P5-5

The reaction
A ---> B + C
was carried out in a constant-volume batch reactor where the following concentration
measurements were recorded as a function of time.
t (min)

15

22

30

40

60

CA (mol/dm3)

1.6

1.35

1.1

0.87

0.70

0.53

0.35

(a) Use nonlinear least squares (i.e., regression) and one other method to determine the reaction
order and the specific reaction rate.
(b) If you were to take more data, where would you place the points? Why?
SOLUTION
This problem is more easily solved in Excel than MathCAD since the linear regression package is
easier to utilize. But we'll solve it using MathCAD. First enter the data

0
5

9
15
t := min
22
30
40

60

2
1.6

1.35
1.1 mole
C A :=

0.87 liter

0.70
0.53

0.35

Since we don't know the reaction order let's do a differential technique to get an estimate of the
order. To do this start with the rate expression for a constant volume batch reactor
dCA/dt = -kCAa
and take the log of both sides to get
ln(-dCA/dt) = ln(k) + a ln(CA)
Thus a plot of ln(-dCA/dt) versus ln(CA) should be a straight line with a slope = reaction order and
an intercept = ln (k). Let's use a central finite difference to approximate the differential. Thus we get
ii := 1 .. 6
dCA :=
ii

(C

ii+ 1

CA

ii 1

( tii+1 tii1)

0.072
0.05
mol
dCA = 0.037

liter min
0.027
0.019
0.012

Now take the logs of this data and the corresponding CA terms and put them into vy and vx vectors,
respectively.
vxii 1 := ln CA

ii

liter

mole

vyii 1 := ln( dCA)

min liter

ii

mole

Doing the regression gives

n := slope( vx , vy)

n = 1.597

lnk := intercept( vx , vy)

lnk = 3.424

corr( vx , vy) = 0.998

ij := 0 .. 5
Yij := lnk + n vxij

Differential Analysis
2.5

ln(-dCA/dt)

3.5

4.5

0.8

0.6

0.4

0.2
0
ln(CA)

0.2

0.4

0.6

let's say that the reaction is 1.6 order. The reaction rate expression then is given by
dCA/dt = -kCA1.6
Separating variables and integrating gives
CA-0.6 - CAo-0.6 = 0.6kt
Thus a plot of CA-0.6 versus time should give a straight line with a slope of 0.6k and an intercept of
CAo-0.6. The analysis and the plot are shown below
i := 0 .. 7

( )

vyyi := CA

0.6

kp := slope( t , vyy)
k :=

kp
0.6
0.6

k = 0.034

liter

0.6

mol min

C Ao := intercept( t , vyy)

1
0.6

mole

C Ao = 2.06

liter

Ycalc := intercept( t , vyy) + 0.6 k ti

i

( )

vxxi := CA

0.6

Integral Analysis
0.03

CA^-0.6

0.025

0.02

0.015

0.01

10

20

30
Time (min)

40

50

60

For a 1.6 order reaction the rate constant would be 0.034 liter0.6/mole0.6-min.
(b) The data is reasonable well distributed. The intercept lies close to the zero time concentration
(2.06 mole/liter versus 2.0 mole/liter). The best place for additional data would be a longer times.

P5-7
The following data were reported [C. N. Hinshelwood and P. J. Ackey, Proc. R. Soc. (Lond)., A115,
215 (1927)] for a gas-phase constant-volume decomposition of dimethyl ether at 504oC in a batch
reactor. Initially, only (CH3)2O was present.
Time(s)
390
Total Pressure (mmHg) 408

777
488

1195
562

3155
799

infinite
931

(a) Why do you think the total pressure measurement at t = 0 is missing? Can you estimate it?
(b) Assuming that the reaction
(CH3)2O ----> CH4 + H2 + CO
is irreversible and goes to completion, determine the reaction order and specific reaction rate k.
(c) What experimental conditions would you suggest if the were to obtain more data?
(d) How would the data and your answers change if the reaction were run at a higher or lower
temperature?
SOLUTION
The reaction rate law can be written as
dCA/dt = -kCAa
where A = (CH3)2O. However, the data is given in terms of total pressure. Thus we need to relate
CA to total pressure (P0 to solve this problem. We know that in a constant volume system the
pressure and total number of moles present are related by
PT = nT (RT/V) = CT(RT)
We know that
nT = nA + nB + nC + nD
where B = CH4, C = H2 and D = CO. We also know that
nB = nC = nD = nAo - nA
This gives
nT = 3nAo - 2nA
or
nA = 0.5( 3nAo - nT)

