CHM 101: Thermochemistry & Chemical Kinetics Lecture Note

CHM 101: THERMOCHEMISRTY & CHEMICAL KINETICS

COURSE UNIT: 3

COURSE SYNOPSIS

Thermochemistry: Standard enthalpy changes of reaction, formation,

combustion and neutralization. Hess law, lattice energy for simple

ionic crystals.

Chemical Kinetics: Simple equations; order of reactions; rate constants;

simple calculations on half-life. Qualitative effects of temperature on

rate constant; catalysis.

Course Lecturer: Dr. A. J. Anifowose

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CHM 101: Thermochemistry & Chemical Kinetics Lecture Note

What is Thermochemistry?

Thermochemistry is an aspect of chemistry that deals with the amount of heat exchange
(i.e., absorbed or released) during a chemical reaction

Types of Heat (Enthalpy) of Reaction

Heat of formation is defined as the change in enthalpy that takes place when one
mole of the compound is formed from its element. It is denoted by change in Hf if the
heat of formation of ferrous sulphide and acetylene may be expressed as

Fe(s) + S(s) ⟶ FeS(s) ΔHθ f = -24.0 Kcal

2C(s) + H2(g) ⟶ C2 H2(g) , ΔHθf = +53.14 Kcal

Similarly, the reaction between gaseous hydrogen and gaseous chlorine to form
gaseous hydrogen chloride is represented by the equation:

H2(g) + Cl2(s) ⟶ 2HCl(s) , ΔHθ f = -44.0 Kcal

½H2(s) + ½Cl2(s) ⟶ HCl, ΔHθf = -22.0 Kcal

Standard Heat of Formation: The standard heat of formation of a compound is

defined as the change in enthalpy that takes place when one mole of the compound is
formed from its element, all substances being in their standard state (298k and 1atm
pressure).

Heat of reaction or Enthalpy of reaction: Heat of reaction may be defined as the

amount of heat absorbed or evolved in a reaction when the number of moles of
reactants, as represented by the balanced chemical equations, changed completely into
the product.

CO(g) + ½O2(g) ⟶ CO2(g), ΔH = -284.5 KJ

The heat exchange accompanying a reaction taking place at 298k and one
atmospheric pressure is called the Standard Heat change or Standard Enthalpy
change. It’s denoted by change in ΔHθ

Standard Heat of Reaction (ΔHθ) from standard heat of formation (ΔHθf)

The standard heat of reaction is equal to the standard heat of formation of product—
the standard heat of formation of reactant

ΔHθ = ΔHθf(products) ⟶ ΔHθf(reactants)

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CHM 101: Thermochemistry & Chemical Kinetics Lecture Note

Let us consider the general reaction

aA + bB ⟶ cC + dD

ΔHθ = ΔHθf(products) ⟶ ΔHθf(reactants)

=[c*ΔHθf(C) + d*ΔHθf(D)] ⟶ [a*ΔHθf(A) + b*ΔHθf(B)]

Heat of Combustion: The heat of combustion of a substance is defined as the change

in enthalpy of a system when one mole of the substance is completely burnt in excess
of air or oxygen. It is denoted by change in HC

CH4(g) + 2O2(g) ⟶ CO2(g) + 2H2O(l), ΔHc = -21.0 Kcal

Heat of combustion is always –ve

Heat of Neutralization: Heat of neutralization is defined as the change in heat content

(enthalpy) of the system when one form equivalent of an acid is neutralized by one
form equivalent of a base or vice versa in dilute solution

HNO3(aq) + NaOH(aq) ⟶ NaNO3(aq) + H2O(l), ΔH = -13.69 Kcal

HESS LAW

Hess law state that if a chemical change can be made to take place in two or more
different ways whether in one step or two or more steps, the amount of total heat
changes is same, no matter by which method the change is brought about.

LATTICE ENERGY

The positive and negative ion in an ionic crystal are held together by electrostatic
forces. The bond energy is expressed in terms of the lattice energy which may be
defined as the change in enthalpy (heat change) that occurs when one mole of a solid
crystalline substance is formed from its gaseous ions.

