 632 1240 2390 7110

Ti 22 661 1310 2720 4170

V 23 648 1370 2870 4600

Cr 24 653 1590 2990 4770

Mn 25 716 1510 3250 5190

Fe 26 762 1560 2960 5400

Co 27 757 1640 3230 5100

Ni 28 736 1750 3390 5400

Cu 29 745 1960 3350 5690

41 42

3
 3 Bond energies
Proton Number First Second Third Fourth

Zn 30 908 1730 3828 5980 3(a) Bond energies in diatomic molecules (these are exact values)

Ga 31 577 1980 2960 6190 Homonuclear Heteronuclear

Ge 32 762 1540 3300 4390 –1
Bond Energy/kJ mol Bond Energy/kJ mol–1
Br 35 1140 2080 3460 4850 H―H 436 H―F 562
Rb 37 403 2632 3900 5080 D―D 442 H―Cl 431
Sr 38 548 1060 4120 5440 944 H―Br 366
N≡N
Ag 47 731 2074 3361 –
O=O 496 H―I 299
Sn 50 707 1410 2940 3930
F―F 158 C≡O 1077
I 53 1010 1840 3200 4030
Cl―Cl 244
Cs 55 376 2420 3300 –
Br―Br 193
Ba 56 502 966 3390 –
I―I 151
Pb 82 716 1450 3080 4080

43 44

4
3(b) Bond energies in polyatomic molecules (these are average values) 4 Standard electrode potential and redox potentials, E⦵ at 298 K (25 oC)

For ease of reference, two tabulations are given:

Homonuclear Heteronuclear
(a) an extended list in alphabetical order;
(b) a shorter list in decreasing order of magnitude, i.e. a redox series.
Bond Energy/kJ mol–1 Bond Energy/kJ mol–1
4(a) E⦵ in alphabetical order
C―C 350 C―H 410

C=C 610 C―F 485 Electrode reaction E⦵ / V

C≡C 840 C―Cl 340 Ag+ + e– ⇌ Ag +0.80

C C (benzene) 520 C―Br 280 ⇌

Al 3+ + 3e– Al –1.66
N―N 160 C―I 240 2+ –
Ba + 2e ⇌ Ba –2.90
N=N 410 C―N 305
Br2 + 2e– ⇌ 2Br– +1.07
O―O 150 C=N 610
Ca2+ + 2e– ⇌ Ca –2.87
Si―Si 222 C≡N 890
– ⇌ –
P―P 200 C―O 360 Cl2 + 2e 2Cl +1.36

S―S 264 C=O 740 2HOCl + 2H+ + 2e– ⇌ Cl2 + 2H2O +1.64

C=O in CO2 805 ClO– + H2O + 2e– ⇌ Cl – + 2OH– +0.81

N―H 390 2+ – ⇌
Co + 2e Co –0.28
N―Cl 310
Co3+ + e– ⇌ Co2+ +1.89
O―H 460
2+ – ⇌
[Co(NH3)6] + 2e Co + 6NH3 –0.43
Si―Cl 359
2+ – ⇌
Cr + 2e Cr –0.91
Si―H 320

Si―O (in SiO2(s)) 460 Cr3+ + 3e– ⇌ Cr –0.74

3+ – ⇌ 2+
Si=O (in SiO2(g)) 640 Cr +e Cr –0.41

P―H 320 Cr2O72– + 14H+ + 6e– ⇌ 2Cr3+ + 7H2O +1.33

P―Cl 330
Cu+ + e– ⇌ Cu +0.52
P―O 340
2+ – ⇌
Cu + 2e Cu +0.34
P=O 540
Cu2+ + e– ⇌ Cu+ +0.15
S―H 347
[Cu(NH3)4]2+ + 2e– ⇌ Cu + 4NH3 –0.05
S―Cl 250
– ⇌ –
S―O 360 F2 + 2e 2F +2.87

S=O 500 Fe2+ + 2e– ⇌ Fe –0.44

3+ – ⇌
Fe + 3e Fe –0.04

45 46

5
 Electrode reaction E⦵ / V Electrode reaction E⦵ / V

Fe3+ + e– ⇌ Fe2+ +0.77 O2 + H2O + 2e– ⇌ HO2– + OH– –0.08

[Fe(CN)6]3– + e– ⇌ [Fe(CN)6]4– +0.36 2H2O + 2e– ⇌ H2 + 2OH– –0.83

– ⇌ – 2+ – ⇌
Fe(OH)3 + e Fe(OH)2 + OH –0.56 Pb + 2e Pb –0.13

2H+ + 2e– ⇌ H2 0.00 Pb4+ + 2e– ⇌ Pb2+ +1.69

– ⇌ – + – ⇌ 2+
I2 + 2e 2I +0.54 PbO2 + 4H + 2e Pb + 2H2O +1.47

+ – ⇌ + – ⇌
K +e K –2.92 SO42– + 4H + 2e SO2 + 2H2O +0.17

Li+ + e– ⇌ Li –3.04 S2O82– + 2e– ⇌ 2SO42– +2.01

2+ – ⇌ – ⇌
Mg + 2e Mg –2.38 S4O62– + 2e 2S2O32– +0.09

Mn2+ + 2e– ⇌ Mn –1.18 Sn2+ + 2e– ⇌ Sn –0.14

Mn3+ + e– ⇌ Mn2+ +1.54 Sn4+ + 2e– ⇌ Sn2+ +0.15

+ – ⇌ 2+ 2+ – ⇌
MnO2 + 4H + 2e Mn + 2H2O +1.23 V + 2e V –1.20

MnO4– + e– ⇌ MnO42– +0.56 V3+ + e– ⇌ V2+ –0.26

MnO4– + 4H+ + 3e– ⇌ MnO2 + 2H2O +1.67 VO2+ + 2H+ + e– ⇌ V3+ + H2O +0.34

+ – ⇌ 2+ + – ⇌ 2+
MnO4– + 8H + 5e Mn + 4H2O +1.52 VO2+ + 2H + e VO + H2O +1.00

NO3– + 2H+ + e– ⇌ NO2 + H2O +0.81 VO3– + 4H+ + e– ⇌ VO2+ + 2H2O +1.00

+ – ⇌ 2+ – ⇌
NO3– + 3H + 2e HNO2 + H2O +0.94 Zn + 2e Zn –0.76

+ – ⇌
NO3– + 10H + 8e NH4+ + 3H2O +0.87 All ionic states refer to aqueous ions but other state symbols have been omitted.
+ – ⇌
Na + e Na –2.71