Dividing by V gives
CA = 0.5(3CAo - CT)
Substitute this into the rate expression to get
- 0.5(dCT/dt) = - k (0.5)a(3CAo - CT)a
Then replace CT and CAo by using the relationship between Ci and Pi (Ci = Pi/RT) to get
(- 0.5/RT) (dP T/dt) = - k (0.5/RT)a (3 PAo - PT)a
But since the initial charge was only A, PAo = PTo so we finally get
dPT/dt = (0.5/RT)a-1 k (3 PTo - PT)a
(a) In order to use this expression we are going to need PTo. A likely reason why this was not in
the original data is that the experiment was probably conducted by first filling the reactor with the
dimethyl ether, then heating it to the reaction temperature. Since the temperature increase was not
instantaneous an accurate value for PTo would be difficult to obtain. However, since the reaction
runs to completion we know that when t =
CA = 0 = 0.5(3CAo - CT)
or
CT = 3 CAo
so
PT = 3 PAo = 3 PTo
Since PT = 931 mmHg at t = , PTo = 931/3 = 310.3 mmHg.
(b) To find the order and rate constant let's start by doing a differential analysis. Taking the log of
both sides of the rate expression (given in total pressure) gives
ln (dPT/dt) = ln [(0.5/RT)a-1k] + a ln(3PTo - PT)
Now enter the data, take a forward finite difference approximation for the differential and perform
the regression (as in P5-5).

 390
777
t :=
s
1195
3155

408
488
PT :=
torr
562
799

ii := 0 .. 2
dPT :=

PT

ii

ii+ 1

PT

ii

tii+ 1 tii

0.207
torr
dPT = 0.177

s
0.121
vx2ii := ln dPT

ii

torr
s

vy2ii := ln( 931) PT

ii

torr
1

a := slope( vx2 , vy2)

a = 0.618
Y2ii := intercept( vx2 , vy2) + slope( vx2 , vy2) vx2ii
corr( vx2 , vy2) = 0.978

Differential Analysis
6.3

ln (dPT/dt)

6.2

6.1

5.9

5.8

2.2

2.1

1.9
1.8
ln(3PTo - PT)

1.7

1.6

1.5

The order is close to 0.6 so let's perform an integral analysis assuming a reaction order of 0.6. This
would give a rate expression of
dPT/dt = (0.5/RT)-0.4 k (3 PTo - PT)0.6
that can be rearranged to give
dPT/(3PTo - PT)0.6 = (0.5/RT)-0.4 k dt
This can be integrated to give
2.5[(2PTo)0.4 - (3PTo - PT)0.4] = (0.5/RT)-0.4 kt
So a plot of (3PTo - PT)0.4 versus time should give a straight line with a slope = - 0.4 (0.5/RT)-0.4 k
and an intercept of (2PTo)0.4. The integral analysis is performed below.
ii := 0 .. 3

vy3ii := 931 torr PT

0.4

ii

vx3ii := tii
m := slope( vx3 , vy3)

m = 0.013

kg

0 1

m s
inter := intercept( vx3 , vy3)

inter = 12.907 torr

0.4

corr( vx3 , vy3) = 1

Y3ii := inter + m tii

Integral Analysis
13

(3PTo - PT)^0.4 (torr^0.4)

12

11

10

500

1000

1500

2000

2500

3000

3500

Time (s)

The straight line fit looks very good (r2 = 1.0) so a 0.6 order rate expression is reasonable. The rate
constant is given by

k :=

m
0.4

cal
777 K
1.987
mole K

0.5

k = 4.711 10

mole

0.4

0.4

0.4

liter s

Calculating PTo from the intercept gives

1

PTo :=

inter

0.4

PTo = 299.271 torr

This is very close to the 310.3 torr we calculated from the t = data.
(c) Additional data in the time range between 1000 and 300 seconds would be helpful as would
data at shorter times (t < 400 s).
(d) If the reaction were run at higher or lower temperatures the order should not change. The rate
constant would go up at higher temperatures and down at lower temperatures. Running at lower
temperatures would require more time. Running at higher temperatures may make data collection
difficult.