Arrhenius Equation

The variation of the rate constant with temperature can be expressed by the Arrhenius Equation. The two-point form of this equation can be written as: k2 ln k1 = R T2 Ea 1 T1 1

Where k2 and k1 are the values of the rate constant at the Kelvin temperatures T2 and T1, respectively, Ea is the activation energy, and R is the ideal gas constant. Notice that k2 is over k1, there is a minus sign preceding Ea/R, and T2 comes before T1. This is the form of the equation used in the OWL feedback.

You may see slightly different, but equivalent, forms of this equation. It's easy to confuse the different forms. They will all give the same result, but not if you mix parts of one form with parts of another! Here are two more forms that you are likely to see. Can you spot the differences between these and the OWL form above? k2 ln k1 = R T1 Ea 1 T2 1

k1 ln k2 =

Ea

1 R T2

T1

Both of these are missing the minus sign preceding Ea/R. In the first one, this is balanced by interchanging the 1/T2 and 1/T1 terms. In the second one, this is balanced by interchanging k2 and k1.

Problem 1: The activation energy for the gas phase decomposition of 1-bromopropane is 200 kJ.

1 Arrhenius Equation

CH3CH2CH2Br

CH3CH=CH2 + HBr

The rate constant at 621 K is 5.73E-4 /s. The rate constant will be 6.70E-3 /s at 663 K. Top of Form Feedback: The variation of the rate constant with temperature is given by the Arrhenius equation, which in its two-point logarithmic form is: k2 l n = k1 R T2 Ea 1 T1 1

Where Ea is the activation energy and k2 and k1 are the rate constants at temperatures T2 and T1, respectively. Here: Ea = 200 kJ k1 = 5.73E-4 /s T1 = 621 K k2 = 6.70E-3 /s R =8.314 J/mol And the Arrhenius equation is used to solve for T2.For R=8.314J/mol K, Ea must be expressed in J: 1000 J 200 = kJ 2.00E+5 J kJ 6.70E-3 l n = 5.73E-4 8.314 T2 2.00E+5 1 621 1

2.45 = 2.406E+ 9 4

1 T2

1 621

1 = T2 -

2.459 + 2.406E+4

1 621 = 1.508E -3

T2 = 663 K

Problem 2:

2 Arrhenius Equation

The activation energy for the gas phase decomposition of trichloromethyl chloroformate is 174 kJ. ClCOOCCl3 2 COCl2

The rate constant at 555 K is 6.26E-4 /s. The rate constant will be 8.14E-3 /s at 596 K. Top of Form Feedback: The variation of the rate constant with temperature is given by the Arrhenius equation, which in its two-point logarithmic form is: k2 l n = k1 Ea R 1 T2 T1 1

Where Ea is the activation energy and k2 and k1 are the rate constants at temperatures T2 and T1, respectively. Here: Ea = 174 kJ k1 = 6.26E-4 /s T1 = 555 K k2 = 8.14E-3 /s And the Arrhenius equation is used to solve for T2. For R=8.314J/mol K, Ea must be expressed in J: 1000 J 174 = kJ 1.74E+5 J kJ 8.14E-3 l n = 6.26E-4 8.314 T2 1.74E+5 1 555 1

2.56 = 2.093E+ 5 4 1 = T2 2.565

1 T2

1 555 1 + 555 = 1.679E -3

2.093E+4

T2 = 596 K

3 Arrhenius Equation

Problem 3: The activation energy for the gas phase decomposition of 2-bromopropane is 212 kJ. CH3CHBrCH3 CH3CH=CH2 + HBr

The rate constant at 689 K is 8.07E-4 /s. The rate constant will be 1.11E-2 /s at 742 K. Top of Form Feedback: The variation of the rate constant with temperature is given by the Arrhenius equation, which in its two-point logarithmic form is: k2 Ea 1 1 l = n k1 R T2 T1

Where Ea is the activation energy and k2 and k1 are the rate constants at temperatures T2 and T1, respectively. Here: Ea = 212 kJ k1 = 8.07E-4 /s T1 = 689 K k2 = 1.11E-2 /s And the Arrhenius equation is used to solve for T2. For R=8.314J/mol K, Ea must be expressed in J: 212 kJ 1000 J kJ 1.11E-2 l n = 8.07E-4 8.314 T2 = 2.12E+5 J

2.12E+5

1 -

1 689

2.62 = 2.550E+ 1 4

1 T2

1 689

1 = T2 -

2.621 + 2.550E+4

1 689 = 1.349E -3

T2 = 742 K

4 Arrhenius Equation

Bottom of Form
1

Bottom of Form

5 Arrhenius Equation