2+ – ⇌
Ni + 2e Ni –0.25

[Ni(NH3)6]2+ + 2e– ⇌ Ni + 6NH3 –0.51

H2O2 + 2H+ + 2e– ⇌ 2H2O +1.77

– ⇌ –
HO2– + H2O + 2e 3OH +0.88

O2 + 4H+ + 4e– ⇌ 2H2O +1.23

O2 + 2H2O + 4e– ⇌ 4OH– +0.40

+ – ⇌
O2 + 2H + 2e H2O2 +0.68

47 48

6
4(b) E⦵ in decreasing order of oxidising power
Electrode reaction E⦵ / V
(a selection only – see also the extended alphabetical list on the previous pages)

Fe2+ + 2e– Fe –0.44

Electrode reaction E⦵ / V
2+ –
Zn + 2e Zn –0.76
F2 + 2e– 2F– +2.87

2H2O + 2e– H2 + 2OH– –0.83

S2O82– + 2e– 2SO42– +2.01

V2+ + 2e– V –1.20

H2O2 + 2H+ + 2e– 2H2O +1.77

Mg2+ + 2e– Mg –2.38

MnO4– + 8H+ + 5e– Mn2+ + 4H2O +1.52

Ca2+ + 2e– Ca –2.87

PbO2 + 4H+ + 2e– Pb2+ + 2H2O +1.47
+ –
K +e K –2.92
Cl2 + 2e– 2Cl – +1.36

Cr2O72– + 14H+ + 6e– 2Cr3+ + 7H2O +1.33

O2 + 4H+ + 4e– 2H2O +1.23

Br2 + 2e– 2Br– +1.07

NO3– + 10H+ + 8e– NH4+ + 3H2O +0.87

– – – –
ClO + H2O + 2e Cl + 2OH +0.81

NO3– + 2H+ + e– NO2 + H2O +0.81

Ag+ + e– Ag +0.80

Fe3+ + e– Fe2+ +0.77

I2 + 2e– 2I– +0.54

– –
O2 + 2H2O + 4e 4OH +0.40

Cu2+ + 2e– Cu +0.34

SO42– + 4H+ + 2e– SO2 + 2H2O +0.17

Sn4+ + 2e– Sn2+ +0.15

S4O62– + 2e– 2S2O32– +0.09

+ –
2H + 2e H2 0.00

Pb2+ + 2e– Pb –0.13

2+ –
Sn + 2e Sn –0.14

49 50

7
5 Atomic and ionic radii (e) Group 14 atomic/nm ionic/nm

(a) Period 1 atomic/nm ionic/nm single covalent C 0.077

single covalent H 0.037 H– 0.208 Si 0.117 Si4+ 0.041

van der Waals He 0.140 Ge 0.122 Ge2+ 0.093

(b) Period 2

metallic Li 0.152 Li+ 0.060 metallic Sn 0.162 Sn2+ 0.112

Be 0.112 Be2+ 0.031 Pb 0.175 Pb2+ 0.120

single covalent B 0.080 B3+ 0.020 (f) Group 17

C 0.077 C4+ 0.015 C4– 0.260 single covalent F 0.072 F– 0.136

3– Cl 0.099 Cl – 0.181
N 0.074 N 0.171
2– Br 0.114 Br– 0.195
O 0.073 O 0.140
–
F 0.072 F– 0.136 I 0.133 I 0.216

At 0.140

van der Waals Ne 0.160 (g) First row d block elements

(c) Period 3 metallic Sc 0.164 Sc3+ 0.075

+ 2+ 3+
metallic Na 0.186 Na 0.095 Ti 0.146 Ti 0.086 Ti 0.067
2+ V 0.135 V2+ 0.079 V3+ 0.064
Mg 0.160 Mg 0.065
3+ Cr 0.129 Cr2+ 0.073 Cr3+ 0.062
Al 0.143 Al 0.050
Mn 0.132 Mn2+ 0.083 Mn3+ 0.058
2+
single covalent Si 0.117 Si4+ 0.041 Fe 0.126 Fe 0.061 Fe3+ 0.055
3– Co 0.125 Co2+ 0.065 Co3+ 0.055
P 0.110 P 0.212

S 0.104 S2– 0.184 Ni 0.124 Ni2+ 0.069 Ni3+ 0.056

2+
– Cu 0.128 Cu 0.073
Cl 0.099 Cl 0.181
Zn 0.135 Zn2+ 0.074

van der Waals Ar 0.190

(d) Group 2

metallic Be 0.112 Be2+ 0.031

2+
Mg 0.160 Mg 0.065

Ca 0.197 Ca2+ 0.099

Sr 0.215 Sr2+ 0.113

Ba 0.217 Ba2+ 0.135

Ra 0.220 Ra2+ 0.140

51 52

8
6 Typical proton (1H) chemical shift values (δ) relative to TMS = 0 7 Characteristic infra-red absorption frequencies for some selected bonds

Type of Chemical Shift Appearance of peak

Environment of proton Example structures Functional groups containing Absorption range (in
proton range (δ) Bond (s = strong,
the bond wavenumbers) / cm–1
w = weak)

alkane ―CH3, ―CH2―, 0.9–1.7 C―Cl chloroalkanes 700–800 s

C―O alcohol 970–1260 s

2.2–3.0 ether 1000–1310 s
alkyl next to C=O CH3―C=O, ―CH2―C=O,
ester 1050–1330 s
carboxylic acids 1210–1440 s

alkyl next to aromatic ring CH3―Ar, ―CH2―Ar, 2.3–3.0 C=C aromatic 1475–1625 s
alkenes 1635–1690 w
CH3―O, ―CH2―O, ―CH2―Cl, C=O amides 1640–1690 s
alkyl next to
3.2–4.0 ketones and aldehydes 1670–1740 s
electronegative atom
C―H carboxylic acids 1680–1730 s
esters 1710–1750 s
attached to alkyne ≡C―H 1.8–3.1
C≡C alkynes 2150–2250 w unless conjugated
attached to alkene =CH2, =CH― 4.5–6.0
C≡N nitriles 2200–2250 w

attached to aromatic ring 6.0–9.0 C―H alkanes, CH2―H 2850–2950 s

alkenes/arenes, =C―H 3000–3100 w

N―H amines, amides 3300–3500 w

aldehyde 9.3–10.5
O―H carboxylic acid, RCO2―H 2500–3000 s and very broad
H-bonded alcohol/phenol, RO―H 3200–3600 s
alcohol RO―H 0.5–6.0 free alcohol, RO―H 3580–3650 s and sharp

O―H phenol 4.5–7.0

(see note
below)

carboxylic acid 9.0–13.0

alkyl amine R―NH― 1.0–5.0

aryl amine 3.0–6.0

N―H
(see note
below)

amide 5.0–12.0

Note: δ values for ―O―H and ―N―H protons can vary depending on solvent and concentration.