Na(s) + ½Cl2 ⟶ NaCl(s)

Na(g) ⟶ Cl(g)

Na+(s) ⟶ Cl-(g)

A Born-Haber cycle for the formation of NaCl crystal from its element

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CHM 101: Thermochemistry & Chemical Kinetics Lecture Note

Determination of Lattice Energy

The lattice energy of an ionic crystal can be found by applying Hess law. Consider an
enthalpy change for the direct formation of NaCl
Na(s) + ½Cl2(g) ⟶ NaCl(s) , ΔHθ = -411 KJmol-1
Step 1: conversion of sodium metal to gaseous atom
Na(s) ⟶ Na(g) , ΔH1θ = +108 KJmol-1
Step 2: Dissociation of chlorine molecules to chlorine atoms
½Cl2 ⟶ Cl(g), ΔH2θ = +121 KJmol-1
Step 3: Enthalpy of ionization; conversion of gaseous sodium to sodium ion by loss of
an electron
Na(g) ⟶ Na+(g) + e- , ΔH3θ = +495 KJmol-1
Step 4: Chlorine atom gains an electron to form chlorine ion. The energy of electron
affinity of chlorine
Cl + e- ⟶ Cl-(g) , ΔH4θ = -348 KJmol-1
Step 5: Sodium and chloride ions get together and form the crystal lattice
Na+(g) + Cl-(g) ⟶ NaCl , ΔH5θ = -(lattice energy)
ΔH1θ + ΔH2θ + ΔH3θ + ΔH4θ + ΔH5θ = -411kJ
108 + 121 +495 – 348 – lattice energy = -411
Lattice energy = +787 KJmol-1.

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CHM 101: Thermochemistry & Chemical Kinetics Lecture Note

CHEMICAL KINETICS

This is the study of the rate of reaction in chemistry and it covers the following.
1. The rate of reactions and rate laws;
2. The factors as temperature, pressure, concentration and catalyst that influences
the rate of reaction;
3. The mechanism or the sequence of steps by which a reaction occurs.
The rate of chemical reaction depends on the nature of reactant, temperature,
concentration or pressure of the reactant, surface area of the reactants and the presence
of catalyst
1. Nature of the reactants: The complexity of the reactant will affect their ability to
collide rightly.
2. Effect of temperature: A chemical reaction is affected by temperature because the
velocity of the reacting molecules is altered by change in temperature. Increase in
temperature increase the rate of reacting molecule. According to Maxwell-Boltzman’s
molecular velocity distribution, higher temperature activates more molecules to attain
high velocity which is required for effective collision
3. Effect of pressure/concentration: With the exception of zero order reaction, the rate
of chemical reaction is directly proportional to the concentration of the reacting specie
or to the pressure of the reacting species (if the reactants are gaseous).
4. Effect of Surface Area: This is important only if the system is heterogenous. The
larger the surface area for contact, the more molecules that are exposed to each other
and the more the number of possible collisions.
5. Effect of catalyst: The presence of catalyst can increase or decrease the speed of a
reaction. For instance, hydrogen and oxygen do not combine but in the presence of
platinum catalyst. Similarly, a small amount of glycerin slows down the decomposition
of hydrogen peroxide.
In chemical kinetics, reaction can be categorized into two:
1. Homogenous reaction: It takes places entirely in one phase.
2. Heterogeneous: It takes place in two or more phases. For example, gaseous
reaction taking place on the surface of a solid catalyst.

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CHM 101: Thermochemistry & Chemical Kinetics Lecture Note

RATE OF REACTION
The rate of a reaction tells us the speed of reaction. Consider a simple reaction:
A ⟶ B.
The concentration of reactant A decreases and that of B increases as time passes.
The rate of reaction is defined as the change in concentration of reactant or product per
unit time. For the given reaction. The rate of reaction may be equal to the rate of
disappearance of A which is equal to the rate of appearance of B. Therefore,
rate = -d[A]/dt = +d[B]/dt.
Where square bracket represents concentration of A and B. The negative sign shows the
concentration of A decreases in the course of the reaction. Whereas the positive sign
indicates increase in the concentration of B as the reaction proceeds.
THE RATE LAW

At a fixed temperature, the rate of a given reaction depends on concentration of reactant.

The exact relationship between concentration and rate is determined by measuring the
reaction rate with different initial reactant concentration. It is shown that the rate of
reaction is directly proportional to the reaction concentration, each concentration being
raised to some powers.
Thus, for a substance A undergoing reaction: rate, r ∝ [A]n, r = k[A]n
For a reaction: 2A + B ⟶ product,
the reaction rate with respect to A or B is determined by varying the concentration of
one reactant, keeping that of the other. Thus, the rate of reaction can be expressed as
rate = k[A]m[B]n
An expression which shows how the rate of reaction is related to concentration of
reactant is called the rate law or rate equation.
The power (exponent) of concentration n or m in the rate law is usually small whole
number integers 1,2,3 or fractional. The proportionality constant, k, is called the rate
constant for the reaction
ORDER OF REACTION
It is defined as the sum of the powers of the concentration in the rate law. Consider the
example of a reaction which has the rate law: rate = k[A]m[B]n.

