CHM 101: Lecture Note Thermochemistry & Chemical Kinetics

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. Activation energy; temperature

dependence of rate constants; catalysis.

Course Lecturer: Dr. A. J. Anifowose

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CHM 101: Lecture Note Thermochemistry & Chemical Kinetics

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

A thermochemical equation is a chemical equation with the ΔH for the reaction

included

Reaction Energy:

a. The study of energy in chemical reactions is called thermodynamics, which literally

means “changes in heat.”

b. The standard conditions for thermodynamics are

i. Standard temperature = 25 °C = 298 K

ii. Standard Pressure = 1 atm

iii. Notice that these are different than STP for gases (where ST=273 K and SP = 1atm).

c. All chemical reactions either release or require (absorb) energy when they occur.

Another way for saying this is that reactions either “give off” or “take in” energy.

d. Heat energy is referred to in this course as enthalpy (H).

i. Enthalpy is the heat absorbed or released by a system at constant pressure.

ii. It is impossible to measure enthalpy directly. Only changes in enthalpy are used in

this course. We only use “ΔH” in this course. ΔH = Hfinal - Hinitial

iii. Units of heat energy. We will use joules (J) or kilojoules (kJ).

iv. System (the chemical reaction under study), surroundings (every place in the
universe except the system), and universe (the system and the surroundings)

v. Exothermic reactions: An exothermic reaction is a reaction in which heat is released

by the system to the surroundings. From the perspective of the system, “heat is given
off.” For an exothermic reaction, the sign of ΔH is negative. When a reaction is
exothermic (ΔH is negative), that is a favourable condition. Enthalpy is just one of the
variables involved when predicting whether or not a reaction will occur, but reactions

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CHM 101: Lecture Note Thermochemistry & Chemical Kinetics

which release heat are more likely to occur than ones in which heat is required, all things
being equal.

Example: As water freezes, it must get rid of (release, give off) heat. Therefore, if the
water is considered the system, then the freezing of water is exothermic

vi. Endothermic reactions: An endothermic reaction is a reaction in which heat is

absorbed by the system from the surroundings. From the perspective of the system,
“heat is taken in.” For an endothermic reaction, the sign of ΔH is positive. When a
reaction is endothermic (ΔH is positive), that is an unfavourable condition. Enthalpy is
just one of the variables involved when predicting whether or not a reaction will occur,
but reactions which absorb heat are less likely to occur than ones in which heat is
released, all things being equal.

Example: As ice melts, it has to absorb heat. Therefore, if ice is defined as the system,
then the melting of ice is endothermic.

Conventions for Thermochemical Equations

1. The sign of ΔH indicates whether the reaction is endothermic or exothermic; ΔH is

directly proportional to the amount of reactant or product

2. The coefficients of the thermochemical equation represent the number of moles of

reactant and product.

3. The phases of all reactant and product species must be stated

4. The value of ΔH applies when products and reactants are at the same temperature,
usually 25 °C

For calculations:

 If a reaction is divided by 2, so is ΔH; if a reaction is multiplied by 6, so is ΔH

 ΔH changes sign when the reaction is reversed
 ΔH has the same value regardless of the number of steps

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 heat of

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CHM 101: Lecture Note Thermochemistry & Chemical Kinetics

formation ΔHf. The enthalpy of formation of an element in its standard state at 25 °C is

“0" for its ΔHθf.

Question: Find the standard change in enthalpy for the evaporation of water, and
state whether the reaction is exothermic or endothermic.

(Water vapour, Hθf = -241.82 kJ/mol; liquid water, Hθf = - 285.82 kJ/mol).

Answer: H2O(l) ⟶ H2O(g)

ΔHθrxn = ΔHθf(products) – ΔHθf(reactants)

ΔHθrxn = -241.82 – (-285.82)

ΔHθrxn = 44 kJ/Kmol. Thus, the reaction is endothermic

Question: Find the standard change in enthalpy for the condensation of water vapour,
and state whether the reaction is exothermic or endothermic

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)

Let us consider the general reaction

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CHM 101: Lecture Note Thermochemistry & Chemical Kinetics

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

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CHM 101: Lecture Note Thermochemistry & Chemical Kinetics

Question:

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CHM 101: Lecture Note Thermochemistry & Chemical Kinetics

ENTROPY

The randomness or disorder of a system is the entropy (S) of that system. The change in
entropy denotes “ΔS”.