53 54

9
 8 The orientating effect of groups in aromatic substitution reactions 9 Qualitative Analysis Notes
[ppt. = precipitate]
The position of the incoming group, E, is determined by the nature of the group, G, already bonded to the
ring, and not by the nature of the incoming group E. 9(a) Reactions of aqueous cations

reaction with
cation
NaOH(aq) NH3(aq)

aluminium, white ppt. white ppt.

Al3+(aq) soluble in excess insoluble in excess

ammonium,
ammonia produced on heating –
NH4+ (aq)
―alkyl ―CHO, ―COR
―OH or ―OR ―CO2H, ―CO2R
G ―Cl, ―Br, ―I barium, no ppt.
―NH2, ―NHR or ―NR2 ―NH3+ no ppt.
Ba2+(aq) (if reagents are pure)
―NHCOR ―NO2, ―CN
calcium, white ppt. with high
Reactivity of ring no ppt.
Ca2+(aq) [Ca2+(aq)]
(compared to Activated Deactivated Deactivated
benzene)
grey-green ppt.
chromium(III), grey-green ppt.
soluble in excess
Position of E Cr3+(aq) insoluble in excess
giving dark green solution
(relative to position 2- and/or 4- 2- and/or 4- 3-
of G)
blue ppt.
copper(II), pale blue ppt.
soluble in excess
Cu2+(aq), insoluble in excess
giving dark blue solution

green ppt., turning brown on green ppt., turning brown on

iron(II),
contact with air contact with air
Fe2+(aq)
insoluble in excess insoluble in excess

iron(III), red-brown ppt. red-brown ppt.

Fe3+(aq) insoluble in excess insoluble in excess

magnesium, white ppt. white ppt.

Mg2+(aq) insoluble in excess insoluble in excess

off-white ppt., rapidly turning off-white ppt., rapidly turning

manganese(II),
brown on contact with air brown on contact with air
Mn2+(aq)
insoluble in excess insoluble in excess

zinc, white ppt. white ppt.

Zn2+(aq) soluble in excess soluble in excess

55 56

10
 9729 CHEMISTRY GCE ADVANCED LEVEL H2 SYLLABUS (2019)
10 The Periodic Table of Elements

Group
1 2 13 14 15 16 17 18
1 2
H He
hydrogen helium
Key 1.0 4.0
3 4 atomic number 5 6 7 8 9 10
Li Be atomic symbol B C N O F Ne
lithium beryllium name boron carbon nitrogen oxygen fluorine neon
6.9 9.0 relative atomic mass 10.8 12.0 14.0 16.0 19.0 20.2
11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
sodium magnesium aluminium silicon phosphorus sulfur chlorine argon
23.0 24.3 3 4 5 6 7 8 9 10 11 12 27.0 28.1 31.0 32.1 35.5 39.9
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
potassium calcium scandium titanium vanadium chromium manganese iron cobalt nickel copper zinc gallium germanium arsenic selenium bromine krypton
39.1 40.1 45.0 47.9 50.9 52.0 54.9 55.8 58.9 58.7 63.5 65.4 69.7 72.6 74.9 79.0 79.9 83.8
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
rubidium strontium yttrium zirconium niobium molybdenum technetium ruthenium rhodium palladium silver cadmium indium tin antimony tellurium iodine xenon
85.5 87.6 88.9 91.2 92.9 95.9 – 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3
55 56 57–71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba lanthanoids Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
caesium barium hafnium tantalum tungsten rhenium osmium iridium platinum gold mercury thallium lead bismuth polonium astatine radon
132.9 137.3 178.5 180.9 183.8 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0 – – –
87 88 89–103 104 105 106 107 108 109 110 111 112 114 116
Fr Ra actinoids Rf Db Sg Bh Hs Mt Ds Rg Cn Fl Lv
francium radium rutherfordium dubnium seaborgium bohrium hassium meitnerium darmstadtium roentgenium copernicium flerovium livermorium
– – – – – – – – – – – – –

57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
lanthanoids La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
lanthanum cerium praseodymium neodymium promethium samarium europium gadolinium terbium dysprosium holmium erbium thulium ytterbium lutetium
138.9 140.1 140.9 144.2 – 150.4 152.0 157.3 158.9 162.5 164.9 167.3 168.9 173.1 175.0
89 90 91 92 93 94 95 96 97 98 99 100 101 102 103
actinoids Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
actinium thorium protactinium uranium neptunium plutonium americium curium berkelium californium einsteinium fermium mendelevium nobelium lawrencium
– 232.0 231.0 238.0 – – – – – – – – – – –

58

colour in hexane

pale yellow

orange-red

purple
gives white ppt. with Ba2+(aq) (insoluble in excess dilute strong acids)

turns aqueous acidified potassium manganate(VII) from purple to

gives pale cream ppt. with Ag+(aq) (partially soluble in NH3(aq))

gives white ppt. with Ba2+(aq) (soluble in dilute strong acids)

colour in aqueous solution

gives yellow ppt. with Ag+(aq) (insoluble in NH3(aq))

NH3 liberated on heating with OH–(aq) and Al foil;

gives white ppt. with Ag+(aq) (soluble in NH3(aq))

NH3 liberated on heating with OH–(aq) and Al foil

test and test result

pale yellow

orange

brown
(colourless NO → (pale) brown NO2 in air)
reaction

turns damp red litmus paper blue

gives a white ppt. with limewater

(ppt. dissolves with excess CO2)
SO2 liberated with dilute acids;

57
CO2 liberated by dilute acids

bleaches damp litmus paper

NO liberated by dilute acids

“pops” with a lighted splint

relights a glowing splint

reddish brown gas / liquid

black solid / purple gas

greenish yellow gas
colour of element
colourless
9(b) Reactions of anions

9(d) Colour of halogens

carbon dioxide, CO2
9(c) Tests for gases

sulfur dioxide, SO2

ammonia, NH3

hydrogen, H2

bromine, Br2
chlorine, Cl2

chlorine, Cl2
oxygen, O2
carbonate,

SO42– (aq)

SO32– (aq)
NO3– (aq)

NO2– (aq)

iodine, I2
bromide,

halogen
chloride,
Cl –(aq)

sulfate,
Br–(aq)

nitrate,
iodide,

sulfite,
nitrite,
anion

CO32–

I–(aq)

gas

11
12
REACTION KINETICS - MCQ

2
13
14
 Kinetics

Section A

For each question there are four possible answers, A, B, C and D. Choose the
one you consider to be correct.

