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CD-ROM Appendix D: Using Semilog Plots in Rate Data Analysis

This document describes methods for determining the specific reaction rate constant (k) from experimental rate data using semilog graph paper. It explains that a plot of the natural log of the concentration (CA) versus time (t) should produce a straight line with a slope of -k. Two methods - an algebraic method and a graphical technique - are presented to calculate k from such a plot using linear regression. The decade method, a modification of the algebraic approach, is also described.

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32 views

CD-ROM Appendix D: Using Semilog Plots in Rate Data Analysis

This document describes methods for determining the specific reaction rate constant (k) from experimental rate data using semilog graph paper. It explains that a plot of the natural log of the concentration (CA) versus time (t) should produce a straight line with a slope of -k. Two methods - an algebraic method and a graphical technique - are presented to calculate k from such a plot using linear regression. The decade method, a modification of the algebraic approach, is also described.

Uploaded by

Sami White
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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CD-ROM Appendix D:

Using Semilog Plots


in Rate Data Analysis

Semilog graph paper is used when dealing with either exponential growth or
decay, such as
y = bemx (CDD-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
dC A
---------------  kC A (CDD-2)
dt
When t = 0, CA = CA0, where the units of CA are g mol/dm3; t is expressed in min-
utes; and k is expressed in reciprocal minutes. Integrating the rate equation, we
obtain
CA
ln --------
- = –kt (CDD-3)
C A0
We wish to determine the specific reaction rate constant, k. A plot of ln CA versus
t should produce a straight line whose slope is –k. We may eliminate the calcula-
tion 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.
TABLE CDD-1
t (min) 0 2 4 8 14
CA (gmol/dm3 ) 2.0 1.64 1.38 0.95 0.60

1
2 Appendices

Figure CDD-1

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:
C A1 C A2
ln --------
- = –kt1 ln --------
- = –kt2
C A0 C A0
lnCA2 – lnCA1 = –k(t2 – t1) (CDD-4)
Rearranging yields
lnC A2  lnC A1 ln( C A2  lnC A1 )
k = ----------------------------------  ----------------------------------- (CDD-5)
t2  t1 t2  t1
When t = 8, CA = 1.05; when t = 12, CA = 0.75. Substituting into Equation
(CDD-5) gives us

k  ln ( 1.05  0.75 )
--------------------------------- 0.336
12  8 min  --------------
1
4 min
 ( 0.084 min )
Sec. 3

Graphical Technique In the preceding example, we had


C A1
ln --------
- = –kt1 (CDD-6)
C A0
Dividing by 2.3, we convert to log base 10:
ln( C A  C A0 )
---------------------------- = log(CA/CA0) =  kt
---------
2.3 2.3
The slope of a plot of log CA versus time should be a straight line with slope
–k/2.3. Referring to Figure CDD-1, we draw a right triangle with the acute
angles located at points CA = 1.6, t = 2.8 and CA = 0.7, t = 12.8. Next, the dis-
tances x and y are measured with a ruler. These measured lengths in y and x
are 1.35 and 4.65 cm, respectively:

∆y = –1.35 cm × 1----------------
cycle –0.35 cycle
-
3.9 cm
∆x = 4.65 cm × 14 min
----------------- 9.7 min
6.7 cm
 0.35
slope = --------------- –0.0361
9.7
k = –2.3 (slope) = –2.3(–0.0361) min–1
= 0.083 min–1
A modification of the algebraic method is possible by drawing a line on semi-
log paper so that the dependent variable changes by a factor of 10. From Equa-
tion (CDD-5) in the form

ln( C A1  C A2 )
k  ------------------------------
-
t2  t1
(CDD-7)
2.3 log ( C A1  C A2 )
 --------------------------------------------
t2  t1
choose the points (CA1, t1) and (CA2, t2) so that CA2 = 0.1CA1:

2.3 log 10  2.3


k  ----------------------- (CDD-8)
- --------------
t2  t1 t2  t1

This modification is referred to as the decade method.

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