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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)

C A

(mol/dm 3 )

 0 5 9 15 22 30 40 60 2 1.6 1.35 1.1 0.87 0.7 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

t

:=

Ê

Á

Á

Á

Á

Á

Á

Á

Á

Á

Ë

0

5

9

15

22

30

40

60

ˆ

˜

˜

˜

˜

˜

˜

˜

˜

˜

¯

min

C A :=

Ê

Á

Á

Á

Á

Á

Á

Á

Á

Á

Ë

2

1.6

1.35

1.1

0.87

0.70

0.53

0.35

ˆ

˜

˜

˜

˜

˜

˜

˜

˜

˜

¯

mole

liter

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

dC A /dt = -kC A a

and take the log of both sides to get

ln(-dC A /dt) = ln(k) + a ln(C A )

Thus a plot of ln(-dC A /dt) versus ln(C A ) 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

dC

A ii

:=

6

(

)

C

A

ii+ 1

-

C

A

ii- 1

(

t ii+1

-

t ii-1

)

dC A =

Ê

Á

Á

Á

Á

Á

Á

Á

Á

Ë

0

-0.072

-0.05

-0.037

-0.027

-0.019

-0.012

ˆ

˜

˜

˜

˜

˜

˜

˜

¯

mol

liter min

Now take the logs of this data and the corresponding C A terms and put them into vy and vx vectors, respectively.

vx ii-1

vy ii-1

Ê

Ë

È

Î

:= ln

:= ln

C A ii

liter

mole

ˆ

¯

(- dC A

) ii

min liter

˘

mole

˚

Doing the regression gives

n := slope(vx, vy)

lnk := intercept(vx, vy)

corr(vx, vy) = 0.998

n = 1.597

lnk = -3.424

ij
:= 0
5
Y
:=
lnk
+
n
ij
vx ij
Differential Analysis
2.5
3
3.5
4
4.5
0.8
0.6
0.4
0.2
0
0.2
0.4
0.6
ln(-dCA/dt)

ln(CA)

let's say that the reaction is 1.6 order. The reaction rate expression then is given by

dC A /dt = -kC A 1.6

Separating variables and integrating gives

C A -0.6 - C Ao -0.6 = 0.6kt

Thus a plot of C A -0.6 versus time should give a straight line with a slope of 0.6k and an intercept of C Ao -0.6 . The analysis and the plot are shown below

i

:= 0

vyy

i :=

7

(

C

A i

)

- 0.6

kp := slope(t , vyy)

k

k

C

C

:=

kp

0.6

=

0.034

liter 0.6

mol 0.6 min

Ao

Ao

:= intercept(t , vyy)

= 2.06 mole liter

1

- 0.6

Y

calc i

:=

vxx

i :=

(

intercept(t , vyy)

C

A i

)

- 0.6

+

0.6 k

t i

Integral Analysis

0.03
0.025
0.02
0.015
0.01
0
10
20
30
40
50
60
CA^-0.6

Time (min)

For a 1.6 order reaction the rate constant would be 0.034 liter 0.6 /mole 0.6 -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 504 o C in a batch reactor. Initially, only (CH 3 ) 2 O was present.

 Time(s) 390 777 1195 3155 infinite Total Pressure (mmHg) 408 488 562 799 931
 (a) Why do you think the total pressure measurement at t = 0 is missing? Can you estimate it? (b) Assuming that the reaction

(CH 3 ) 2 O ----> CH 4 + H 2 + 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

dC A /dt = -kC A a

where A = (CH 3 ) 2 O. 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

P T = n T (RT/V) = C T (RT)

We know that

n T = n A + n B + n C + n D

where B = CH 4 , C = H 2 and D = CO. We also know that

n B = n C = n D = n Ao - n A

This gives

n T = 3n Ao - 2n A

or

n A = 0.5( 3n Ao - n T )

Dividing by V gives

C A = 0.5(3C Ao - C T )

Substitute this into the rate expression to get

- 0.5(dC T /dt) = - k (0.5) a (3C Ao - C T ) a

Then replace C T and C Ao by using the relationship between C i and P i (C i = P i /RT) to get

(- 0.5/RT) (dP T /dt) = - k (0.5/RT) a (3 P Ao - P T ) a

But since the initial charge was only A, P Ao = P To so we finally get

dP T /dt = (0.5/RT) a-1 k (3 P To - P T ) a

(a) In order to use this expression we are going to need P To . 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 P To would be difficult to obtain. However, since the reaction

runs to completion we know that when t =

or

so

C

C

A = 0 = 0.5(3C Ao - C T )

T = 3 C Ao

P T = 3 P Ao = 3 P To

Since P T = 931 mmHg at t = , P To = 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 (dP T /dt) = ln [(0.5/RT) a-1 k] + a ln(3P To - P T )

Now enter the data, take a forward finite difference approximation for the differential and perform the regression (as in P5-5).

t

:=

390

Á 777

Ê Á

Á

ˆ

˜

˜

Á ˜

1195

Ë 3155

¯

s

P

T

:=

ii := 0

Ê Á

Á

Á

Á

Ë

408

488

562

799

2

ˆ

˜

˜

˜

¯

torr

P T ii+ 1

- P T ii

dP

T ii

:=

dP T =

t ii+1

0.207

0.177

-

ˆ

˜

˜

Ê

Á

Á

Ë ¯

0.121

t ii

torr

s

Ê

vx2 ii := ln dP

Ë T ii

s

torr

È

vy2 ii := ln (931)

Î

-

P

ˆ

¯

T

ii

1

˘

torr

˚

a := slope(vx2, vy2)

a = 0.618

Y2 ii

:=

intercept(vx2, vy2)

+

corr(vx2, vy2) = 0.978

slope(vx2, vy2) vx2 ii

Differential Analysis

6.3
6.2
6.1
6
5.9
5.8
2.2
2.1
2
1.9
1.8
1.7
1.6
1.5
ln (dPT/dt)

ln(3PTo - PT)

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

dP T /dt = (0.5/RT) -0.4 k (3 P To - P T ) 0.6

that can be rearranged to give

dP T /(3P To - P T ) 0.6 = (0.5/RT) -0.4 k dt

This can be integrated to give

2.5[(2P To ) 0.4 - (3P To - P T ) 0.4 ] = (0.5/RT) -0.4 kt

So a plot of (3P To - P T ) 0.4 versus time should give a straight line with a slope = - 0.4 (0.5/RT) -0.4 k and an intercept of (2P To ) 0.4 . The integral analysis is performed below.

ii := 0

vy3 ii :=

vx3

ii

:=

3

(

931 torr -

t ii

P

T ii

) 0.4

m := slope(vx3, vy3)

inter := intercept(vx3, vy3)

m

=

-0.013 kg 0 m 0 s 1

inter

=

12.907 torr 0.4

corr(vx3, vy3) = -1

:=
inter
+
m
Y3 ii
t ii
Integral Analysis
13
12
11
10
9
8
7
0
500
1000
1500
2000
2500
3000
3500
(3PTo - PT)^0.4 (torr^0.4)

Time (s)

The straight line fit looks very good (r 2 = 1.0) so a 0.6 order rate expression is reasonable. The rate constant is given by

k :=

m

-0.4

È 0.5

Í cal

˘ - 0.4

˙

˙

Ê

Í

Î Ë

1.987

mole K

ˆ

¯ ˚

777 K

k

=

4.711

¥

10 - 5

mole 0.4

liter 0.4 s

Calculating P To from the intercept gives

P

To

:=

inter

1

0.4

2

P To = 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.