PromoHCI07/I/13

1 Consider the reaction between gaseous compounds A, B and C to form D:

A(g) + B(g) + C(g) D(g)

The mechanism for the reaction was found to be as follows:

Step 1: A(g) + B(g) X(g) fast

Step 2: X(g) + C(g) Y(g) slow

Step 3: Y(g) D(g) fast

Which of the following statements about the reaction and its mechanism is
not correct?

A The units of the rate constant, k, are mol−1 dm3 s−1.

B The intermediates in the reaction are X(g) and Y(g).

C The rate of reaction increases with increasing pressure.

D The reaction is first order with respect to C(g).

Hwa Chong Institution

15
PromoHCI07/I/14

2 Which of the following graphs shows that the decomposition of hydrogen

peroxide is a first order reaction?

A B

C D

PromoHCI07/I/15

3 In an experiment, it was found that the rate of reaction doubled when the
reaction mixture was heated. Which of the following statements best
explains the observation?

A The average speed of the particles doubles when heated.

B The activation energy of the reaction is halved when heated.

C The temperature of the reaction mixture doubles when heated.

D The frequency of effective collisions between the particles

doubles when heated.

16
PromoHCI09/I/10

4 Consider the reaction between gaseous compounds A and B to form C:

A(g) + B(g) C(g)

The mechanism for the reaction was found to be as follows:

Step 1: 2 A(g) J(g) fast

Step 2: J(g) + B(g) C(g) + A(g) slow

Which of the following is the correct rate equation?

A Rate = k[A]2 B Rate = k[A]2[B]

C Rate = k[A][B] D Rate = k[J][B]

PromoHCI09/I/11
5 The decomposition of hydrogen peroxide is a first order reaction with
respect to hydrogen peroxide. The rate equation is
rate = k[H2O2] where k = 0.0495 min−1

Which of the following statements is not correct?

A The half-life of decomposition of hydrogen peroxide is 14 min.

B Graph of rate against concentration of hydrogen peroxide is

linear.

C Doubling the concentration of hydrogen peroxide will double

the rate of decomposition.

D Doubling the concentration of hydrogen peroxide will reduce

the half-life by a factor of 2.

Hwa Chong Institution

17
PromoNYJC12/I/16
6 The diagram shows the Maxwell-Boltzmann energy distribution curves for
molecules of a sample of a gas at two different temperatures.

Which letter on the axes represents the most probable energy of the
molecules at the lower temperature?

PromoNYJC12/I/17
7 The rate equation for the reaction
_ _ _
S2O82 (aq) + 2I (aq) 2SO42 (aq) + I2 (aq)
_ _
is rate = k[S2O82 (aq)][I (aq)], where k is the rate constant.
Which of the following conclusions can be drawn from this information?
A The value of k depends on the concentrations of S2O82 and I .

B The value of k depends on the rate of the reaction.

C The value of k is dependent only on changes in temperature.

D The rate of reaction is dependent on concentrations of S2O82

and I .

18
PromoNYJC12/I/18
8 Lead is the final product formed by a series of changes in which the rate-
determining stage is the radioactive decay of uranium-238. This
radioactive decay is a first-order reaction with a half-life of 4.5 × 109 years.

What would be the age of a rock sample, originally lead-free, in which the
molar proportion of uranium to lead is now 1:3?

A 1.5 x 109 years

B 2.25 x 109 years

C 4.5 x 109 years

D 9.0 x 109 years

PrelimACJC12/I/8

9 Which graph correctly represents an auto-catalytic reaction (reaction in

which one of the products catalyses the reaction)?

A B

C D

Hwa Chong Institution

19
PrelimAJC12/I/14

10 Na2S2O3 reacts with dilute HCl to give a pale yellow precipitate. If 1 cm3 of
0.1 mol dm–3 HCl is added to 10 cm3 of 0.02 mol dm–3 Na2S2O3 the
precipitate forms slowly. If the experiment is repeated with 1 cm3 of
0.1 mol dm–3 HCl and 10 cm3 of 0.05 mol dm–3 Na2S2O3 the precipitate
forms more quickly.

Which of the following helps to explain this observation?

A The activation energy of the reaction is lower when

0.05 mol dm–3 Na2S2O3 is used.

B The reaction proceeds by a different pathway when

0.05 mol dm–3 Na2S2O3 is used.

C The collisions between reactant particles are more violent

when 0.05 mol dm–3 Na2S2O3 is used.

D The reactant particles collide more frequently when

0.05 mol dm–3 Na2S2O3 is used.

20
PrelimDHS12/I/7

11 An exothermic chemical reaction proceeds by two stages.

stage 1 stage 2
reactants intermediate products

The activation energy of stage 1 is 50 kJ mol–1. The overall enthalpy

change of reaction is –100 kJ mol–1.

Which diagram could represent the energy level diagram for the reaction?

A B
100 100
75 75
50 50
25 25
0 0
-25
reactants -25
reactants
-50 -50
-75 -75
-100
products -100
products

progress of reaction progress of reaction

C D
100 100
75 75
50 50
25 25
0 0
-25
reactants -25
reactants
-50 -50
-75 -75
-100 -100
products products

progress of reaction progress of reaction

Hwa Chong Institution

21
PrelimDHS12/I/11

12 Ozone in the earth’s atmosphere decomposes according to the equation:

2O3(g) 3O2(g)

This reaction is thought occur via a two–step mechanism:

Step 1 O3(g) O2(g) + O(g) fast, reversible

Step 2 O3(g) + O(g) 2O2(g) slow

What rate law is consistent with this mechanism?

A Rate = k[O3]2 / [O2] B Rate = k[O3]2 / [O2]3

C Rate = k[O3] D Rate = k[O3]2

PrelimMJC12/I/7(modified)

13 An experiment is conducted to investigate the kinetics of reaction between

bromopropane and 0.1 mol dm-3 sodium hydroxide in excess.