Highlights:
 When a reaction has a positive ΔS, that is a favourable condition. Entropy is just
one of the variables involved when predicting whether or not a reaction will
occur, but reactions which increase entropy are more likely to occur than ones in
which the entropy decreases, all things being equal.
 When a reaction has a negative ΔS, that is an unfavourable condition. Entropy is
just one of the variables involved when predicting whether or not a reaction will
occur, but reactions which decrease entropy are less likely to occur than ones in
which the entropy increases, all things being equal.
 Units of ΔS is J/(K.mol)

GIBBS FREE ENERGY AND REACTION SPONTANEITY

The spontaneity of a chemical reaction is the possibility of the reaction occurring or not
without the aid of outside energy.
Highlights:
 If a reaction occurs without a net input of energy, it is called “spontaneous.” This
type of reaction actually releases (“gives off”) useful energy.
 If a reaction requires energy in order to occur, it is called “nonspontaneous.” This
type of reaction “takes in” energy when it occurs.
 Gibbs free energy is the energy that is “free” to do work.
 Units of Gibbs free energy: most often kJ/mol.
 Important formula: ΔG = ΔH – TΔS, where ΔG is the change in Gibbs free energy.
Table summarizing favorability and spontaneity
End Result Sign of ΔH Sign of ΔS Overall Sign of
ΔG
Spontaneous -ve (favourable) +ve (favourable) –
Depends on T -ve (favourable) -ve (unfavourable) ?
Depends on T +ve (unfavourable) +ve (favourable) ?
Nonspontaneous +ve (unfavourable) -ve (unfavourable) +

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CHM 101: Lecture Note Thermochemistry & Chemical Kinetics

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 energy required (enthalpy change) to convert one mole of an ionic solid
into gaseous ionic constituents.

NaCl (s) ⟶ Na+ (g) + Cl- (g)

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

Hess Law Application in the Determination of Lattice Energy

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.

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 (s), ΔH5θ = -(lattice energy, L.E.)
ΔHfθ = ΔH1θ + ΔH2θ + ΔH3θ + ΔH4θ + ΔH5θ
-411kJ = 108 + 121 +495 – 348 + (–L.E.)
Lattice energy = +787 KJmol-1.

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CHM 101: Lecture Note Thermochemistry & Chemical Kinetics

CHEMICAL KINETICS

This is the study of the rate of reaction in chemistry. A typical reaction rate unit is M/s,
the change in concentration of a species per unit time. Increasing reaction rates is the
goal of many industrial (and biological) processes.
Chemical kinetics 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: Lecture Note Thermochemistry & Chemical Kinetics

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

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CHM 101: Lecture Note Thermochemistry & Chemical Kinetics

ORDER OF REACTION
It is defined as the sum of the powers of the concentration in the rate law. Reactant
orders are typically 0, 1, 2, 3, or sometimes 0.5. A zero order reactant means that the rate
of the reaction is not influenced by the concentration of that particular reactant.
Consider the example of a reaction which has the rate law: rate = k[A]m[B]n.
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

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CHM 101: Lecture Note Thermochemistry & Chemical Kinetics

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

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 N 2O5(g)

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

0.1 0.016
0.2 0.032
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CHM 101: Lecture Note Thermochemistry & Chemical Kinetics

0.4 0.064

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

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CHM 101: Lecture Note Thermochemistry & Chemical Kinetics

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)
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

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CHM 101: Lecture Note Thermochemistry & Chemical Kinetics

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
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:
𝟏 𝒅[𝑨] 𝒅[𝑩]
Rate = =
𝟐 𝒅𝒕 𝒅𝒕
𝟏 ∆[𝑨] ∆[𝑩]
r= × =
𝟐 ∆𝒕 ∆𝒕
In general, for the reaction aA + bB ⟶ cC + dD . The rate is given by:
−1 ∆[𝐴] −1 ∆[𝐵] 1 ∆[𝐶] 1 ∆[𝐷]
𝑟𝑎𝑡𝑒 = = = =
𝑎 ∆𝑡 𝑏 ∆𝑡 𝑐 ∆𝑡 𝑑 ∆𝑡

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:
∆[ ] ∆[ ] ∆[ ] ∆[ ]
i. 𝑟𝑎𝑡𝑒 = = = =
∆ ∆ ∆ ∆

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CHM 101: Lecture Note Thermochemistry & Chemical Kinetics

ii. calculate on your own, following the solved question in (i) above

Question: 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?
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

The rate of a first-reaction depends only on the concentration of one reactant, A.
A → products
By definition, rate = - ∆[A]/∆t; rate = k[A]
Therefore, - ∆[A]/∆t = k[A]
d[A]/dt = -kt (Instantaneous rate of change described by calculus.)
ln([A]/[Ao]) = - kt (Calculus solution to the equation by integration)
ln[A] - ln[Ao] = - kt or
ln[At] = -kt + ln[Ao]
y = mx + c

