Differential method of analysis of laboratory kinetic data:

The following reaction between potassium persulfate and potassium iodide is kinetically analyzed as an example:

K2 S2 O8 + 2KI = 2K2 SO4 + I 2

In this reaction iodine is liberated as a product which may be analyzed at any time by titrating a sample of the reaction
mixture against standard sodium thiosulfate. In a typical experiment following data was obtained:

 0   0.0 
 303   0.90 
   
 604   1.70 
 1204   3.65 
t :=  ⋅s VN2S2O3 :=   ⋅ mL
1804 4.55
   
 2703   6.20 
 3603   7.50 
   
 4803   9.10 
Concentration of Product:

Reaction involved in the analysis of the reaction mixture: I 2 + 2Na2 S2 O3 = 2NaI + Na2 S4O6
mol
CNa2S2O3 := 0.01⋅ VI2 := 10⋅ mL ν Na2S2O3 := 2 ν I2 := 1
L

 0.000 
 − 4
 4.500 × 10 
 8.500 × 10− 4 
 
CNa2S2O3 ⋅ VN2S2O3⋅ ν I2  1.825 × 10− 3  mol
CI2 = 
− 3
CI2 :=
ν Na2S2O3 ⋅ VI2  2.275 × 10  L
 3.100 × 10− 3 
 
 3.750 × 10− 3 
 −3

 4.550 × 10 
Construction of smooth kinetic curve and tangents to the curve:
A smooth curve from the experimental data may be drawn by fitting the kinetic data either to a polynomial or to a general
exponential function. In this example a second degree polynomial is used for this purpose:

 t CI2   t CI2 
z := regress , ,2 Fitting function: f ( x) := interp  z , , ,x β := submatrix( z , 3 , length ( z) − 1 , 0 , 0 )
 s mol   s mol 
 L   L 
 →
Slopes of the tangents to the curve will be:  t  mol
S :=  β 1 + 2 ⋅ β 2⋅  ⋅
 s  L⋅ s
→
 t  mol
2
y-intercepts of the tangents will be: I :=  β 0 − β 2⋅    ⋅
  s  L
〈i〉
i := 0 .. rows( S) − 1 Tangents := ( Si⋅ t + Ii)

 
→ 2
 t L 
Goodness of fit: R_sqr := corr f   , CI2⋅  R_sqr = 0.9968
  s mol 
 0.004

0.003
Concentation of Iodine (mol/L)

0.002

0.001

0
0 500 1000 1500 2000 2500 3000 3500 4000 4500
Time (s)
Experimental data
Exponential model function
Tangents
The slope of the tangents represents the rate of production of iodine at various times:

 0.000 × 10 
0  1.434 × −6
10 
 3.030 × 10 
2  1.370 × 10 
−6
   
−6
 6.040 × 10 
2
 1.306 × 10 
 3  −6
1.204 × 1.179 ×
t=
10 
S=
10  mol
s
 1.804 × 10 
3  1.052 × 10  L⋅ s
−6
   
−7
 2.703 × 10 
3
 8.611 × 10 
 3  −7
 3.603 × 10   6.703 × 10 
 4.803 × 3  4.160 × −7
 10   10 

According to the stoichiometry of the reaction the rate of consumption of potassium persulfate will be:
RK2S2O8 := −S

If the initial concentration of potassium persulfate is 0.0125 mol/L the concentration at various times will be:
mol
CK2S28_0 := 0.0125⋅ CK2S28 := ( CK2S28_0 − C I2)
L

Now come to the actual differential method

 CK2S28   −RK2S2O8 
X := ln Y := ln
 mol   mol 
 L   L⋅min 
 9.2 Slope: B := slope ( Re( X) , Re( Y) )

Intercept: A := intercept ( Re( X) , Re( Y) )

9.4

9.6

9.8
ln(R)

10

10.2

10.4

10.6
4.9 4.8 4.7 4.6 4.5 4.4 4.3
ln(C)
Data points
Slope = 2.565
Slope = 2

The slope of this line will be equal to the order of the reaction: n := B n = 2.565

A
The intercept of this line may be used to estimate the rate constant: k := e k = 7.283

The described reaction between potassium persulfate and potassium iodide is in fact a second order reaction. The results
of the experimental kinetic data analysis is in close agreement to this fact.

In this manner just by following the concentration of a product in the time domain, one is able to establish the entire kinetic
model of a reaction.