The rate equation is as follows:

Rate = k [bromopropane] [OH‒]

The half-life of bromopropane in one of the experiments is t minutes.

What is the new half-life (in minutes) of bromopropane when the

concentration of bromopropane is doubled and concentration of sodium
hydroxide is reduced to 0.01 mol dm-3? Assume NaOH to be in excess.

A 0.05t

B 0.1t

C 5t

D 10t

22
PrelimNYJC12/I/7

14 The radioactive decay is a first order reaction. If the rate of decay of a

radioactive isotope decreases from 200 counts per minute to 25 counts per
minute after 21.6 hours, what is its half-life?

A 2.4 hours

B 6.5 hours

C 7.2 hours

D 7.8 hours

PrelimNYJC12/I/8

15 Which of the following statements correctly explains why a small increase

in temperature leads to a significant increase in the rate of a gaseous
reaction?

A The average kinetic energy of the molecules is slightly greater

at a higher temperature.

B The proportion of molecules with any given energy increases.

C The frequency of collisions between molecules is greater at a

higher temperature.

D The frequency of collisions between molecules with kinetic

energy greater than the activation energy is greater at a
higher temperature.

Hwa Chong Institution

23
PrelimRI12/I/10

16 When [X][Y], the product of concentrations of X and Y, is plotted against

time, t, for the second-order reaction

X + Y → Z

which of the following graphs would be obtained?

A B

C D

24
PrelimRI12/I/11

17 For the Maxwell-Boltzmann distribution curve shown below for a chemical

reaction in living systems, which statement is not true?
fraction of molecules
with a given energy

fraction of molecules with

energy > Ea at a particular
temperature

kinetic
0 Ea energy
(activation energy)

A The total area under the curve is 1.

B The activation energy will decrease with an increase in

temperature.

C When temperature is increased, the peak of the curve

becomes lower.

D The shaded area of the curve will decrease when enzymes

are denatured.

Hwa Chong Institution

25
PrelimTJC12/I/12

18 Ethyl ethanoate undergoes a slow acid-catalysed hydrolysis in water

where the concentration of acid in the solution remains constant.

H+
CH3CO2CH2CH3 + H2O CH3CO2H + CH3CH2OH

The rate equation is found to be

rate = k[CH3CO2CH2CH3][H+]

When 0.1 mol dm-3 of HCl is reacted with 0.2 mol dm-3 of ethyl ethanoate,
the half-life was found to be 62 min.

Another reaction was carried out with 0.2 mol dm-3 of HCl and 0.2 mol dm-3
of ethyl ethanoate. How long does it take for the concentration of ethyl
ethanoate to fall to 0.025 mol dm-3?

A 31 min B 62 min C 93 min D 124 min

26
PrelimVJC12/I/10

19 The reaction between substances A and B is found to follow the rate law

rate = k[A]m[B]

where k is the rate constant and has units of mol–2 dm6 s–1.

Two experiments to study the kinetics of this reaction were carried out and
the data obtained are tabulated below.

Experiment Initial [A] Initial [B] Initial rate

/ mol dm–3 / mol dm–3 / mol dm–3 s–1

1 0.040 0.080 S
2 0.020 y S/2

What is the value of y in experiment 2?

A 0.020 B 0.040 C 0.160 D 0.320

PrelimYJC12/I/8

20 The reactants A and B react in the presence of a dilute acid as follows:

A(aq) + B(aq) C(aq) + D(aq)

It is found that the rate equation for the reaction is: rate = k [A]2 [H+]

Which one of the following statements is not correct?

A The magnitude of k increases with temperature.

B H+ lowers the activation energy of the reaction.

C Increasing [A] by a factor of 3 at constant temperature causes

a six-fold increase in the reaction rate.

D Increasing [H+] by a factor of 2 at constant temperature

causes a two-fold increase in the reaction rate.

Hwa Chong Institution

27
PrelimYJC12/I/10

21 The rate of removal of the pain-killing drug paracetamol from the body is a
first-order reaction with a rate constant, k = 0.26 h 1.

How long will it take for 25% of the paracetamol to remain in the body?

A 2.3 h

B 2.7 h

C 5.3 h

D 8.0 h

Section B

For each of the questions in this section, one or more of the three numbered
statements 1 to 3 may be correct.

Decide whether each of the statements is or is not correct (you may find it
helpful to put a tick against the statements you consider to be correct).

The responses A to D should be selected on the basis of

A B C D

1 and 2 2 and 3
1, 2 and 3 1 only is
only are only are
are correct correct
correct correct

No other combination of statements is used as a correct response.

28
PromoHCI07/I/28

22 The rate equation for a reaction between P and Q is given by: rate = k [P].

Which of the following statements about the reaction are true?

1 P is involved in the rate-determining step in the reaction

mechanism.

2 The rate constant, k, increases with increasing concentration

of P.

3 A graph of [P] against time gives a straight line passing

through the origin.

PromoHCI08/I/26

23 The following mechanism was proposed for the reaction between nitric (II)
oxide and hydrogen gas: 2 H2 (g) + 2NO (g) N2 (g) + 2H2O (g)

2NO ⇌ N2 O2 fast

N2O2 + H2 N2O + H2O slow

N2O + H2 N2 + H2O fast

Which of the following statements are incorrect?

1 The units of the rate constant, k, is mol–1 dm3 s–1 .

2 The rate constant increases with increasing pressure.

3 The intermediates in the reaction are N2O2 and N2O.

Hwa Chong Institution

29
PromoHCI09/I/27

24 The following kinetics data were obtained for the reaction between
nitrogen(II) oxide and hydrogen at 700 oC.

2NO(g) + 2H2(g) N2(g) + 2H2O(g) ∆H < 0

Initial [NO] / mol dm−3 Initial [H2] / mol dm−3 Initial rate / mol dm−3 s−1
0.250 0.05 1.2 10−6
0.250 0.10 2.4 10−6
0.125 0.10 6.0 10−7

Which of the following statements about the reaction are true?

1 The order of reaction with respect to hydrogen is 1.

2 The overall order of reaction is 3.

3 The initial rate would decrease with increasing temperature.

PromoNYJC12/I/34

25 The rate equation for the reaction 2A + B C + D is given as

Rate = k[A][B]. The initial concentration of A = 0.20 mol dm-3 and the initial
concentration of B = 0.001 mol dm-3.

