WEEK 2 LECTURE NOTE: RATE LAWS AND ORDER OF REACTION

REACTION CONCENTRATION AND TIME

Apart from using the rate expression for determining the rate of a reaction from the rate constant
and reactant concentration, the rate expression can also be used to determine the concentrations of
reactants at any time during the course of a reaction. Integrated rate equations can be developed
relating reaction concentration with time as follow:

First-Order Reactions
The first-order reaction is a reaction whose rate depends on the reactant concentration raised to the
first power. In a first-order reaction of the type
A Product
∆[𝐴]
𝑟𝑎𝑡𝑒 = − (1)
∆𝑡
𝑟𝑎𝑡𝑒 = 𝑘[𝐴] (2)
combining equations 1 and 2
∆[𝐴]
− = 𝑘[𝐴] (3)
∆𝑡
by rearranging
∆[𝐴]
= −𝑘∆𝑡 (4)
[𝐴]
by integration
[𝐴]
ln = −𝑘𝑡 (5)
[𝐴]𝑜
OR
[𝐴]𝑜
ln = 𝑘𝑡 (6)
[𝐴]
Where [A]o = original concentration of reactant
[A] = concentration of reactant at time t
K = first-order rate constant
ln = Natural logarithm
𝑎
but ln 𝑏 = ln 𝑎 − ln 𝑏
therefore, the equation becomes
𝑙𝑛[𝐴]𝑜 − 𝑙𝑛[𝐴] = 𝑘𝑡 (7)
Solving for ln [A],
𝑙𝑛[𝐴] = ln[𝐴]0 − 𝑘𝑡 (8)
Comparing (7) with the general equation of a straight line, y = mx + c in which
m = slope of the line,
c = intercept on y axis
𝑙𝑛[𝐴] = −𝑘𝑡 + ln[𝐴]0
y = mx + c
It is clear that a plot of ln[A] versus t should be a straight line with a y-intercept of ln[A]o and a
slope of –k.
ln [A]

Intercept

= ln [A] o

Slope = - k

Fig. 1.1 Plot of ln[A] versus t

Example 5
For the first-order decomposition of N2O5 at 67oC, where k = 0.35/min, calculate:
i. The concentration after six minutes, starting at 0.200M
ii. The time required for the concentration to drop to 0.150M
iii. The time required for half a sample of N2O5 to decompose.

Solution
i. The concentration after six minutes, starting at 0.200M
Using

[𝐴]𝑜
ln = 𝑘𝑡
[𝐴]
0.200
ln = 0.35 × 6
[𝑁2 𝑂5 ]
 0.200
ln = 2.1
[𝑁2 𝑂5 ]
Taking inverse logarithm
𝑙𝑛 0.200 – 𝑙𝑛[𝑁2 𝑂5 ] = 2.1
𝑙𝑛 [𝑁2 𝑂5 ] = 𝑙𝑛0.200 – 2.1
𝑙𝑛 [𝑁2 𝑂5 ] = −1.609 – 2.1
𝑙𝑛 [𝑁2 𝑂5 ] = −3.709
[N2O5] = 𝑒 −3.709
[N2O5] = 0.024M
ii. The time required for the concentration to drop to 0.150M
[𝐴]𝑜
ln [𝐴]
= 𝑘𝑡

1 [𝐴]𝑜
𝑡= ln
𝑘 [𝐴]
1 0.200
= ln
0.35 0.150
𝑡 = 0.82 𝑚𝑖𝑛

iii. When half of the sample has decomposed

[𝑁2 𝑂5 ]𝑜
[𝑁2 𝑂5 ] =
2

[𝑁2 𝑂5 ]𝑜 = 2[𝑁2 𝑂5 ]