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CHM 101: Thermochemistry & Chemical Kinetics Lecture Note

The order of such a reaction is m + n.

The order of a reaction can also be defined with respect to a single reactant. Thus, the
reaction order with respect to A is m, and n with respect to reactant B. the overall order
of the reaction (m + n) may range from 1 to 3 and can be fractional. Examples of order
of reaction.
The reaction will be classified as first order (m + n = 1); second order (m + n = 2); third
order, if m + n = 3. A zero order reaction is the reaction which does not depend on the
concentration of the reactant. A reactant whose concentration does not affect the
reaction rate is not included in a rate law.
NO2(g) + CO(g) ⟶ NO(g) + CO2(g) at 200 oC

rate = k[NO2]2

Here, the rate does not depend on the concentration of CO, so it (CO) is not included
in the rate law and the power of CO is understood to be zero. Therefore, the reaction is
zero order with respect to CO, but second order with respect to NO2. The overall
reaction order is 2+0 = 2.

MOLECULARITY OF A REACTION
Molecularity of an elementary reaction is defined as the number of reactant molecules
involved in a reaction.
Differences between order and molecularity of a reaction

S/N Order or a reaction Molecularity of a reaction

1 It is the sum of powers of the It is no of reacting species undergoing
concentration terms in the rate law simultaneously collision in the
expression elementary or simple reaction
2 It is an experimentally determined It is a theoretical concept
value
3 It can have fractional value It is always a whole number
4 It can assume zero value It cannot have zero value
5 Order of a reaction can change with It is invariant of reaction condition for a
the reaction condition such as given chemical equation
pressure, temperature
concentration

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CHM 101: Thermochemistry & Chemical Kinetics Lecture Note

METHODS FOR THE DETERMINATION OF THE ORDER OF REACTION AND

ITS RATE CONSTANT
(a) The Inspection method
Examples:
(i) For a reaction represented by the equation
A(g) + B(g) ⟶ C(g) , the following data were obtained

Experiment [A] (M) [B‾] (M) rate (Ms-1)

1 1.0 1.0 2.0
2 1.0 2.0 4.0
3 2.0 1.0 4.0

The data show that three experiments were carried out such that the concentrations of
A and B are kept constant in two of the experiments. Looking at the data when [A] was
maintained constant and [B] was doubled (experiment 1 and 2), the rate of reaction
doubled. This implies that the rate is directly proportional to [B]. Hence, the order with
respect to B is 1. Similarly, when [B] was kept constant and [A] was doubled
(experiments 1 and 3), the rate of reaction doubled. Hence, rate was also first order in
[A]. Therefore, the overall order of the reaction was 2. The rate constant, k, can be
calculated by substituting a pair of values in the rate equation: rate = k[A][B].
NOTE: If you double a reactant concentration for a second-order, the rate should
increase four-fold and for a third-order, the rate should increase eight-fold.
(ii) For a reaction: 2N2O5(g) ⟶ 4NO2(g) + O2(g)
the initial rates of the reaction were determined for different concentrations of N2O5(g)

[N2O5] (mol/L) Rate (mol/L/h)

0.1 0.016
0.2 0.032
0.4 0.064

The data indicate that the rate is doubled as the concentration is doubled. Thus, rate ∝
[N2O5]1.

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CHM 101: Thermochemistry & Chemical Kinetics Lecture Note

The reaction is therefore first-order and the rate equation is rate = k[N2O5]1. The rate
constant for the reaction is obtained by substitution of any pair of values from the table
into the rate reaction:
k = rate/[N2O5]
k = 0.016/0.1, k = 0.16 h-1.
(b) The rate curve method
The rate at a given concentration is the slope of the tangent to the concentration-time
curve at that concentration. By assuming an order of reaction, a plot of the rate against
concentration raised to the power which is equal to the assumed order is carried out. If
the assumed order tallies with the actual order of the reaction then a linear plot will be
obtained.
For a reaction:
Mg(s) + 2HCl(aq) ⟶ MgCl2(aq) + H2(g),
The rate curve is obtained by plotting [HCl] (mol/L) against time. The reaction rate
obtained from rate curve is then plotted against [HCl]n, where n stands for the assumed
order. If a linear plot is obtained, then n represents the actual order of the reaction.
Experimentally, the value of n was found to be 2. The rate constant for the reaction can
be obtained by substituting a pair of values into the rate equation:
Rate = k[HCl]2.
(c) Integrated rates method (for your further read)

