Chemistry 415 Fall 2014

Assignment 1 P&S 1: 3,4,6

PS 1.3
The following data give the pseudo-first-order rate coefficient for
CH + O2 = products
under conditions where [CH]<<[O2]:

[O2]/10-7 mol/l 2.56 6.41 9.19 13.12 17.28 21.43 24.09

k’/s-1 19600 29850 34590 45700 59700 64700 80700
Determine the bimolecular rate coefficient.

presumably R=k[CH][O2] ≈ k'[CH] where k'= k [O2]

O2 k'
2.5600e-07 1.9600e+04
6.4100e-07 2.9850e+04
9.1900e-07 3.4590e+04
1.3120e-06 4.5700e+04
1.7280e-06 5.9700e+04
2.1430e-06 6.4700e+04
2.4090e-06 8.0700e+04

we plot k' vs [O2]; slope = k = 2.70e+10 liter/molsec.

9 104

y = 11539 + 2.7011e+10x R= 0.99137

8 104

7 104

k'
6 104

5 104
k'

4 104

3 104

2 104

1 104
0 5 10-7 1 10-6 1.5 10-6 2 10-6 2.5 10-6

O2
 Chemistry 415 Fall 2014
Assignment 1 P&S 1: 3,4,6

1.4 The thermal decomposition of dimethyl ether has been studied by measuring the
increase of pressure with time
Me2O = CH4 + H2+ CO

The following data were obtained at 777 K with initial pressure of ether 312 Torr.
Time/sec 390 777 1195 2000 3155
Pressure increase/Torr 96 179 250 363 467

At 777 K, all species are gases. We’re given the increase in pressure at various times.
We need to relate the increase in P with the reaction.

Presumably we start with pure Me2O, and its pressure is P0. The concentration of Me2O
is n/V =PE/RT where PE the partial pressure of the ether. Similar relations hold for the
other gases.

At any stage in the reaction,

P(total) = PE + PM + PH + PC (1)
accounting for the ether, methane, hydrogen and CO, respectively.

One ether gives M + H + C. If we start with pure E, then PH=PM=PC

So P0 - PE (pressure change of E) = PM=PH=PC.

Substitute in eqn 1 and we get
P(total) = PE + 3 (P0 - PE) = 3P0 - 2PE (2)

or PE = 1/2(3P0 - Ptot) = 1.5 P0 -.5Ptot

∆P = Ptot - P0

PE = P0 - 0.5 ∆P = 312 - 0.5∆P (3)

plotting ln Pe vs t gives a straight line so reaction is 1st order. Slope is -4.39e-04 = -k

units are sec-1. (you get k=1.9e-4 if you use log10.)

 Chemistry 415 Fall 2014
Assignment 1 P&S 1: 3,4,6

Pilling & Seakins, P 1.4

5.8

5.6

a=5.749
5.4
sa=0.0035788
b=-0.000438812
5.2 sb=1.99205e-06

4.8

4.6

4.4

4.2
0 500 1000 1500 2000 2500 3000 3500
time (sec)

PS 1.6

The rate of a certain reaction doubles on increasing T from 290 K to 300K. Evaluate the
activation energy.

∂(ln k) R∆lnk Rln 2

Ea = - ∂(1/T) * R ≈ ∆(1/T) ≈ (1/290-1/300) = .0695*2/1.1494e-04 = 1.1982e+04
cal/mol= 11.98 kcal/mol=50kJ/mole