Handout # 1 Nechar Draoui, Charif

a) We use the kinetic data at 25ºC for the reaction A → B to determine what is the order
of the reaction:

t, s 25º C Ca M ln(CA0/CA) 1/Ca

0 0,75 0 1,33333333
900 0,648 0,14618251 1,54320988
1800 0,562 0,28857136 1,77935943
2700 0,514 0,37784994 1,94552529
3600 0,46 0,48884672 2,17391304
4500 0,414 0,59420723 2,41545894
5400 0,385 0,66682987 2,5974026

It doesn’t matter what kind of temperature’s kinetic data we use because the order of the
reaction doesn’t depends of the temperature.

We make a graph of Ca Vs time to determine if its order 0. We can see that R² = 0,9621.

y = -7E-05x + 0.7117
Zeroth Order R² = 0.9621
0.8
0.7
concentración, M

0.6
0.5
0.4
Series1
0.3
0.2 Linear (Series1)
0.1
0
0 1000 2000 3000 4000 5000 6000
tiempo, s
 Handout # 1 Nechar Draoui, Charif

We make another graph with ln(CA0/CA) Vs time to determine if its order 1. We can see that
R² = 0, 9897. It’s better than zeroth order.

y = 0.0001x + 0.0343
First Order R² = 0.9897

0.8
0.7
0.6
ln concentración

0.5
0.4
Series1
0.3
0.2 Linear (Series1)

0.1
0
0 1000 2000 3000 4000 5000 6000
tiempo, s

Finally we make another graph with 1/CA Vs time to determine if its order 2. We can see that
R² = 0, 9987. It’s the best option so we can say that this reaction is a Second Order Reaction.

Second Order y = 0.0002x + 1.3343

3 R² = 0.9987

2.5
1/concentración

1.5
Series1
1 Linear (Series1)

0.5

0
0 1000 2000 3000 4000 5000 6000
tiempo, s

Once determined the kinetic law (second order), we can get the k from the equation of the
line because it is the value of the slope. In this case the slope of this equation is 0,0002 so we
can say that the value of k at 25ºC is 0,0002 L/mol.s
 Handout # 1 Nechar Draoui, Charif

b) The value of k depends of the temperature so in this table we can see the variation of
k respecting the temperature. We get this table doing the steps that we have done
before to find out k.

T ºC 25 30 35 40 45
k L/mol.s 0,0002 0,0003 0,0004 0,0005 0,0007

c) To find out the activation energy value (that it doesn’t change with the temperature)
we can draw a graph with ln k Vs 1/T and use the Arrhenious equation.

T ºK k L/mol.s 1/T ln k
298 0,0002 0,0033557 -8,51719319
303 0,0003 0,00330033 -8,11172808
308 0,0004 0,00324675 -7,82404601
313 0,0005 0,00319489 -7,60090246
318 0,0007 0,00314465 -7,26443022

According to the Arrhenious equation  ln k = ln A – (E/R)*(1/T) we can say that the slope of
this equation line is equal to – (E/R).

-7.2
0.0031 0.00315 0.0032 0.00325 0.0033 0.00335 0.0034
-7.4

-7.6

-7.8
ln k

ln k
-8 Linear (ln k)

-8.2
y = -5722x + 10.724
-8.4
R² = 0.9926
-8.6
1/ Temperature

So -5722 = - (E/R), we know R which is 8.314 J/mol*K, we isolate E and get his value which is
47572 J/mol. And with all this data we can calculate the pre-exponential factor using the
Arrhenious equation with each k and T and isolating the A.
 Handout # 1 Nechar Draoui, Charif

These are the values of k and A for each temperature:

T ºK k L/mol.s 1/T ln k Ea J/mol A sec-1

298 0,0002 0,0033557 -8,51719319 47572 43491
303 0,0003 0,00330033 -8,11172808 47572 47648
308 0,0004 0,00324675 -7,82404601 47572 46611
313 0,0005 0,00319489 -7,60090246 47572 43306
318 0,0007 0,00314465 -7,26443022 47572 45504