arrhenius.

mcd

S.E. Van Bramer

7/3/01

Chemistry 146 Lecture Problems Arrhenius Equation

The Arrhenius Equation k A. e
Ea R .T

From Example 21.8 in Kask and Rawn A Ea R

14 1.0 .10 .sec 1

3 joule 75 .10 . mole 1 8.314 . joule .mole .K 1

At 27 C: T ( 273
Ea R .T 1

27 ) .K

A. e

k = 8.72707 sec At 37 C: T ( 273

Ea R .T

37 ) .K

A. e

k = 23.02134 sec

arrhenius.mcd

S.E. Van Bramer

7/3/01

Calculate the change in the rate constant at different temperatures (for a known activation energy)

The Arrhenius expression at T1 and T2:

k 1 A .e

Ea R .T 1

k 2 A .e

Ea R .T 2

Divide the two expressions:

k 1 A .e k2 A .e

Ea R .T 1 Ea R .T 2

k1 e k2 e

Ea R .T 1 Ea R .T 2

Cancel A

k1 k2

Ea R .T 1

Ea R .T 2

Rearange exponents (dividing numbers, subtract exponent)

k1 k2

Ea

R .T 2

Ea R .T 1

Rearange

k1 k2

Ea

1 T2

1 T1

Extract activation energy from expression:

ln

k1 k2

Ea R

1 T2

1 T1

Take the natural log

arrhenius.mcd

S.E. Van Bramer

7/3/01

Determine change in reaction rate constant from 273 K to 284 K for different activation energies: Given: T1 T2 k2 273 .K 283 .K 1 Set k2 as 1, and will calculate k 1 (will show relative rate constant
-1

Ea = 1 kJ mole

Ea

3 joule 1 . 10 . mole Ea
.

k1

1 T2

1 T1

.k

k 1 = 0.98455 k 2

Ea = 10 kJ mole -1
3 joule 10 .10 . mole Ea
.

Ea

k1

1 T2

1 T1

.k

k 1 = 0.85583 k 2

Ea = 100 kJ mole -1
3 joule 100 .10 . mole Ea
.

Ea

k1

1 T2

1 T1

.k

k 1 = 0.2108 k 2

arrhenius.mcd

S.E. Van Bramer

7/3/01

Calculating the activation energy from the rate constant at two different temperatures The expression from above: k1 k2 Ea R
.

ln

1 T2

1 T1

Rearange and solve for the activatiion energy: Ea R ln k 2 1 T1

ln k 1

ln k 2 ln k 1 1 T2

1 T2
.R

1 T1

Ea

Calculate the activation energy for the reaction: 2 N2O5(g) -> 4 NO2(g) + O2(g) (data from Kask and Rawn) Given k1 k2 7.78 . 10 3.46 . 10
7

T1 T2

273 .K 298 .K

Solve for the activation energy: ln k 1 1 T2

5

Ea

ln k 2 1 T1

.R

E a = 1.02671 .10 joule . mole

arrhenius.mcd

S.E. Van Bramer

7/3/01

Graphical determineation of the activation energy

k A. e

Ea R .T

The Arrhenius Equation

Ea R .T

ln( k ) ln A .e

Take the natural log

ln( k ) ln( A )

ln e 1

Ea R .T

Expand expression (multiplied inside log so add)

ln( k ) ln( A )

R .T Ea R
.

.E

Expand expression (power in log so multiply)

ln( k ) ln( A )

1 T

This has the form y=mx + b where x axis is 1/T y axis is ln(k) y intercept is ln(A) slope is -Ea/R

Calcuate the activation energy and the pre-exponental factor from the following data: Data Set N 5 i 0 , 1 .. N 1

Temp (K) Ti 273 298 318 328 338

Rate Constant (sec-1) ki 7.78 . 10 3.46 . 10 4.98 . 10 4.87 . 10

7 5 4 6 4

Arrhenius Plot of Kinetics Data

3 1.50 . 10 3 ln ki 8

10

12

14

16 0.0029

0.003

0.0031

0.0032

0.0033 1 T i

0.0034

0.0035

0.0036

arrhenius.mcd
Regression Analysis: xi 1 Ti yi ln ki

S.E. Van Bramer

7/3/01

Calculation of line: Slope: Intercept: m b slope ( x , y ) intercept( x , y ) m = 1.23912 .10 b = 31.32107

4

Calculation of Activation Energy and Collision Frequency Ea A m . R .K

b e .sec 1

E a = 1.03021 .10 joule . mole

5

A = 4.00467 .10

13

sec

Regression Analysis of Arrhenius Data

8 y i ln[k] x .m i b 10

12

14

16 0.0029

0.003

0.0031

0.0032

0.0033 x i 1/T

0.0034

0.0035

0.0036

Slope of regression line

m = 1.23912 .10 Ea R Ea m.R

Slope of plot

Activation Energy

E a = 1.03021 .10 mole

5

joule . K