ChE 125 WFR/WFU

LE 1 Exercises/Practice

Feb 27, 2016

Problem 1
A small reaction bomb fitted with a sensitive pressure-measuring device is flushed out and then filled
with pure reactant A at a pressure of 1 atm. The operation is carried out at 25C, a temperature low
enough that the reaction does not proceed to any appreciable extent. The temperature is then raised
as rapidly as possible to 100C by plunging the bomb into boiling water, and the readings in the
following table are obtained. The stoichiometry of the reaction is 2 A B , and after leaving the
bomb in the bath over the weekend the contents are analyzed for A; none can be found. Find a rate
equation which will satisfactorily fit the data. Use the integral method of analysis.
a. in units of moles, liters, and minutes
b. in units of atmosphere and minutes
t, min
1
2
3
4

P, atm
1.14
1.04
0.982
0.940

t, min
5
6
7
8

P, atm
0.905
0.870
0.850
0.832

t, min
9
10
15
20

P, atm
0.815
0.800
0.754
0.728

Problem 2
In 1906 Bodenstein and Lind investigated the gas phase homogeneous reaction between molecular
bromine and molecular hydrogen at pressures in the neighbourhood of 1 atm. They fitted their
experimental data with a rate expression of the form
1 /2

d [ HBr ] k [ H 2 ][ B r 2 ]
=
dt
[ HBr ]
1+ k '
[ B r2 ]

( )

Where k is a constant independent of temperature and k follows the normal Arrhenius form for a
reaction rate constant with an activation energy of 40.2 kilocalories per mole.
In 1919, Christiansen, Herzfeld, and Polanyi all suggested the same mechanism for this reaction. The
key factor leading to their success was recognition that hydrogen atoms and bromine atoms could
alternately serve as chain carriers and thus propagate the reaction. By using a steady-state
approximation for the concentration of these species, these individuals were able to derive rate
expressions that were consistent with that observed experimentally.
Their original mechanism consists of the following elementary reactions:
Initiation:

B r 2 k 1 2 Br

Propagation:

Br + H 2 k 2 H + HBr

H + Br 2 k 3 Br + HBr

H + HBr k 4 H 2+ Br
Termination:

2 Br k 5 B r 2

Show that the mechanism suggested by Christiansen, Herzfeld, and Polanyi agree with Bodenstein and
Linds expression. Evaluate k and k in terms of k1, k2, k3, k4, and k5
Problem 3
g