RATE OF REACTION

Introduction: The rate of a reaction is the rate at which products are formed or the rate
at which reactants are used up in the reaction. Rate of reaction is the change in the
concentration of a reactant or product with time. By definition, it is necessary to
monitor the concentration of the reactant (or the product) as a function of time.
Consider a reaction of molecular bromine and formic acid:

Br2(aq) + HCOOH(aq) ⟶ 2Br-(aq) + 2H+(aq) + CO2(g)

Average rate = Δ[Br2]/ΔT
= -([Br2]final – [Br2]initial)/(Tfinal-Tinitial)

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CHM 101: Thermochemistry & Chemical Kinetics Lecture Note

Molecular Bromine is reddish brown in color. All other species in the reaction are
colourless. As the reaction progresses, the concentration of Bromine steadily decreases
and its colour fades. This loss of colour and, hence, concentration can be monitored
easily with a spectrometer, which registers the amount of visible light absorbed by
bromine. Measuring the change (decreases) in bromine concentration at some initial
time and then at some final time enables us to determine the average rate of the reaction
during that interval.
The rate of any reaction depends on a number of factors, among which are concentration
or pressure of reactants, temperature, presence of catalyst and nature of reactants. For
instance, rate of reaction increases as the surface of the reactant is increased and this is
why solid reactant reacts with less rate than powdered reactant.
Question
Using the data provided below
i. Calculate the average rate over the first 50secs.
ii. Calculate the average rate over the first 100secs.

Time (s) [Br2] (M) Rate(M/s) k = rate(s-1)/[Br2]

0 0.012 4.2 x 10-5 3.50 x 10-3
50 0.0101 3.52 x 10-5 3.49 x 10-3
100 0.00846 2.96 x 10-5 3.50 x 10-3
150 0.00710 2.49 x 10-5 3.51 x 10-3
250 0.00500 1.75 x 10-5 3.50 x 10-3

(i) average rate over the first 50sec:

rate = -(0.0101 – 0.012)/(50 – 0)
rate = 1.9 x 10-3/50 = 3.8 x 10-5 M/s
(ii) calculate on your own following worked example in (i) above

Let us consider the effect the bromine concentration has on the rate of reaction. Looking
at the data, the concentration at t = 50 s is double the concentration at t = 250 s and the
rate of reaction at t = 50 sec is double the rate at t = 250 sec. Thus, as the concentration
of bromine is doubled the rate of the reaction also doubles therefore, the rate of reaction
is directly proportional to the bromine concentration
rate ∝ [Br2], thus r = k [Br2]
Where k is known as the rate constant

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CHM 101: Thermochemistry & Chemical Kinetics Lecture Note

Because the rate of reaction has the unit of M/s and bromine concentration is in M, the
unit of k is “s-1”. It is important to note that k is not affected by bromine concentration.
To be sure, the rate is greater at a higher concentration and smaller at lower
concentration of bromine, but the ratio of rate/[Br2] remains the same provided the
temperature does not change.
Reaction rate and Stoichiometry
We have seen that for stoichiometrically simple reactions of type A ⟶ B, the rate can
either be expressed in terms of decrease in the reactant concentration or increase in
product concentration. For more complex reactions, we must be careful in writing the
rate expression.
Consider for example, 2A ⟶ B:
ି૚ ࢊ[࡭] ࢊ[࡮]
Rate = =
૛ ࢊ࢚ ࢊ࢚
ି૚ ∆[࡭] ∆[࡮]
r= × =
૛ ∆࢚ ∆࢚
In general, for the reaction aA + bB ⟶ Cc + dD . The rate is given by:
−1 ∆[‫ ]ܣ‬−1 ∆[‫ ]ܤ‬1 ∆[‫ ]ܥ‬1 ∆[‫]ܦ‬
‫= ݁ݐܽݎ‬ = = =
ܽ ∆‫ݐ‬ ܾ ∆‫ݐ‬ ܿ ∆‫ݐ‬ ݀ ∆‫ݐ‬

Question
Find the rate expression for the following reaction in terms of disappearance and
appearance of the product.

i. 4NH3(g) +5O2(g)→ 4NO(g) +6H2O(g)

ii. CH4(g) + ½ Br2 (g) → CH3Br(g) + HBr(g)

