Section 7.

4 Differential Method of Analysis 255

Before solving an example problem, review the steps to determine the reaction
rate law from a set of data points (Table 7-1).

Example 7-2 Determining the Rate Law

The reaction of triphenyl methyl chloride (trityl) (A) and methanol (B) discus ed in
Example 7-1 is now analyzed using the differential method.
0
II
(C 6 H 5 ) CCI+CH 3 0H~(C 6 H 5 ) CCH 3 +HCI
3 3
A + B ~ c +D
The concentration-time data in Table E?-2. 1 was obtained in a batch reactor
T ABLE E7-2.1. RAw DATA

Time (min) 0 50 I00 150 200 250 300

Concentration of A (mol/dm 3 ) x 101 50 38 30.6 25.6 22.2 19.5 17.4

(At t = 0, CA = 0.05 M)

The initial concentration of methanol was 0.5 mol/dm 3 .

Part (1) Determine the reaction order with respect to triphenyl methyl chloride.
Part (2) In a separate set of experiments, the reaction order wrt methanol was
found to be first order. Determine the specific reaction rate constant.

Solution
Part (1) Find reaction order with respect to trityl.
Step 1 Postulate a rate law.

-rA = kCa ,.,a

ALB (E?-2.1)

Step 2 Process your data in terms of the measured variable, which in this
case is CA-
Step 3 Look for simplifications. Because the concentration of methanol is I 0
times the initial concentration of triphenyl methyl chloride, its concentra-
tion is essentially constant
CB =CBo (E7-2.2)

Substituting for C9 in Equation (E7-2.1)

-rA = kdo~
~A

k'

-rA = k'd (E7-2.3)

Step 4 Apply the CRE algorithm.

Mole Balance

dN
_A=r V (E7-2.4)
dt A
256 Collection and Analysis of Rate Data Chapter 7

Rate Law:

,.,
-rA = k'd (E7-2.3)

Stoichiometry: Liquid V = V0
~
,;~ CA-- NA
-
Vo
Following the Algorithm Combine: Mole balance, rate law, and stoichiometry

(E7-2.5)

Evaluate: Taking the natural log of both sides of Equation (E7-2.5)

ln [- d~A J =Ink'+ a ln CA (E7-2.6)

The slope of a plot of In [- d~A J versus In CA will yield the reaction

order a with respect to triphenyl methyl chloride (A).

Step 5 Find [- d~A J as a function of CA from concentration-time data.

Step SA.la Graphical Method. We now construct Table E7-2.2.
The derivative (-dCA/dt) is detem1ined by calculating and plotting
(-t1.CA/t1.t) as a function of time, t, and then using the equal-area differ-
entiation technique (Appendix A.2) to determine (-dCA/dt) as a function
of CA- First, we calculate the ratio (-t1.CA/t1.t) from the first two columns
of Table E7-2.2; the result is written in the third column.

TABLE E7-2.2 PROCESSED DATA

_t1.CA X 104 _dCA X 104

/).( dt
t (min) CA x I0 3 (mol/dm 3) (moUdm 3 · min) (molldm 3 · min)
0 50 3.0
2.40t
50 38 1.86
1.48
100 30.6 1.2
1.00
150 25.6 0.8
0.68
200 22.2 0.5
0.54
250 19.5 0.47
0.42
300 17.4
Section 7.4 Differential Method of Analysis 257

Next we use Table E7-2.2 to plot the third column as a function of the first column
in Figure E7-l.l [i.e., (-!J.CA/!J.t) versus t]. Using equal-area differentiation, the
value of (-dCA/dt) is read off the figure (represented by the arrows); then it is used
to complete the fourth column of Table E7-2.2.

2.5

- dC, X 10'
d1
15
- 1\C" X 1o-
A1

{dm~1n) .5

50 100 150 300 250 300 350

1(mln)

Figure E7-2.1 Graphical differentiation.

The results to find (-dCA/dt) at each time, t, and concentration, CA, are summarized
in Table E7-2.3.

We will now use Table E7-2.3 to plot column 2 (- dCA X I 0, 000) as a func-
dt
tion of column 3 (CA x I ,000) on log-log paper as shown in Figure E7-2.2. We
could also substitute the parameter values in Table E7-2.3 into Excel to find a and
k'. Note that most of the points for all methods fall virtually on top of one another.

TABLE E7-2.3 SUMMARY OF PROCESSED DATA 10.-------------~

G.raahical
I • Grnphocal I
- dCA X 10,000
I dt CAx 1,000
(min) (mol/dm 3 • min) (mol/dm 3)
0 3.0 50
50 1.86 38
100 1.20 30.6
mol
150 0.80 25.6
dm 3 min Slope= 1.99
200 0.68 22.2
250 0.54 19.5 -dCA = 0.125C.:
99
dl
300 0.42 17.4
0.1 +-------~
10 100
CA x 103 (mol/dm3)

Figure E7-2.2 Excel plot to

determine a and k.

From Figure E7-2.2, we found the slope to be 1.99, so that the reaction is said
to be second order (a= 2.0) with respect to triphenyl methyl chloride. To evaluate k',
we can evaluate the derivative in Figure E7-2.2 at CAp= 20 x 10-3 mol/dm 3 , which is

( - dCA) = 0.5 x l0-4 mol/dm3 · min (E7-2.7)

dt p
258 Collection and Analysis of Rate Data Chapter 7

then

(E7-2.8)

-4 3 .
0.5 X 10 mol / dm ·mm d .
= 0 . 125 m31 mo 1 · m1n
-3 3 2
(20 X 10 mol / dm)

As will be shown in Section 7-5, we could also use nonlinear regression on Equa-
tion (E7-1.5) to find k':

k' = 0.122 dm 3/mol · min (E7-2.9)

The Excel graph shown in Figure E7-2.2 gives a= 1.99 and k' = 0.13 dm 3/mol · min.
We could set a= 2 and regress again to find k' = 0.122 dm 3/mol · min.

~ummary Note~
ODE Regression. There are techniques and software becoming avai lable whereby
an ODE solver can be combined with a regression program to solve differential
equations. such as

_dCA=k'Ca (E5-7-2.5)
dt A A

to find kA and a from concentration-time data.

Part (2) The reaction was said to be first order with respect to methanol,~= 1,

(E7-2.10)

Assuming C 80 is constant at 0.5 mol/dm 3 and solving fork yields 1

3
dm
0.122--=..:..:..:._.,-
k = .!{_ = mol· min
Cso 0 5mol
. dm 3

k = 0.244 (dm 3/mol) 2 I min

The rate law is

(E7-2. 11 )

Analvsis: In this example the differential method of data analysis was used to find
the reaction order with respect to trityl (a = 1.99) and the pseudo rate constan t
(k' = 0.125 (dm 3/mol)/min). The reaction order was rounded up to a = 2 and the
data was regressed again to obtain k' = 0.122 (dm 3/mol)/mjn, again knowing k' and
C80 and the true rate constant is k = 0.244 (dm 3/mol)2/min.

Integral method By comparing the methods of analysis of the rate data presented in
normally used to Examples 7-1 and 7-2, we note that the differential method tends to accentuate the
find k when order
is known uncertainties in the data, while the integral method tends to smooth the data,

1
M. Hoepfner and D. K. Roper. "Describing Temperature Increases in Plasmon-Resonant
Nanoparticle Systems," Journal of Thermal Analysis and Calorimetry, Vol. 98( l),
197-202 (2009).