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Reaction Kinetics
Know the definitions of the following:
Term Definition
rate of The change in concentration of a
rxn reactant or product with time.
i.e. rate at a given time t
= d [reacdt tan t ] = d[ product
dt
]
.
rate The rate equation or rate law is a
eqn mathematical equation that shows
how the rate of reaction is dependent
on the concentrations of the
reactants; it relates the rate of the
reaction to the concentration of
reactants raised to the appropriate
power. E.g. rate = k[A]m[B]n
order The order of reaction with respect
of to a reactant is the power to which
reactio the concentration of that reactant is
n raised to in the rate law.
(must The overall order of reaction is the
give sum of the powers to which the
both concentrations of the reactants are
& raised to in the rate law.
rate The rate constant, k is a
consta proportionality constant in the rate
nt equation of the reaction.
half-life The time required for the
of a rxn concentration of a limiting reactant to
decrease to half of its initial
concentration.
rate- The slowest step in the sequence of
determi steps leading to the formation of the
ning product.
step
activati The minimum amount of energy that
on the reactant particles must possess
energy, before they can collide successfully
Ea to form products
(Two criteria:
reaction:
A + B C + D
in which the rate equation is given by:
rate = k [A]m [B]n
Solution:
rate = k [H2O2] [I ]
Alternative approach
(aii)
Two different mechanisms have been
suggested for this reaction.
Mechanism A:
H2O2 + I H2O + IO(Step 1-slow)
H+ + IO HIO (Step 2)
HIO + H+ + I H2O + I2 (Step 3)
Mechanism B:
H2O2 + I + H+ H2O + HIO(Step 1-slow)
HIO + I I2 + OH (Step 2)
OH + H+ H2O (Step 3)
Solution:
79 kJ mol-1
H2O2 98 kJ mol-1
H2O + O2
Progress of reaction
T2 > T1
No. of molecules with energy Ea at T2
T2
No. of molecules with energy Ea at T1
0
Ea energy
Additional Question:
The diagram shows the Boltzmann distribution
of the speeds of the molecules of a gas. Point
X represents the most probable speed.
Solution
0.050 Expt 2 To find order of reaction with
0.025 respect to H2O2, use one of the
0.020
Expt I graphs and find the half life. If
0 t/ min
1 2 3 4 5 6 half life is constant, order is 1 wrt
H2O2.
To find order of reaction with
respect to OH, draw a tangent
at t = 0 for both expts and
compare the value of the
gradient (which represents rate)
when [OH] in expt 2 is half that
in expt 1. If grad of curve from
Question 2
Dinitrogen oxide, N2O, is used as an anesthetic. It
decomposes when heated as follows.
Additional Question:
A 3 hours D 8 hours
B 4 hours E 12 hours
C 6 hours N89/III/8
Ans: D
[product]/mol dm-3
Co
7
Co
8
3
Co
4
1
2
Co t1 = t2 = t3
i.e. t 1 is constant
2
0
time/s
t1 t2 t3
Time Volume of
/s CO2 / cm3
0 0
30 24.00
60 45.60
90 64.80
120 81.60
180 112.80
240 134.40
360 170.40
480 194.40
600 208.80
Table 1
All volumes are measured at room temperature and
pressure.
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
0
0 30 60 90 120 150 180 210 240 270 300 330 360 390 420 450 480 510 540 570 600 630
time / s
150
140 a(iv)
130
120
110
100
90
80
70
60
50
40
30
20
10
0
0 30 60 90 120 150 180 210 240 270 300 330 360 390 420 450 480 510 540 570 600 630
time / s
Additional Question
The kinetics of the acidcatalysed reaction of
propanone with iodine
CH3COCH3(aq) + I2(aq)
CH2ICOCH3(aq) + HI(aq)
can be investigated experimentally by varying the
concentrations of the three substances involved.
The following results were obtained in an
experiment.
Question 4
Samples of 2-bromo-2-methylpropane were
dissolved in dilute aqueous ethanol (80% ethanol
and 20% water by volume) and reacted with sodium
hydroxide solution. Several experiments were
carried out at constant temperature. The initial rate
of reaction was determined in each case.
Rate = k [(CH3)3CBr]
From Expt 1 data, 20.2 = k (0.020)
k = 1010 s-1
SN 2
%SN 2 = x 100%
SN 1 + SN 2
4.7[OH ]
= = X 100%
4.7[OH ] + 0.24
Ea,SN2 < Ea,SN1 : [1m]
Shape of Curve, Axis Labels : [1m]
(bviii) Explain how the rate constant will change if
CH(CH3)2Cl is used instead of CH(CH3)2Br.