Answer:
ିଵ ∆[ேுయ ] ିଵ ∆[ைమ ] ଵ ∆[ேை] ଵ ∆[ுమ ை]
i. ‫= ݁ݐܽݎ‬ = = =
ସ ∆௧ ହ ∆௧ ସ ∆௧ ଺ ∆௧
ii. calculate on your own following the solved question in (i) above

Question 1. Consider the reaction: 4NO2(g) + O2(g) ⟶ 2N2O5(g)

Suppose that at a particular moment during the reaction molecular oxygen is reacting
as the rate of 0.0024 Ms-1
a) At what rate is N2O5 being formed?
b) At what rate is NO2 reacting?

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CHM 101: Thermochemistry & Chemical Kinetics Lecture Note

Answer
a. r = ½∆ [N2O5]/∆t
0.0024 = ½ ∆ [N2O5]/∆t
∆[N2O5]/∆ t = 0.0024 x 2
∆[N2O5]/∆ t = 0.0048 M/s

b. r = -1/4 ∆[NO2]/∆t
0.0024 = -1/4 ∆[NO2]/∆t
∆[NO2]/∆ t = 4 x 0.0024
∆[NO2]/∆t = -9.6 x 10-3 M/s

RATE LAW OF FIRST ORDER REACTION

A ⟶ Product
Suppose at the beginning of a reaction time (t = 0), the concentration of A = a mol/L. If
after time t, x mol of A has changed, the concentration of A is a–x.
We know that for a first order reaction, the rate of reaction (dx/dt) is directly
proportional to the concentration of the reactant. Thus,
dx /dt = k(a-x)
dx/(a-x) = kdt………………(1)
௫ ௗ௫ ௧
Integration of equation (1) gives ‫׬‬଴ = ‫׬‬଴ ݇݀‫ݐ‬
(௔ି௫)

-ln(a–x) + lna = kt………………….(ii)

k = 2.303/t log (a/a-x)
k = 1/t ln (a/a-x)
In terms of volume,
k = 2.303/t log (Vo/Vo–Vt)
Calculation of half-life of first order reaction
k = (2.303/t) log ([A]o/[A])
Where [A]o is the initial concentration of A; [A] is the concentration of A with respect to
time.
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CHM 101: Thermochemistry & Chemical Kinetics Lecture Note

Half life, t½ is the time when initial concentration of A reduces to half.

A reduces to half i.e [A] = ½[A]o, substituting value in the integration rate equation we
have,
k = 2.303/t log ([A]o/½[A]o
k = 2.303/t½log 2
t½ = 2.303 log 2/k
t½ = (2.303 × 0.3010)/k
t½ = 0.693/k
Rate law and order of reaction
Q1: The reaction of nitric oxide (NO) with hydrogen at 1280oC
2NO(g) + 2H2(g) ⟶ N2(g) + 2H2O(g)
From the following data collected at this temperature, determine (i) the rate law (ii) the
rate constant (iii) the rate of the reaction when the concentration of NO = 12 ×10-3 M and
concentration of H2 = 6 × 10-3 M

Experiment [NO] (M) [H2] (M) Initial rate (M/s)

1 5 ×10-3 2 ×10-3 1.3 ×10-5
2 10 ×10-3 2 ×10-3 5 ×10-5
3 10 ×10-3 4 ×10-3 10 ×10-5

Answer:
Generally, the rate law for the reaction is written as: r = k[NO]x[H2]y
In Exp 1, r = 1.3 ×10-5, then
1.3×10-5 = k(5×10-3)x(2×10-3)y ……..(1)
In Exp 2, r = 5 ×10-5
5×10-5 = k(10×10-3)x(2×10-3)y ………(2)
In Exp 3, r = 10 ×10-5
10×10-5 = k(10×10-3)x(4×10-3)y ………(2)
Equation 2÷1 results:

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CHM 101: Thermochemistry & Chemical Kinetics Lecture Note

5 × 10ିହ ݇ × (10 × 10ିଷ )௫ × (2 × 10ିଷ )௬

=
1.3 × 10ିହ ݇ × (5 × 10ିଷ )௫ × (2 × 10ିଷ )௬
10௫
3.85 = ௫
5
2ଶ = 2 ௫
‫=ݔ‬2
Equation 3÷2 results:
10 × 10ିହ ݇ × (10 × 10ିଷ )௫ × (4 × 10ିଷ )௬
=
5 × 10ିହ ݇ × (10 × 10ିଷ )௫ × (2 × 10ିଷ )௬
2 = 2௬
‫=ݕ‬1
Hence, the rate law for the reaction is, r = k[NO]2[H2]
(ii) from equation 1,
1.3×10-5 = k(5×10-3)2(2×10-3)
ଵ.ଷ×ଵ଴షఱ
݇=
(ହ×ଵ଴షయ )మ × (ଶ ×ଵ଴షయ )

k = 260 M-2 s-1.

