Lecture 5: CHE 316

The Arrhenius Equation

 In 1888, Arrhenius (Swedish chemist) noted that, for most reactions, the increase in rate with
increasing temperature is nonlinear.
 He found that most reaction-rate data obeyed the equation: k = Ae-Ea/RT [*]
 This equation is called the Arrhenius equation.
Where k is the rate constant
The term Ea is the activation energy
R is the gas constant (8.314 jK-1 mol-1)
T is absolute temperature.
 The term A is constant, or nearly so, as temperature is varied. Called the frequency factor,
A is related to the frequency of collisions and the probability that the collisions are favorably
oriented for reaction.
NB: The value of A and Ea are specific to each chemical reaction.
 Notice that as the magnitude of Ea increases, k becomes smaller.
 Thus, reaction rates decrease as the energy barrier increases.
 The Arrhenius equation (k = Ae-Ea/RT) can be written in a non-exponential form that is more
convenient to use and to interpret graphically.
 Taking the logarithms of both sides and separating the exponential and pre-exponential terms
yields;
ln k = ln(Ae-Ea/RT)
Ea
In k    In A [*1]
RT
1
 Equation [*1] has a form of a straight line; it predicts that a graph of Ink versus will be a
T
 Ea
line with a slope equal to and y - intercept equal to In A.
R

1
 To evaluate Ea in a non-graphically, we need to know the rate constant of a reaction at two or
more temperatures.
 For example, suppose that at two different temperatures T 1 and T2, a reaction has rate
constants k1 and k2. For each condition we have;
𝐸𝑎 𝐸𝑎
ln 𝑘1 = − + ln 𝐴 & ln 𝑘2 = − + 𝑙𝑛𝐴
𝑅𝑇1 𝑅𝑇2
 Subtracting In k2 from In k1 gives:
  Ea    Ea 
In k1  In k 2    In A     In A 
 RT1   RT2 
 Simplifying and rearranging gives:
𝑘2 𝐸𝑎 1 1
𝑙𝑛 = { − } … … … … … … … . .2
𝑘1 𝑅 𝑇1 𝑇2

 Equation [*2] provides a convenient way to calculate the rate constant, k1, at some
temperature, T1, when we know the activation energy and rate constants, k2, at some other
temperature, T2.
Workings;
  Ea    Ea 
In k1  In k 2    In A     In A 
 RT1   RT2 
𝑬𝒂 𝑬𝒂
𝐥𝐧 𝒌𝟏 − 𝐥𝐧 𝒌𝟐 = − + 𝒍𝒏 𝑨 + − 𝒍𝒏 𝑨
𝑹𝑻𝟏 𝑹𝑻𝟐
𝑬𝒂 𝑬𝒂
𝐥𝐧 𝒌𝟏 − 𝐥𝐧 𝒌𝟐 = − +
𝑹𝑻𝟏 𝑹𝑻𝟐
𝒌𝟏 𝑬𝒂 𝑬𝒂 𝑬𝒂 𝟏 𝟏
𝒍𝒏 = − = { − }
𝒌𝟐 𝑹𝑻𝟐 𝑹𝑻𝟏 𝑹 𝑻𝟐 𝑻𝟏

OR
𝑬𝒂 𝑬𝒂
〈𝐥𝐧 𝒌𝟏 − 𝐥𝐧 𝒌𝟐 = − + 〉 × −𝟏
𝑹𝑻𝟏 𝑹𝑻𝟐
𝑬𝒂 𝑬𝒂
−𝐥𝐧 𝒌𝟏 + 𝐥𝐧 𝒌𝟐 = −
𝑹𝑻𝟏 𝑹𝑻𝟐
𝒌𝟐 𝑬𝒂 𝑬𝒂 𝑬𝒂 𝟏 𝟏
𝒍𝒏 = − = { − }
𝒌𝟏 𝑹𝑻𝟏 𝑹𝑻𝟐 𝑹 𝑻𝟏 𝑻𝟐

Sample exercise
2
1. The value of rate constant for the decomposition of nitrogen pentoxide (N2O5  N2O4 +
½O2) is 3.46 x 10-5 at 250C and 4.87 x 10-3 at 65 °C. Calculate the energy of activation for the
reaction.