[𝑁2 𝑂5 ]𝑜
=2
[𝑁2 𝑂5 ]
1 [𝑁2 𝑂5 ]𝑜
But 𝑡= 𝑙𝑛 [𝑁2 𝑂5 ]
𝑘

1
𝑡=
ln 2
𝑘
0.693
𝑡=
𝑘
0.693
𝑡= = 2.0𝑚𝑖𝑛
0.35
The above example shows that the time required for one-half of a reactant to decompose via a first-
order reaction has a fixed value, independent of concentration. This quantity is called the half-life
and is given by the expression
ln 2 0.693
𝑡1⁄ = = first − order reaction
2 𝑘 𝑘
where k = rate constant; t1/2 = half − life
The half-life, t1/2, is the time required for the concentration of reactant to decrease to half of its
initial concentration. The half-life gives an estimate of the magnitude of the rate constant – the
shorter the half-life, the larger the k.
Example 6
For the decomposition of N2O5 in carbon tetrachloride (CCl4) solvent at 45oC
2N2O5 4NO2 + O2
if the data below show the variation of N2O5 concentration with time
t (s) [N2O5] (M)
0 0.91
300 0.75
600 0.64
1200 0.44
3000 0.16
Show graphically that the reaction if first-order, determine the rate constant and ln[N2O5]o.

Solution
Hint: Determine ln[N2O5] and plot a graph of ln[N2O5] (M) vs t (s).
The reaction is first order from the nature of the plot i.e. straight line with negative slope.
From the graph, k = -0.0006, ln[N2O5]o = -0.1091
For gas-phase reaction, we can replace concentration with pressure of the gaseous reactant.
Consider the first-order reaction
A(g) Products
Using the ideal gas equation
𝑃𝑉 = 𝑛𝑅𝑇
𝑛𝐴 𝑃
𝑜𝑟 = [𝐴] =
𝑉 𝑅𝑇
Substituting for [𝐴] = 𝑃/𝑅𝑇 in the equation
[𝐴]𝑜
ln = 𝐾𝑡
[𝐴]
[𝐴]𝑜 𝑃𝑜 ⁄𝑅𝑇 𝑃𝑜
ln = ln = ln = 𝑘𝑡
[𝐴] 𝑃⁄𝑅𝑇 𝑃
𝑃𝑜
i. e. 𝑙𝑛 = 𝑘𝑡; thus 𝑙𝑛 𝑃𝑜 − 𝑙𝑛 𝑃 = 𝑘𝑡
𝑃
ln 𝑃 = −𝑘𝑡 + ln 𝑃𝑜
The equation corresponds to y = mx + c
Example 7
The decomposition of ethane (C2H6) to methyl radical is a first-order reaction with a rate constant
of 5.36 x 10-4s-1 at 700oC. C2H6 2CH3*
Calculate the half-life of the reaction in minutes

Solution
0.693
𝑡1/2 =
𝑘
0.693
=
5.36 × 10−4
= 1.29 × 103 𝑠
But 60s = 1min

1.29 × 103
3
1.29 × 10 𝑠 = = 21.5𝑚𝑖𝑛
60
Second – Order Reaction
A second-order reaction is that whose rate depends on the concentration of one reactant raised to
the second power or on the concentration of two different reactants, each raised to the first power.
For a second-order reaction involving a single reactant
A Products
− ∆[𝐴]
𝑟𝑎𝑡𝑒 =
∆𝑡
𝑟𝑎𝑡𝑒 = 𝑘[𝐴]2
Equating the two equations and integrating to obtain a concentration-time relationship,
1 1
− = 𝑘𝑡
[𝐴] [𝐴]𝑜
1 1
= 𝑘𝑡 +
[𝐴] [𝐴]𝑜
Where [𝐴]𝑜 = Original concentration of reactant
[𝐴] = Concentration of reactant at time, t
k = rate constant
1
A plot of 1/[𝐴] versus t is a straight line graph with the slope k and intercept [𝐴] .
𝑜

1/[A]