ALTERNATIVELY:

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CHM 101: Lecture Note Thermochemistry & Chemical Kinetics

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)

Integration of equation (1) gives ∫ = ∫ 𝑘𝑑𝑡

( )

-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)
Half-life of first order reaction
The half-life of a reaction is a useful parameter. The half-life of a first-order reaction is
characteristic of the reaction and is independent of the starting concentration of A as
proven in the equation below:
t = (1/k) × ln [Ao]/[A]
t½ = 1/k × ln (1/0.5)
t½ = (1/k) × ln 2 = (1/k) × 0.693 = 0.693/k
t½ = 0.693/k
RATE LAW OF SECOND ORDER REACTION
Second order reactions in A can be easily described mathematically. (Note: Second
order involving [A] and [B] reactants and third order reactions will not be covered here.
For second order reactions in A:
A → products
rate = -∆[A]/∆t, but now rate = k[A]2

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CHM 101: Lecture Note Thermochemistry & Chemical Kinetics

The graphable equation becomes: 1/[A] = 1/[A o] + kt

The half-life equation can be obtained by substituting ½[Ao] = [A]
The half-life, t½ then becomes, t½ = (k[Ao])-1
This makes sense because a large rate constant leads to a faster reaction and short half-
life. In second order reactions, half-life does depend on the initial concentration of A
because a higher [Ao] means more frequent collisions between A molecules

Calculations involving Rate law and order of reaction

Q1: For a reaction with k = 5.50 x 10-3 s-1 at 45.0 ºC, what will be the concentration of A
remaining after 12.0 min if the initial concentration of A is 0.200 M?
Answer: Since the unit of k (the reaction rate constant) is s-1 in the question, it shows
that the reaction is a first order. The unit of k for a second order reaction is M-1 s-1 (k is
invariant when temperature is constant).
ln[A] = - kt + ln[Ao] = - 5.50 x 10-3 s-1 (12.0 min x 60 s/1 min) + ln (0.200)
ln[A] = - 3.96 + (- 1.61) = - 5.57
[A] = 3.81 x 10-3 M.
Q2: The reaction of nitric oxide (NO) with hydrogen at 1280 oC
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

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CHM 101: Lecture Note Thermochemistry & Chemical Kinetics

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:
5 × 10 𝑘 × (10 × 10 ) × (2 × 10 )
=
1.3 × 10 𝑘 × (5 × 10 ) × (2 × 10 )
10
3.85 =
5
2 =2
𝑥=2
Equation 3÷2 results:
10 × 10 𝑘 × (10 × 10 ) × (4 × 10 )
=
5 × 10 𝑘 × (10 × 10 ) × (2 × 10 )
2=2
𝑦=1
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)
. ×
𝑘=
( × ) ×( × )

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.

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CHM 101: Lecture Note Thermochemistry & Chemical Kinetics

Q3: The reaction of S2O82- with iodide is S2O82-(aq) + 3I‾(aq) ⟶ 2SO42-(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 S2O82- 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)

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 equation Half-life (t½)

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

Q4: 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

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CHM 101: Lecture Note Thermochemistry & Chemical Kinetics

k = 6.7 x 10-4 s-1

t = 8.8 min (= 528 s)
ln(𝑥/0.25) = -(6.7 x 10-4 ×528)
(𝑥/0.25) = e-0.3538
𝑥 = 0.176 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
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.

ACTIVATION ENERGY AND TEMPERATURE DEPENDENCE OF RATE

CONSTANTS
The Collision Theory of Chemical Kinetics
A reaction between two particles can occur only if they collide (usually in a gas or liquid
phase). Therefore, a reaction rate is proportional to the rate of collision or the number
of collisions per second.
The percentage of successful collisions in chemical systems varies greatly. In some
systems, almost every collision results in chemical change; i.e., instantaneous reaction.
In other systems, collisions rarely produce chemical change; i.e., a slow reaction.
Therefore, the reaction rate is not the same as the collision rate but is often directly
proportional to it. Chemical reactions occur when the energy of collision is enough to
break reactant bands and form product bonds. If there is not enough kinetic energy in
colliding species, reactant bonds will not break and new, product bonds will not form.
It stands to reason that higher temperatures (which increase the frequency of collisions
and increase the energy of collisions) will increase all or most reaction rates.
The kinetic energy of the colliding particles must equal or exceed a certain minimum
value in order for a reaction to proceed. This minimum energy is called the Activation
Energy, Ea. If a collision has enough energy to break some reactant bonds, an Activated