Which of the following statements regarding the experiments are correct?

1 The half-life for the [B] against time curve is approximately

constant.

2 The mechanism for the above reaction involves more than

one step.

3 Changing the initial concentration of A to 0.002 mol dm-3 will

not affect the half-life of B.

30
PromoACJC12/I/34

26 In a chemical reaction, X reacts with Y to form Z. The initial rates of the

reaction are shown for the following experiments:

Experiment [X]/ mol dm–3 [Y]/ mol dm–3 Initial rate/ mol dm–3
1 0.150 0.250 2.80 x 10–5
2 0.150 0.500 5.60 x 10–5
3 0.075 0.500 2.80 x 10–5
4 0.075 0.250 1.40 x 10–5

The energy profile diagram for the reaction is as shown:

Which of the following is/are possible overall equation(s) of the above

reaction?

1 X+Y Z

2 X+ 2Y Z

3 2X + Y Z

Hwa Chong Institution

31
PrelimNYJC12/I/33

27 In the reaction between iodide and peroxodisulfate, iron (III) ion is used as
a catalyst.

Which of the statements are incorrect?

1 The rate constant remains the same.

2 One of the equations involve:

2Fe3+ + 2S2O32+ 2Fe2+ + S4O62‒.

3 This reaction is an example of a homogeneous catalysis.

PrelimTJC12/I/33

28 The table below shows the experimental results obtained for the following
reaction.

2YO + O2 2YO2

partial pressure of 100 100 50 25

YO (in arbitrary units)

partial pressure of O2 100 50 50 D

(in arbitrary units)

relative rate 1.00 0.50 0.25 1.00

Which of the following statements are correct?

1 The value of D is 400.

2 The reaction is first order with respect to YO.

3 Keeping partial pressure of YO constant, increasing partial

pressure of O2 does not change the relative rate.

32
REACTION KINETICS - STRUCTURED

2
33
Structured and Free Response Questions

PrelimACJC12/III/1a(modified)

1 When hydrochloric acid is added to sodium thiosulfate, Na2S2O3, a fine

precipitate of sulfur appears. This gradually makes the solution opaque.

Na2S2O3(aq) + 2 HCl(aq) S(s) + SO2(g) + 2 NaCl (aq) + H2O(l)

The rate of the reaction may be determined by measuring how long it

takes for the solution to become opaque such that a cross marked on a
piece of paper placed under the beaker containing the reaction mixture
just becomes obscured.

A series of experiments were carried out to study the order of reaction with
respect to Na2S2O3 and the following results were obtained.

Experiment Volume / cm3 Time / s

Number HCl Na2S2O3 H2O
1 20.0 40.0 40.0 39
2 20.0 30.0 50.0 50
3 20.0 20.0 60.0 83
4 20.0 10.0 70.0 170

(a) Explain why the total volume of the reaction mixture is kept constant
for all the four experiments.

(b) 1
Calculate the values of ( )/s 1
for the various volumes of Na2S2O3
Time
used.

(c) Hence or otherwise, state how the rate changes with the volume of
Na2S2O3 used.

(d) Explain why the rate changes with the volume of Na2S2O3 used.

[5]

Hwa Chong Institution

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PrelimAJC12/III/5a(modified)

2 The oxidation of acidified iodide ions by hydrogen peroxide is represented

by

2I–(aq) + H2O2(aq) + 2H+(aq) I2(aq) + 2H2O(l)

To determine the order of reaction, n, with respect to iodide ions, the rate
can be followed by adding a small but fixed volume of sodium thiosulfate
solution to the constant volume system of reaction mixture together with
1 cm3 of starch solution and measuring the time taken for the blue black
colour to appear. The results are given below.

Experiment [I–(aq)] / mol dm–3 Time (t) / s

1 0.0040 74.0

2 0.0060 49.4

3 0.0080 37.0

4 0.010 30.0

5 0.012 25.0

(a) Explain the relationship between the time taken for the formation of
the blue black colour and the initial rate of reaction.

(b) In the experiments, the concentrations of hydrogen peroxide and

hydrogen ions used are very much higher than that of the iodide
solution.

Explain why this is necessary.

(c) Evaluate 1/t for each experiment and hence plot a suitable graph to
determine the order of reaction, n, with respect to iodide ions.

State clearly your reasoning.

(d) Further studies show that the rate equation for the reaction is

Rate = k [I–]n [H2O2]

Based on this information and your answer to (c), state two

conclusions you can make about the mechanism of this reaction. [9]

38


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PrelimDHS12/III/1a(modified)

3 The kinetics of the hydrolysis of the ester, CH3CH2CO2CH3, may be

investigated by the following method.

CH3CH2CO2CH3 + H2O CH3CH2CO2H + CH3OH

In a 1 dm3 mixture, 0.350 mol of the ester was hydrolysed by heating with
water and using hydrochloric acid as catalyst. The following results were
obtained.

Time/s Concentration of CH3CH2CO2H/mol dm–3

0 0
340 0.105
680 0.185
1080 0.243
1440 0.278

(a) Suggest how the progress of this reaction may be followed in order
to obtain the results as stated.

(b) By drawing a suitable graph using the data given above, show that
the reaction is first order with respect to the ester. It has been found
that the hydrolysis reaction is first order with respect to the
hydrochloric acid.

(c) Deduce the units of the rate constant.

(d) State and explain the effect of a catalyst on the rate constant.

(e) Using suitable bond energy values from the Data Booklet, calculate
the ∆H for the hydrolysis of the ester.

(f) Given that the standard enthalpy change of reaction for the
hydrolysis is +7.6 kJ mol–1, suggest a reason for the difference
between this given value and the value that you have calculated in
(e).

[11]

Hwa Chong Institution

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PrelimNYJC12/III/3c(modified)

4 The hydrolysis of 2-bromo-2-methylpropane takes place as follows.

(CH3)3CBr + H2O (CH3)3COH + H+ + Br

An experiment was conducted to determine the order of reaction with

respect to 2-bromo-2-methylpropane. The following results were obtained.

time/s 19 28 50 69 154
[(CH3)3COH]/mol dm 3 0.0030 0.0040 0.0060 0.0072 0.0095

It was found that the order of reaction with respect to

2-bromo-2-methylpropane is one and the half-life of the reaction is 34.5 s.