Slope = k
Intercept = 1/[A] o

Fig. 1.2 Plot of 1/[A] versus t

For a second-order reaction of the type
A+B Product
rate = k[A][B]
The reaction is first-order in A and first order in B, so it has an overall reaction order of 2
Zero-Order Reaction
First- and second-order reactions are the most common. Reaction whose orders are zero are rare.
For a zero-order reaction,
A Products
rate = k[A]o = k
Thus, the rate of a zero-order reaction is a constant, independent of reactants concentrations. The
concentration-time relations for a zero-order reaction is
[𝐴] = [𝐴]𝑜 − 𝑘𝑡
i.e. [𝐴] = −𝑘𝑡 + [𝐴]𝑜
This compares with the equation of a straight line, y = mx + c, with intercept [A]o and slope –k. If
a plot of concentration versus time is linear, the reaction must be zero-order. The rate constant k
is numerically equal to the slope of that line but has the opposite sign.
[A]

Slope = -k
Intercept = [A] o

Fig. 1.3 Plot of [A] versus t

PRACTICE QUESTION
The following data were obtained for the gas-phase decomposition of hydrogen iodide.
Time (h) 0 2 4 6
[HI] 1.00 0.50 0.33 0.25
Is this reaction zero-, first-, or second-order in HI?
Summary of Kinetics of Zero-, First-, Second – Order Reactions
Order Rate Expression Concentration-Time Equation Half-life
0 rate = k [A] = -kt + [A]o [A]o/2k
1 rate = k[A] ln [A] = - kt + ln [A]o 0.693/k
2 rate = k[A]2 1/[A] = kt + 1/[A]o 1/k[A]o
MODELS FOR REACTION RATE
Different models have been developed by chemists to predict the rate constants for reactions. These
include:
(i) Collision Model
(ii) Transition-State Model

Collision Model
Chemical reactions occur as a result of collisions between reacting molecules. The rate of a
reaction is therefore directly proportional to the number of molecular collisions per second or to
the frequency of molecular collision.
𝑁𝑜 𝑜𝑓 𝑐𝑜𝑙𝑙𝑖𝑠𝑖𝑜𝑛
𝑟𝑎𝑡𝑒 𝛼
𝑠
Consider, the reaction of A molecules with B molecules to form some products. Suppose that each
product molecule is formed by the direct combination of an A molecule and a B molecule. If we
double the concentration of A, then the number of A – B collision would also double, because
there would be twice as many A molecules that could collide with B molecules in any given
volume. Consequently, the rate would increase by a factor of 2. Similarly, doubling the
concentration of B molecules would increase the rate twofold. Thus the rate expression can be
written as
𝑟𝑎𝑡𝑒 = 𝑘 [𝐴] × [𝐵]
The reaction is first-order in both A and B and obeys second-order kinetics.
The implication of this is that a reaction always occur when an A and B molecule collide. However,
not all collisions lead to reactions otherwise, most reactions would be complete almost
instantaneously. In practice, rates of reactions differ greatly. This shows that collisions alone do
not guarantee that a reaction will take place.

A molecule in a motion possesses kinetic energy, K.E. The faster it moves, the greater the K.E.
To react, it must collide with another molecule. Molecules however, are held together by strong
chemical bonds. Only if the colliding molecules are moving very rapidly will the K.E. be large
enough to supply the energy required to break these bonds. Molecules with small K.E. bounce off
one another without reacting. For every reaction, there is a minimum collision energy below which
no reaction occurs. This is referred to as the activation energy. It is the minimum amount of energy
required to initiate a chemical reaction. The activation energy for a reaction is a positive quantity
(Ea > 0) whose value depends on the nature of the reaction. The larger the activation energy, the
smaller the fraction of molecules having enough energy to react on collision so, the slower the rate
of reaction.

Transition – State Model

When molecules collide, they form an activated complex (also called a transition state) which is a
temporary, unstable, high energy species formed by the reactant molecules as a result of the
collision before they form the product.
𝐴 + 𝐵 → 𝐴𝐵 ∗ → 𝐶 + 𝐷
AB* denotes an activated complex formed by the collision of A and B. If the products are more
stable than the reactant, then the reaction will be followed with a release of heat; i.e. the reaction
is exothermic.
P.E.
AB*

Ea

A+ B

C+D

Reaction Progress

Fig. 1.4 Potential Energy Profile for a Reaction 𝐴 + 𝐵 → 𝐴𝐵∗ → 𝐶 + 𝐷

However, if the products are less stable than the reactants, then heat will be absorbed by the
reacting mixture from the surroundings and an endothermic reaction occurs.