6. Catalysis
(a) for most reactions (b) explosive reactions (c) enzyme-catalysed reactions
Hsolno solute dissolved The heat change when 1 mole of solute is completely dissolved in enough
solvent so that no further heat change takes place on adding more solvent
(infinite dilution) at 298 K and 1 atm.
NaCl(s) + aq Na+(aq) + Cl(aq)
Hneuto water formed The heat change when an amount of acid neutralises a base to form 1
mole of water (in dilute aqueous solution) at 298 K and 1 atmosphere
pressure.
NaOH(aq) + HCl(aq) NaCl (aq) + H2O(l)
Hato gaseous atoms The enthalpy change when 1 mole of atoms in the gas phase is formed
formed from the element in the defined physical state under standard
conditions.C(s) C(g) or Cl2(g) Cl(g)
LE pure ionic Lattice energy is the enthalpy change when one mole of a pure solid ionic
compound compound is formed from its constituent gaseous ions under standard
formed conditions.
Na+(g) + Cl(g) NaCl (s)
BE particular bond The bond energy of a X-Y bond is the average energy absorbed when 1
broken mole of X-Y bonds are broken in gaseous state. The stronger the bond,
the higher the bond energy.
Cl2(g) 2Cl(g)
BDE particular bond Bond Dissociation Energy of a X-Y bond is the energy required to break 1
in a particular mole of that particular X-Y bond in a particular compound in gaseous
compound state.
broken
1st IE gaseous M+ First ionisation energy is the energy required to remove 1 mole of
ions formed electrons from one mole of gaseous atoms in the ground state to form one
from one mole mole of gaseous unipositive charged cations.
of M atoms Na(g) Na+(g) + e
1st EA gaseous X ions First electron affinity is the energy change when 1 mole of electrons are
formed from added to one mole of atoms in the gaseous state to form one mole of
one mole of X gaseous X ions.
atoms Cl(g) + e Cl(g)
Summary of problem solving approach for
Chemical Energetics
(i) q = mcT
(ii) Shortcuts: Use of formulae/ bond energies.
(iii) Hess' Cycle
(iv) Energy Level Diagram
Question 2
MTBE as well as its isomer MTBE A is added to car
petrol as oxygenates. There has been concern over
the leakage of MTBE and MTBE A into water
supplies, mainly because of the foul taste it gives to
water supplies.
By Hess Law,
380 = 5(715) + 6(436) + (496) [4(350) +
11(410) + 360 + BE(OH)] 50.7
O
(i) By constructing an appropriate energy cycle,
calculate the enthalpy of the following reaction of
furan at 298K :
(CH)4O (l) 4C (g) + 4H (g) + O (g)
Use the following given enthalpy values:
Hf[(CH)4O] = -62 kJ mol-1
Hat (C) = +717 kJ mol-1
Hat (H) = +218 kJ mol-1
Hat (O) = +250 kJ mol-1
[Ans: Hr = +4052 kJ mol-1]
Ans:
In a(ii), furan is a liquid at room temperature and
bond energy is applicable for gaseous
molecules
or delocalisation effect in furan is not considered.
= 8.02 105 Pa
(ii) In fact, the pressure inside the engine
cylinder was found to be slightly lower than
the value calculated in d(i). Explain this
discrepancy in values observed.
Question 3
Iron(III) bromide is a fairly strong Lewis acid, and is
used as a catalyst in organic synthesis. Iron(III)
bromide dissolves in water to give a brown, acidic
and corrosive solution.
Checklist:
Axis with units
By Hess Law,
350 + 3(112) + 762 + 1560 + 2960 + 3(325) +
LE = 320
LE = 5313 kJ mol1
(c) The experimental value for the lattice energy of
iron(III) bromide is found to be 5268 kJ mol1.
Comment on and suggest reasons for the
difference between this value and the value you
obtained in (b).
Enthalpy/ kJ mol-1
2C(g) + 5H(g) + H(g)
2H2 + 6 H3
H1
CH3CH2(g) + H(g)
0 2C(s) + 3H2(g)
H4 H5
CH3CH3 (g)
By Hesss Law,
H1 = H4 + H5 2H2 6H3
= 435 + (85) 2(717) 6(218)
= 2392 kJ mol-1
C)
4 BE (Pb
Pb(C2H5)4(g) Pb (g) + 4CH3CH2(g)
H7 4H1
H6+ 8 H2 + 20 H3
Pb(s) + 6C(s) + 10H2(g) Pb(g)+ 8C(g) + 20H(g)
By Hess Law,
Hreaction = 395.4 ( 283 109)
= 3.4 kJ mol1
= +726 kJ mol-1
Progress of reaction
Question 1
Question 2
Explain the following observations:
(a) Sulfur has a lower first ionisation energy than
phosphorus.
Ga Ga
Cl Cl Cl
m CO
n
OCH2(CF2)6CF3