(a) Using a non-graphical method, show that the concentration of

2-bromo-2-methylpropane at the start of the experiment is
0.0096 mol dm 3.

(b) Hence, deduce how long the reaction has proceeded when
concentration of (CH3)3COH obtained is 0.0084 mol dm 3.

(c) The following two mechanisms are both consistent with the reaction
being overall first order.

mechanism X (CH3)3CBr + H2O (CH3)3COH + H+ + Br

mechanism Y (CH3)3CBr (CH3)3C+ + Br slow

(CH3)3C+ + H2O (CH3)3COH + H+ fast

Explain why both mechanisms X and Y show overall first order

kinetics.

(d) The rate of reaction for the hydrolysis of 2-bromo-2-methylpropane

increases when the temperature is increased. Explain this
observation with the aid of a suitable diagram.

(e) The rate of reaction for the hydrolysis of 2-bromo-2-methylpropane is

R at T oC. What is the new rate if temperature is increased to (T+50)
o
C? Explain your answer.

[10]

46
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PrelimTJC12/III/3b(modified)

5 A bromoalkane, RBr, can be hydrolysed by aqueous sodium hydroxide.

The following results were obtained from two experiments on such a

hydrolysis. In each experiment, the overall [NaOH(aq)] remained virtually
constant as indicated in the table.

Experiment 1 Experiment 2
Time/ min [RBr]/ mol dm when [RBr]/ mol dm-3 when
-3

[OH-] = 0.10 mol dm-3 [OH-] = 0.15 mol dm-3

0 0.0100 0.0100
40 0.0079 0.0070
80 0.0062 0.0049
120 0.0049 0.0034
160 0.0038 0.0024
200 0.0030 0.0017
240 0.0024 0.0012

Using the same axes, plot graphs for the two experiments. Use your
graphs to answer the following questions. (Show your working clearly.)

(a) Deduce the order with respect to bromoalkane.

(b) Deduce the order with respect to OH‒.

(c) Construct a rate equation for the reaction and use it to calculate a
value for the rate constant.

(d) Explain the effect on the half-life of the reaction in experiment 1, if

the experiment is repeated with the concentration of NaOH(aq)
doubled from 0.10 mol dm-3 to 0.20 mol dm-3.

[9]

Hwa Chong Institution

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PrelimVJC12/II/3b(modified)

6 In a study of the reaction

2NO(g) + O2(g) 2NO2(g)

the following measurements were obtained from several experiments,

performed at a temperature of 25 oC.

initial [NO(g)] initial [O2(g)] initial rate

Expt
/ mol dm–3 / mol dm–3 / mol dm–3 s–1
1 1.16 x 10–4 1.21 x 10–4 1.15 x 10–8
2 1.15 x 10–4 2.41 x 10–4 2.28 x 10–8
3 1.18 x 10–4 6.26 x 10–4 6.24 x 10–8
4 2.31 x 10–4 2.42 x 10–4 9.19 x 10–8
5 5.75 x 10–4 2.44 x 10–4 5.78 x 10–7

(a) Determine the rate equation.

(b) Calculate the rate constant at 25 oC for experiment 1, stating its

units.

(c) Predict the initial rate when the volume of the vessel used for the
first set of experiment was suddenly halved.

[5]

54
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PrelimYJC12/III/3a(modified)

7 Propanone is an active ingredient found in household items such as nail

polish, paint thinner and sanitary cleaner. It also occurs naturally in the
human body in small quantities.

The bromination of propanone is acid-catalysed as shown below:

CH3COCH3 + Br2 CH3COCH2Br + H+ + Br

The rate of disappearance of bromine was measured for several different

concentrations of propanone, bromine and H+ ions at a certain
temperature.
Experiment [CH3COCH3] [Br2] [H+] Rate of disappearance of Br2

No. / mol dm-3 / mol dm-3 / mol dm-3 / mol dm-3 s-1

1 0.300 0.050 0.050 5.7 x 10-5

2 0.300 0.100 0.050 5.7 x 10-5

3 0.300 0.050 0.100 1.2 x 10-4

4 0.400 0.050 0.200 3.1 x 10-4

5 0.400 0.050 0.050 7.6 x 10-5

The proposed mechanism involved the following steps:

H+
CH3COCH3 CH 3C CH2
slow
OH
Br
CH 3C CH2 + Br CH 3C CH 2Br
2
OH fast OH

Br
CH 3C CH 2Br CH3COCH2Br + HBr
fast
OH

Hwa Chong Institution

57
(a) From the experimental data, deduce the rate equation for the
bromination of propanone.

(b) With a high concentration of CH3COCH3 as compared to H+, the rate

equation appears to be pseudo first-order and is given as
rate = k’ [H+] where k’ = k [CH3COCH3].

If the initial [H+] is 1.6 mol dm-3 and the half-life is 5 minutes, sketch
a graph of [H+] against time for the first 20 minutes of the reaction.

(c) Explain the role of H+ in the reaction using the concept of activation
energy.

(d) Given that the activation energy is +80 kJ mol 1 in the slow step,
sketch a labelled potential energy profile diagram for the above
reaction.

[8]

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SUGGESTED SOLUTIONS

2
63
 MCQ Answers 2 (a) Since a fixed volume of thiosulfate is used in each experiment, rate
can be measured by the time taken for fixed amount of iodine
1 2 3 4 5 6 7 8 9 10
liberated, i.e. rate α 1/t.
A A D B D C D D B D
11 12 13 14 15 16 17 18 19 20 (b) So that [H2O2] and [H+] are kept effectively constant and will not
C A D C D D B C C C affect the rate of reaction / rate is only affected by the concentration
21 22 23 24 25 26 27 28 of [I–].
C D B B B C B B
(c) evaluate (1/t)
Structured and Free Response Question Answers labelled axes: y–axis – (1/t); x–axis – [I–]
1 (a) This is so that the concentration of Na2S2O3 is directly proportional to best–fit straight line drawn through the origin
the volume used.
correctly plotted points
(b) Volume / cm3 Time / s 1 1
( )/s
Time Rate α [I–]n [H2O2]y [H+]z
Na2S2O3
Since rate α 1/t and [H2O2] and [H+] are effectively constant,
40.0 39 0.0256 1/t α [I–]n.

