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CD-ROM D

CD.1 Using Semilog Plots in Rate Data Analysis


Semilog graph paper is used when dealing with either exponential growth or
decay, such as
y 5 bemx (CD-1)
For the first-order elementary reaction
A products
which is carried out at constant volume, the rate of the disappearance of A is
given by
2dCA
--------------- 5 kCA (CD-2)
dt
When t 5 0: CA 5 CA0 , where the units of CA are g mol/dm3, t is expressed
in minutes, and k is expressed in reciprocal minutes. Integrating the rate equa-
tion, we obtain
CA
- 5 2kt
ln -------- (CD-3)
CA0
We wish to determine the specific reaction rate constant, k. A plot of ln CA ver-
sus t should produce a straight line whose slope is 2k. We may eliminate the
calculation of the log of each concentration data point by plotting our data on
semilog graph paper. The points in Table CDD-1 are plotted on the semilog
graph shown in Figure CDD-1.

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TABLE CDD-1
t (min) 0 2 4 8 14

CA (gmol/dm3 ) 2.0 1.64 1.38 0.95 0.60

10
8
6
5
4
3

2
CA (g mol/liter)

1.0 y
0.8
0.6 x
0.5
0.4
0.3

0.2

0.1
0 2 4 6 8 10 12 14 16
t (min)
Figure CDD-1

Fogler/PrenHall/CDD.1 S/S
Algebraic Method Draw the best straight line through your data points.
Choose two points on this line, t1 and t2, and the corresponding concentrations
CA1 and CA2 at these times:
CA1 CA2
- 5 2kt1
ln -------- - 5 2kt2
ln --------
CA0 CA0
ln CA2 2 ln CA1 5 2k (t2 2 t1 ) (CDD-4)
CD-ROM 3

Rearranging yields
ln CA2 2 ln CA1 ln ( CA1 / CA2 )
k 5 2-----------------------------------
- 5 ------------------------------
- (CDD-5)
t2 2 t1 t2 2 t1
When t 5 8, CA 5 1.05; when t 5 12, CA 5 0.75. Substituting into Equation
(CDD-5) gives us
ln ( 1.05 / 0.75 ) 0.336
k 5 ---------------------------------- 5 --------------
( 12 2 8 ) min 4 min
5 0.084 min21

Graphical Technique In the preceding example, we had


CA
- 5 2kt
ln -------- (CDD-6)
CA0
Dividing by 2.3, we convert to log base 10:
ln ( CA / CA0 ) 2kt
- 5 log ( CA / CA0 ) 5 ---------
----------------------------
2.3 2.3
The slope of a plot of log CA versus time should be a straight line with slope
2k/2.3. Referring to Figure CDD-1, we draw a right triangle with the acute
angles located at points CA 5 1.6, t 5 2.8 and CA 5 0.7, t 5 12.8. Next, the
distances x and y are measured with a ruler. These measured lengths in y and
x are 1.35 and 4.65 cm, respectively:
1 cycle
Dy 5 21.35 cm 3 ----------------- 5 20.35 cycle
3.9 cm
14 min
Dx 5 4.65 cm 3 ----------------- 5 9.7 min
6.7 cm
20.35
slope 5 --------------- 5 20.0361
9.7
k 5 22.3 (slope) 5 22.3 ( 20.0361 ) min21
5 0.083 min21
A modification of the algebraic method is possible by drawing a line on
semilog paper so that the dependent variable changes by a factor of 10. From
Equation (CDD-5) in the form
ln ( CA1 / CA2 )
k 5 ------------------------------
-
t2 2 t1
2.3 log ( CA1 / CA2 )
5 ------------------------------------------- (CDD-7)
t2 2 t1
choose the points (CA1 , t1 ) and (CA2 , t2 ) so that CA2 5 0.1CA1 :
2.3 log 10 2.3
k 5 ------------------------ 5 -------------- (CDD-8)
t2 2 t1 t2 2 t1
This modification is referred to as the decade method.

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