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(a) Show by suitable integration of the first order rate equation that the half

ID: 509022 • Letter: #

Question

(a) Show by suitable integration of the first order rate equation that the half life tau_1/2 is independent of the initial reactant concentration C_0 and is given by tau_1/2 = ln 2/k where k denotes the first order rate constant. What are the units of k? (b) The Arrhenius parameters which define the Arrhenius equation for the decomposition reaction of Cyclobutane C_4H_8(g) rightarrow 2C_2H_4 (g), are In(A/s^-1) = 15.6 and E_A = 261 kJmol^-1. Determine the ratio of the half lives of cyclobutane at the temperatures 293 K and 773 K.

Explanation / Answer

1. for 1st order reaction, -dCA/dt= KCA, CA= concentration of reactant at any time , t

K= rate constant

when integrated with the condition at t=0, CA=CAO( initial concentration of A)

lnCA= lnCAO-Kt

half life is defined as the time required for the concentration to drop to 50% of its initial value

CA=CAO/2

ln(CAO/2)= lnCAO-K* half life

K* half life= lnCAO-ln(CAO/2)

K* half life= ln2

half life= 0.693/K

b) lnK= lnA- Ea/RT

K= rate constant, lnA= 15.6, Ea= 261 KJ/mol= 261*1000 J/mole

at T1= 293 K

lnK1= ln(15.6)- 261*1000/(8.314*293)

at T2= 773K

lnK2= ln(15.6) -261*1000/(8.314*773)

lnK2-lnK1= {261*1000/8.314}(1/293-1/773)

ln(K2/K1)= 66.53

K2/K1= 7.8*1028

but K= 0.693/half life

0.693/t1/0.693/t2= 7.8*1028

t1 and t2 are half lifes fot reaction at 293K and 773K respectively

t2/t1= 7.8*1028

t1/t2= 1.3*10-29