30.0 50 0.0200 Since a straight line which passes through the origin is obtained
when (1/t) is plotted against [I–], n = 1.
20.0 83 0.0120
(d) 1. It is a multi–step mechanism.
10.0 170 0.00588
2. H+ is not involved in the rate–determining step.
(c) The rate increase is directly proportional to the increase in the
volume of thiosulfate used. 3. 1 (mol) of I– and 1 (mol) of H2O2 are involved in the rate–
determining step.
(d) As the volume of Na2S2O3 increases, its concentration increases.
There are more reactant particles per unit volume and hence they
are closer together. They collide more frequently and collision    
frequency increases. Therefore rate of reaction increases.

   

64
 3 (a) Taking samples of reaction at the stated intervals (i.e. at 340 s, 4 (a) The first t1/2 corresponds to the time taken for half the final
680 s, 1080 s and 1440 s) and quenching it with large amount of [(CH3)3COH] to be formed while the sum of two t1/2 corresponds to
cold water. Titrate sample with dilute NaOH and suitable indicator. the time taken for ¾ of the final [(CH3)3COH] to be formed.

The [(CH3)3COH] at time = 34.5 s is not given in the table but the
2
(b) 0.3 y = -1E-07x + 0.0003x + 0.001 [(CH3)3COH] at time = 2 x 34.5 = 69 s is given.
0.25 Hence, ¾ x final [(CH3)3COH] = 0.0072 mol dm 3 ,
0.2
3
final [(CH3)3COH] = 4/3 x 0.0072 = 0.0096 mol dm
0.15

0.1 Since the mole ratio of (CH3)3CBr : (CH3)3COH = 1:1 and assuming

[RCOOH]/mo ldm
0.05 that the total volume of the reaction mixture remains constant,
0
[(CH3)3CBr] at the start of the experiment = final [(CH3)3COH]
0 200 400 600 800 1000 1200 1400 1600 = 0.0096 mol dm 3
Time/s
  (b) 0.0084 = 7/8 x 0.0096
The half-life of the ester is approximately 640 seconds based on the Hence, three half-lives have passed by.
data. Hence, the order of reaction with respect to the ester is 1 since
a constant half-life is established. Reaction has proceeded for 3 x 34.5 = 103.5 s.

(c) Rate = k[ester][HCl] (c) H2O is usually present in excess; hence its concentration is kept
relatively constant. Since the given equation in mechanism 1 shows
Units for k is mol–1 dm3 s–1 1 molecule of (CH3)3CBr participating in the reaction, the reaction is
(d) The catalyst increases the rate constant by providing an overall first order kinetics.
alternative pathway for reaction with lower activation energy. In mechanism 2, the slow step involves 1 molecule of (CH3)3CBr.
(e) ∆H = [ 8 410 + 2   350 + 2 360 + 740 + 2 460] Hence the rate equation is rate = k[(CH3)3Br] which shows that the
– [8 410 + 2 350 + 2 360 + 740 + 2 460] reaction is overall first order kinetics.

= 0 kJ mol–1

(f) The ester is not in gaseous phase which would make the
calculation by bond energy inaccurate.

65
 [RBr]/mol dm-3
(d) 5

[OH-]= 0.10 mol dm-3 

[OH-]= 0.15 mol dm-3 

(
(e) Ratee doubleed when n tempeerature increased by 1 10oC. Siince
o 5
temp d by 2 tiimes. He
perature increased by 20 C, rate increased ence
(a) For [OH‒] = 0.15 mol dm-3,
the n
new rate is 32R.
1st t½ = 78 mins; 2nd t½ = 78 mins Average t½ = 78 mins

Or

For [OH‒] = 0.10 moldm-3,

1st t½ = 116 mins; 2nd t½ = 114 mins Average t½ = 115 mins

Since t½ is a constant, order of reaction is 1st order wrt

[bromoalkane].

[Note: no mark is awarded for correct answer without working]

   

66
 (b) From the graphs, 6 (a) Comparing experiments 1 and 2, when the initial [O2(g)] doubles, the
3 5 initial rate doubles. Hence, the reaction is first order with respect to
Initial rate of reaction when [OH-] = 0.15 mol dm is 8.06 10 mol
O2(g).
dm 3 min 1
3 5
Comparing experiments 2 and 4, when the initial [NO(g)] doubles,
Initial rate of reaction when [OH-] = 0.10 mol dm is 5.43 10 mol the initial rate quadruples. Hence, the reaction is second order with
dm 3 min 1 respect to NO(g).
When [OH-] increases by 1.5 times, rate increases by Rate = k[NO]2[O2]
8.06 10 5 / 5.43 10 5 = 1.48 ≈ 1.5
(b) From experiment 1,
Hence 1st order wrt OH‒
1.15 x 10–8 = k (1.16 x 10–4)2 (1.21 x 10–4)
‒
(c) rate = k [RBr] [OH ]
k = 7063 mol–2 dm6 s–1
-
[RBr] [OH ] Initial rate of reaction k
(c) Initial rate = 1.15 x10–8 x 22 x 2
3 3 3 1 1 3 1
/ mol dm / mol dm / mol dm min / mol dm min
= 9.20 x 10–8 mol dm–3 s–1
5
0.010 0.10 5.43 10 0.0543

Or
7 (a) Comparing expts 1 and 5, when [CH3COCH3] increases 1.33 times
5 and [Br2], [H+] remains constant, rate increases 1.33 times. Hence,
0.010 0.15 8.06 10 0.0537
1st order wrt CH3COCH3.
Student can use values from either experiment to calculate k.
Comparing expts 1 and 3, when [H+] doubles and [CH3COCH3], [Br2]
‒
(d) Since [OH ] is constant, remains constant, rate doubles. Hence, 1st order wrt H+
Let rate = k’[RBr] where k’ = k[OH‒] Comparing expts 1 and 2, when [Br2] doubles, and [CH3COCH3], [H+]
t½ = ln2/ k’ when [OH‒] is doubled, k’ is doubled remains constant, rate of reaction remains unchanged. Hence, order
of reaction with respect to Br2 is 0.
thus t½ is halved (115/2 = 57.5 min).
Rate = k[CH3COCH3][H+]

   

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 (b)

(c) H+ acts as a homogeneous catalyst. It provides an alternative

pathway for the reaction with a lower activation energy (Ea). This
leads to an increase in the number of particles with energy greater
than or equal to Ea, thus the frequency of effective collision
increases, hence increasing the rate of the reaction.

(d)

80 

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 JC CHEMISTRY Topical Revision – Reaction Kinetics

CM-JC-EXM-009-V1