Tutorial 6

Question 2

1)

0th order w.r.t. A & B:

= = 1

= 1 + 0

Plot of CA vs. time gives:

25

cA
[mol.m-3]

20
15
10
5
0
0

20

40

t [s]

60

80

100

k1 = 0.1546 mol.m-3.s-1
R2 = 0.9451
Better line can be fitted to these data. Therefore, it is concluded that the reaction is not a zero
order with respect to A or B.

2)

1st order w.r.t. A & 0th order w.r.t. B:

= = 2

0
= 2

ln(cA0/cA)

Plot of ln(CA0/CA) vs. t is:

1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0

20

40

60

80

100

t [s]

k2 = 0.0107 s-1
R2 = 0.9960

The data does appear to be randomly assorted around the line of best fit, which supports the idea
that the reaction is first order with respect to A, but let's check the reaction order with respect to
B.

3)

1st order w.r.t. A & B:

= = 3

3
1
1

ln
= = 3
( 3)0
1
Plot of y vs. t gives:

0.008
0.007
y
[mol-1.m3]

0.006
0.005
0.004
0.003
0.002
0.001
0
0

20

40

t [s]

60

80

100

k3 = 8.07 10-5 mol-1.m3.s-1

R2 = 0.9994

It is immediately evident that the line is a very good fit (R2 = 0.999), and the data points are
randomly scattered about the line, indicating an appropriate model. Thus, the reaction appears to
be first order with respect to both ethylene dibromide (A) and potassium iodide (B). The rate
constant is therefore approximated as 8.07 10-5 mol-1.m3.s-1

Question 3

1) Operating the experiment with species B in excess:

0 = 8 . 1

Using the method of excess:

if = 0 :

where

= 0

= + 0

Plot of CA vs. t:
1.2
1
0.8
0.6
0.4
0.2
0
0

50

100

= 1.24 10-3 mol.L-1.s-1

R2 = 0.9952

if = 1:

150

200

0
=

Plot of ln(cA0/cA) vs. t :

0.2500
0.2000
0.1500
0.1000
0.0500
0.0000
0

50

100

150

200

150

200

= 1.35 10-3 s-1

R2 = 0.9988

if = 2:

1
1
= +

Plot of (1/cA) vs. t :

1.4000
1.2000
1.0000
0.8000
0.6000
0.4000
0.2000
0.0000
0

50

100

 = 1.46 10-3 mol-1.L.s-1

R2 = 0.9997

if = 3:

1
1
2 = +
2
20
2

Plot of (cA-2/2) vs. t is:

1.0000
0.9000
0.8000
0.7000
0.6000
0.5000
0.4000
0.3000
0.2000
0.1000
0.0000
0

50

100

150

200

250

300

= 1.66 10-3 mol-2.L2.s-1

R2 = 0.9970

The second-order case displays the best linearity, thus the coefficient is assumed to be 2. For
this case, the lumped rate constant ( ) is determined to be approximately 1.46 10-3 mol-1.L.s-1
2) Operating the experiment with species A in excess:
0 = 15 . 1
Using the method of excess:
6

=
if = 0:

where

= 0

= + 0

Plot of CA vs. t is:

2.5
2
1.5
1
0.5
0
0

50

100

150

= 2.24 10-3 mol.L-1.s-1

R2 = 0.9736

if = 1:

Plot of ln(CB0/CB) vs. t is:

0
=

200

250

300

0.3500
0.3000
0.2500
0.2000
0.1500
0.1000
0.0500
0.0000
0

50

100

150

200

250

300

200

250

300

= 1.26 10-3 s-1

R2 = 0.9830

if = 2:

1
1
= +

Plot of (1/cB) vs. t gives:

0.8000
0.7000
0.6000
0.5000
0.4000
0.3000
0.2000
0.1000
0.0000
0

50

100

150

= 7.16 10-4 mol-1.L.s-1

8

 R2 = 0.9884

if = 3:

1
1
=

2
22
20

Plot of (CB-2/2) vs. t is:

0.3
0.25
0.2
0.15
0.1
0.05
0
0

50

100

150

200

250

300

350

= 4.08 10-4 mol-2.L2.s-1

R2 = 0.9940

The third-order case displays the best linearity, thus the coefficient is assumed to be 3. For this
case, the lumped rate constant ( ) is determined to be approximately 4.08 10-4 mol-4.L2.s-1

3)

From definition:

as well as

Use the average value:

1

= 2 +

1 (4.08 104 mol2 .L2 .s1 )

= 2

(15 .1 )2

(1.46 103 mol1 .L.s1 )

(8 .1 )3

2.33 106 mol4 L4 s 1

Thus, the constants of the rate expression can be approximated as:

=2

=3

= 2.33 106 mol4 L4 s1

(2.33 106 mol4 L4 s1 ) 2 3

10

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