P.E.

Ea

C+D

A+ B

Reaction Progress

Fig. 1.5 Potential Energy Profile for a Reaction 𝐴 + 𝐵 → 𝐴𝐵 ∗ → 𝐶 + 𝐷

The Ea thus represents a barrier that prevents less energetic molecules from reacting.
REACTION RATE AND TEMPERATURE
The rate of most reactions increase as the temperature increases. Raising the temperature increases
the fraction of molecules having very high speeds and hence high K.E. The higher the temperature,
the larger the fraction of molecules that can provide the Ea required for reaction.

The Arrhenius Equation

The dependence of the rate constant of a reaction on temperature can be expressed by the Arrhenius
equation given as
−𝐸𝑎⁄
𝐾 = 𝐴𝑒 𝑅𝑇

Where A = the collision frequency i.e. frequency factor. It is a constant.

Ea = Activation energy of the reaction (KJ/mol)
R = Gas constant (8.314 J/K.mol)
T = Absolute temperature (K)
e = Base of the natural logarithm
Taking the natural log of both sides of the equation
−𝐸𝑎⁄
ln 𝐾 = ln 𝐴𝑒 𝑅𝑇

𝐸𝑎⁄
𝑂𝑅 ln 𝐾 = 𝑙𝑛 𝐴 − 𝑅𝑇
Rearranging the equation
−𝐸𝑎 1
ln 𝐾 = ( ) ( ) + ln 𝐴
𝑅 𝑇
This compares with the equation of a straight line
𝑦 = 𝑚𝑥 + 𝑐
𝐸𝑎⁄
Thus, a plot of ln K vs 1/𝑇 gives a straight line with slope − 𝑅 and intercept ln A.
Example 8
The rate constants for the decomposition of acetaldehyde were measured at five different
temperatures. The data are shown in the table below. Plot ln K versus 1/T and determine the Ea (in
KJ/mol) for the reaction. CH3CHO CH4 + CO
K 0.011 0.035 0.105 0.343 0.789
T (k) 700 730 760 790 810
Solution. From the graph, -Ea/R = -2188, but R = 8.314J/k.mol, therefore Ea = 18.191kJ/mol.
The Arrhenius equation can also be used to calculate the activation energy or find the rate constant
at another temperature if the Ea is known.
At two different temperature, T1 and T2
𝐸𝑎
ln 𝑘1 = ln 𝐴 − (1)
𝑅𝑇1
𝐸𝑎
ln 𝑘2 = ln 𝐴 − (2)
𝑅𝑇2

Subtracting equation 1 from 2

−𝐸𝑎 1 1
ln 𝑘2 − ln 𝑘1 = ( − )
𝑅 𝑇2 𝑇1
𝑘2 𝐸𝑎 1 1 𝑘1 𝐸𝑎 1 1
ln = ( − ) 𝑂𝑅 ln = ( − )
𝑘1 𝑅 𝑇1 𝑇2 𝑘2 𝑅 𝑇2 𝑇1

Example 9
The rate constant of a first-order reaction is 3.46 x 10-2s-1 at 298K. What is the rate constant at
350K if the Ea for the reaction is 50.2 kJ/mol?
Solution
𝑘1 𝐸𝑎 1 1
ln = ( − )
𝑘2 𝑅 𝑇2 𝑇1
Given: k1 = 3.46 x 10-2s-1 k2 = ?
T1 = 298K T2 = 350K
Ea = 50.2 kJ/mol R = 8.314 J/K.mol

3.46 𝑥 10−2 50.2 𝑥 103 1 1

ln = (350 − )
𝑘2 8.314 298
ln 3.46 𝑥 10−2 − ln 𝑘2 = 6.038 𝑥 103 (−4.986 𝑥 10−4 )
𝑙𝑛 𝑘2 = −3.364 + 3.011
ln 𝑘2 = −0.353
𝑘2 = 𝑒 −0.353
𝑘2 = 0.702𝑠 −1