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CHM 101: Lecture Note Thermochemistry & Chemical Kinetics

Complex may form. This is an intermediate state, higher in energy than the reactants
that may lead to products or may lead back to the original reactants. The products that
form may be lower in energy than the reactants (exergonic or exothermic reaction) or
may be higher in energy than the reactants (endergonic or endothermic reaction)
The Arrhenius Equation
The Arrhenius Equation relates the rate constant k to the Ea (activation energy, J/mol or
kJ/mol), R (the gas law constant, 8.314 J mol-1 K-1) and T (the absolute temperature, K):
k = Ae-Ea/RT, A is not the reactant species, but a dimensionless constant
(Arrhenius constant) called the collision frequency or frequency factor.
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:
To adapt the equation to graphing, take the natural log of both sides. The equation
becomes:
ln k = ln A - Ea/RT
or
ln k = (- Ea/R) (1/T) + ln A
The equation corresponds to y = mx +c. Thus, a graph of ln k against 1/T is linear; where
m (the slope, –ve) = Ea/R and ln A = intercept of the graph.
Calculations involving use of Arrhenius Equation
For using the Arrhenius Equation algebraically to compare rate constant value at
different temperatures, write two equations for different temperatures and therefore
different k values.

ln k1 = ln A - Ea/RT1 and ln k2 = ln A - Ea/RT2

ln k1 – ln k2 = – Ea/RT1 + Ea/RT2

ln (k1/ k2) = Ea/R(1/T2 – 1/T1) useful for solving for T1 or T2

Question: The rate constant for a first-order reaction is 4.5 × 10-4 s-1 at 25 oC. What is its
rate constant at 50 oC if the activation energy is 35.6 kJ/mol?

Answer: Note that the collision frequency A, being the same, has cancelled out of the
equation.

T1 = (25 + 273.2) K = 298.2 K, and T2 = (50 + 273.2) K = 323.2 K.

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CHM 101: Lecture Note Thermochemistry & Chemical Kinetics

Ea = 35.6 kJ/mol which after conversion is 35600 J mol-1, since R is 8.314 J mol-1 K-1

Using ln k1 – ln k2 = – Ea/RT1 + Ea/RT2

ln k1 + Ea/RT1 – Ea/RT2 = ln k2; ln k2 = ln k1 + Ea/R( − )

ln k2 = -7.71 s-1 + 4281.93 K (2.597 × 10-4 K-1)

ln k2 = - 6.60, k2 = 1.36 10-3 s-1.

CATALYSIS

A catalyst is a substance that increases a reaction rate without itself being consumed in
the reaction. In principle, all of a catalyst can be recovered unchanged at the end of a
reaction.

The energy released or absorbed by a chemical reaction is exactly the same whether a
catalyst is present or not.

A catalyst serves to lower the Activation Energy of a reaction, allowing the bonds to
break and reform with much less input of energy.

Three main types of catalysis are (i) Heterogeneous Catalysis, (ii) Homogeneous
Catalysis and (iii) enzyme Catalysis.

Heterogeneous Catalysis

Heterogeneous two-phase) Catalysis is widely used in industrial manufacture of

chemicals. The catalyst is usually in the solid phase and the reactants are either gaseous
or liquid. The gas or liquid molecules bond temporarily to the atoms at the surface of
the catalyst, which allows their internal bonds to break more rapidly or at a lower
temperature.

Homogeneous Catalysis

Homogeneous implies that the reaction takes place in solution, with the soluble catalyst
also in solution. The classic example is the catalysis of ester hydrolysis by hydrogen ion.

CH3COC2H5 + H2O → CH3COOH + C2H5OH.

Enzyme Catalysis

Enzymes are biological catalysts, always or almost always protein in nature that speed
up many biological reactions. Enzymes have an active site, where the substrate attaches

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CHM 101: Lecture Note Thermochemistry & Chemical Kinetics

in order for its bonds to be weakened. Life as we know it would not exist without
enzymes to speed up otherwise sluggish reactions.

Enzymes are very substrate specific, since their active sites will only accept a substrate
of the right size, shape and charge distribution. Low temperatures slow down enzyme-
catalyzed reactions because collision rates are lowered. High temperatures also slow
sown enzyme-catalyzed reaction rates because high temperatures denature (damage)
proteins

Further Reading
 Carey F. A. and Giuliano R. M. (2014) Organic Chemistry, 9 th 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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