(iii) from the rate law, r = k[NO]2[H2],
When [NO] = 12 ×10-3 M and [H2] = 6 × 10-3 M
Then,
r = 260 (12×10-3)2(6×10-3)
r = 2.25×10-4 M s-1.
Q2: The reaction of S2O82- with iodide is S2O82-(aq) + 3I‾(aq) ⟶ 2S042-(aq) + I3‾(aq)
From the following data collected at a certain temperature determine the rate law
i. the rate constant
ii. the order of reaction
iii. the rate of reaction when the initial concentration of S2082- and I‾ are halved and
doubled respectively
iv. Compare the rate of reaction I question (4) obtained in experiment (1)

Experiment [S2O82-] (M) [I‾] (M) Initial rate (M/s)

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CHM 101: Thermochemistry & Chemical Kinetics Lecture Note

1 0.08 0.034 2.2 × 10-4

2 0.08 0.017 1.1 × 10-4
3 0.16 0.017 2.2 × 10-4

Summary of Kinetics of Zero order, first order and second order reactions

Order Rate law Conc.-time Half-life (t½)

equation
0 rate = k [A]t = -kt + [A]o t½ = [A]o/2k
1 rate = k[A] ln([A]t /[A]o) = -kt t½ = 0.693/k
2 rate = k[A]2 (1/[A]t) = kt + t½ = 1/k[A]o
(1/[A]o)

Q3:The conversion of cyclopropane to propene in the gas phase is a first order reaction
with a rate constant of 6.7 x 10-4 s-1 at 500 oC
a) If the initial concentration of cyclopropane was 0.25 M, what is the
concentration after 8.8 min?
b) How long (in minutes) will it take the concentration of cyclopropane to
decrease from 0.25 to 0.15 M
c) How long (in mins) will it take to convert 74% of the starting material
Answer:
(a) Since the reaction is a first order and concentration-time dependent,
the equation ln([A]t /[A]o) = -kt applies to solve the problem
[A]t = ?
[A]o = 0.25
k = 6.7 x 10-4 s-1
t = 8.8 min (= 528 s)
ln(‫ݔ‬/0.25) = -(6.7 x 10-4 ×528)
(‫ݔ‬/0.25) = e-0.3538
‫ = ݔ‬0.176 M
(b) ln([A]t /[A]o) = -kt which is the same as ln[A]t -ln[A]o = -kt
ln0.15-ln0.25 = -(6.7 x 10-4)t
-0.5108 = -(6.7 x 10-4)t
t = 762.4 s (or 12.7 min)
(c) If at time t, 74% of the starting material is converted, then what remains as [A]t is
26% of 0.25 M

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CHM 101: Thermochemistry & Chemical Kinetics Lecture Note

Hence, [A]t = 0.065 M

ln[A]t -ln[A]o = -kt
ln0.065-ln0.25 = -(6.7 x 10-4)t
-1.347 = -(6.7 x 10-4)t
t = 33.5 min.

THE EFECT OF TEMPERATURE ON THE RATE OF REACTION

The rate of reaction doubles for every 10K rise in temperature. The relationship between
temperature and rate constant is given by Arrhenius equation which is expressed as:
k = Ae-Ea/RT, where K is the rate constant for the reaction, A is the Arrhenius
constant, Ea is the activation energy, R is the gas constant and T is the temperature in
Kelvins.
logk = logA – Ea/(2.303RT)
A graph of log K against 1/T is linear and Ea and A can be calculated from the slope and
intercept of the graph, respectively.
By determining the rate constant at two different temperatures, you obtain:
log(k2/k1) = (Ea/2.303R)(T2-T1/T1T2).
Ea can be calculated from the expression.

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CHM 101: Thermochemistry & Chemical Kinetics Lecture Note

Further Reading

Carey F. A. and Giuliano R. M. (2014) Organic Chemistry, 9th edn. McGraw-Hill
Education, New York.

Bahl A, Bahl B.S and Tull G.D (2012). Essentials of Physical Chemistry, S. Chand
& Company LTD, 2012 Edition, New- Delhi.

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