72

The Arrhenius Equation

The Arrhenius Equation. As the name suggests, it's a bit heinous to learn l'm afraid, but super useful. lt links together
reaction constants, activation energies and temperatures all pretty important in the world of reaction rates.
-
The Arrhenius Equation Links k with Temperature and Activation Energy
The Arrhenius equation (nasty-looking thing in the green box) shows how the rate constant (k) varies with
temperature (T) and activation energy (E.,, the minimum amount of kinetic energy particles need to react).
This is probably the worst equation you're going to meet. Luckily, it'll be given to you in your exams if you need it,
so you don't have to learn it off by heart. But you do need to know what all the different bits mean, and how it works.
Here it is:

r I ll I l\\\ I I I \\ l\l/-
Ir - AeE if, ,n
erPonenl\a\ :-
=t relationshiP This -
1
k = rate constant i 'e' is the .x [utton -
'-. on You, calcuiator', 1
fn = activation energy U) )',",', (i,,r I \ \ | \ \ I r\\
T = temperature (K)
What be a pirale's R - gas constant (8.31 J K-l mol-l)
lavourite parl ol chemislry? A = the Arrhenius constant
The ARR-henius equationl
(another constant)

r) As the activation energy, {,

gets bigger, k gets smaller.
You can test this out by trying different numbers for {
in the equation... ahh go on, have a go.
2) So, a large will mean a slow rate. This makes sense when you think about it if a reaction has
{
a high activation energy, then not many of the reactant particles will havq enough energy to react.
-
So only a few of the collisions will result in the reaction actually happening, and the rate will be slow.

3) The equation also shows that as the temperature rises, k increases.

(You can test this out by trying different numbers for T as well. Will the fun hever cease?)

4) The temperature dependence makes sense too. Higher temperatures mean reactant particles
move around faster and with more energy so they're more likely to collide and more likely
to collide with at Ieast the activation energy, so the reaction rate increases.

Use the Arrhenius Equation to Calculate the Rate Constant or E,

You might be given four of the five values from the Arrhenius equation and asked to use the equation
to find the value of the fifth. Here's how you'd go about getting the answer...

Example: Thedecompositionof NrOrat30BKhasarateconstantof 1.35x10-as-l . TheArrheniusconstantfor

this reaction is 4.79 x 1013 s-l . Calculate the activation energy of this reaction. (R = 8.31 J K-] mel-1)

First it's a good idea to get the Arrhenius equation into a simpler form so it's easier to use. That means getting
rid of the nasty exponential bit so you need to take the natural log (ln) of everything in the equation:
-
-fa F \\ll lllllllllll\11\llll/-
ln k ln A - 1-
k= Aeffi = ffi -:
Thankfully there should
be a handy'1n' bullan i
-
Nowrearrangetheequationtoget{onthelefthandside: #:,nA-lnk -"Lff:;;:i:X5'iirl'
' /i I I I I I i l I L I I I / I / I I l\' ..

And another quick rearrangement to get { on its own: g = (ln A - ln k) x RT

Now you can just pop the numbers from the question into this formula:
fu = (ln (4.79 x 1013) - ln (1.35 x 10-a)) x (8.31 x 308)
= (31.5... - (-8.91...)) x (8.31 x 308) = 1O3 429.54 J mol-l = I03 kl mol-l (3 s.f.)

Uxt l: Srcnox 7 - R,qrr Eeu,qrtoNs AND Kp

 73

The Arrhenius Equation

Use an Arrhenius Plot to Find the E. and the Arrhenius Constant
1) As you saw on the previous page, putting the Arrhenius equation
into logarithmic form generally makes it a bit easier to use. ln/r:*ft*ln,{
2) You can use the equation in this form to create an Arrhenius plot by plotting ln k against .
f r
3) The line of best fit for the points on the Arrhenius plot will be a straight line graph with a gradient of 3
4) Once you know the gradient, you can use it to find both the activation energy and the Arrhenius constant
Example: The graph below shows an Arrhenius plot for the decomposition of hydrogen iodide.
Calculate the activation energy and the Arrhenius constant for this reaction. R = 8.31 J K 1 mol-l .

To find the gradient, pick two points on the Iine with

'nice' coordinates, e.g. (0.002, -20) and (0.0038, -60).

gradient = t, * = _22 222

= _22 222.
"Or*
E,=-(-22222x8.31)=1S4666J mol-l .'""'1'; "'-
= 18s kl mol-!13 s.f.) ;
; i??,3/ '
To find ln A, substitute the gradient and the coordinates
of any point on the line into ln/< : -# h+lnn \\./iirr tt\ttttt/-
-E1r
-E^,1
,1r-->-tr.,-L4-
45, =- -n
At (0.002, -20): -20= (Oiffi x o.oozfflnn ;,,1,,,f,,,,,11,;
^T- -nr -
-\\ l I | | I I J I I I I l i I I I I I r I I I I I I I I I I I I I / I I I I I I I | | 1t I t //
-: -20 = -44.4 + ln A
-- The values of k and T used to draw lhe Arrhenius plot
-- come lrom experimenls. To galher lhe dala you repeat 1 ln A = 24.4,so A = e244 - 4 x "1010 dm3 mol-1 s*1
-- lhe same experimenl al several disere"t temperatu.es. .]
'rt \t tt I | | I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I lr' |
tr\l\
.1
r /I | I I I I I l'ta,r \ I I I I I I I I | | I | | | \ t //
i tt". va.ue of ln A is g ve. io one '--
- deci..tal pla.ehere, so yo" should give :
://ll' rt^is answer to one siqniftca.l ltqLre :
t\llli I ltt, I l/\ \i r rlr \lirt t,t'-
Q1 In the Arrhenius equation, what do the terms k, T and R represent?
Q2 How does increasing the temperature of a reaction affect the value of k?
Q3 The Arrhenius equation is k = 4s-r'rnr. Which one of the following answers is true as E increases?
A k increases and rate of reaction increases. B k increases and rate of reaction decreases.
C k decreases and rate of reaction increases. D k decreases and rate of reaction decreases.
Q4 Describe how you would find activation energy from a graph of In k against 1/T.

Exam Question

Ql The table on the right gives values for the rate constant of the reaction
between hydroxide ions and bromoethane at different temperatures.

a) Complete the table. [2 marks]

b) Use the table to plot a graph that would allow you
to calculate the activation energy ofthe reaction. [3 marks]
c) Calculate the activation energy ofthe reaction.
(R: 8.31 J K-tmol 1) [2 marks]
d) Calculate the value of the Arrhenius constant, A. I mark]

...rhenius? You don't need to learn the Arrhenius equation, but you do need to know how to use it. There's some
vicious-looking maths here, but the best way to get your head around it is to do loads of practice questions. Then, if any
of the different rearrangements of thegquation pop up in the exam, you can lookthem in the eye without panicking.

UNr 1: Srcnox 7 - R,qrr Eeu,qrtoxs AND K