Solution
The absolute temperature (in Kelvin) must be used. Therefore T1 = 273 + 25 K and
T2 = 273 + 65 K. Substituting temperature and rate constants:
𝑘1 𝐸𝑎 1 1
𝑙𝑛 = { − }
𝑘2 𝑅 𝑇2 𝑇1
3.46 × 10−5 𝐸𝑎 1 1
𝑙𝑛 −3
= { − }
4.87 × 10 8.314 338 298
𝐸𝑎 1 1
𝑙𝑛 7.105 × 10−3 = { − }
8.314 338 298
and solving we get Ea = 103.6 kJ mol-1

2. The gas-phase reaction between methane and diatomic sulfur is given by the equation;
CH4(g) + 2S2(g) → CS2(g) + 2H2S(g)
At 550 °C the rate constant for this reaction is 1.1 L/mol.s and at 625 °C the rate constant is 6.4
L/mol.s, using these values, calculate Ea for this reaction.

Solution
The relevant data is provided in the table below;
k (L/mol.s) T (°C) T (K)
1.1 = k1 550 823 = T1
6.4 = k2 625 898 = T2

𝑘2 𝐸𝑎 1 1 6.4 𝐸𝑎 1 1
𝑙𝑛 = { − } = 𝑙𝑛 = { − }
𝑘1 𝑅 𝑇1 𝑇2 𝐽
1.1 8.3145 . 𝑚𝑜𝑙 823 898
𝐾
𝐽 6.4
(8.3145 . 𝑚𝑜𝑙)𝑙𝑛
𝐸𝑎 = 𝐾 1.1 = 𝟏. 𝟒 × 𝟏𝟎𝟓 𝑱/𝒎𝒐𝒍
1 1
( − )
823 898
3. The decomposition of hydrogen iodide; 2HI(g) → H2(g) + I2(g), has rate constants of 9.51x10 -
9
L/mol·s at 500 K and 1.10x10-5 L/mol·s at 600 K. Find Ea.

Solution

3
 k (L/mol.s) T (K)
9.51x10-9 L/mol·s = k1 500

1.10x10-5 L/mol·s = k2 600

We are given two rate constants and two temperatures, so we can use the Arrhenius equation
to solve for Ea.
𝑘2 𝐸𝑎 1 1 1.10 × 10−5 𝐸𝑎 1 1
𝑙𝑛 = { − } = 𝑙𝑛 = { − }
𝑘1 𝑅 𝑇1 𝑇2 9.51 × 10 −9 𝐽
8.3145 𝐾 . 𝑚𝑜𝑙 500 600

𝐽 1.10 × 10−5
(8.3145 𝐾 . 𝑚𝑜𝑙)𝑙𝑛
𝐸𝑎 = 9.51 × 10−9 = 𝟏. 𝟕𝟔 × 𝟏𝟎𝟐 𝒌𝑱/𝒎𝒐𝒍
1 1
(500 − 600)

4. The rate constants of a reaction at 500K and 700K are 0.02s–1 and 0.07s–1 respectively.
Calculate the values of Ea and A.
(Ea = 18280.8 J; A = 1.62)
5. The first order rate constant for the decomposition of ethyl iodide by the reaction: C2H5I(g) →
C2H4 (g) + HI(g) at 600K is 1.60 × 10–5 s–1. Its energy of activation is 209 kJ/mol. Calculate the
rate constant of the reaction at 700K.
(k2 = 6.36 × 10–3 s–1)
6. The data below is for the experiment done in 1889 by Hecht and Conrad on ethoxide and
methyl iodide;
Temp. (°C) Rate constant (L/mol.s)
0 168
6 354
12 735
18 1463
24 3010
30 6250
Calculate the activation energy and the frequency factor from the data.