For the decomposition of azoisopropane to hexane and nitrogen at 543 K, the following data are obtained.


t (sec)



P(mm of Hg)



0



35.0



360



54.0



720



63.0



Calculate the rate constant.

When t = 0, the total partial pressure is P0 = 35.0 mm of Hg



When time t = t, the total partial pressure is Pt = P0 + p


P0-p = Pt-2p, but by the above equation, we know p = Pt-P0


Hence, P0-p = Pt-2( Pt-P0)


Thus, P0-p = 2P0 – Pt


We know that time


Where, k- rate constant


[R]° -Initial concentration of reactant


[R]-Concentration of reactant at time ‘t’


Here concentration can be replaced by the corresponding partial pressures.


Hence, the equation becomes,


equation 1


At time t = 360 s, Pt = 54 mm of Hg and P0 = 30 mm of Hg,


Substituting in equation 1,



k = 2.175 × 10-3 s-1


At time t = 720 s, Pt = 63 mm of Hg and P0 = 30 mm of Hg,


Substituting in equation 1,



Thus, k = 2.235 × 10-3 s–1


Taking average, k = (2.235 × 10-3 s–1 + 2.175 × 10-3 s–1)/2


k = 2.21 × 10-3 s–1.


21