3.

0 REACTION KINETICS (STUDENTS 3)

The reaction of dichloroethane was determined in the pyrolysis reactor to produce

vinyl chloride and hydrochloric acid. The equation for the process is shown below.

C 2 H 4 Cl 2 → C2 H 3 Cl+ HCl

Referring to the equation above, it is found that the equation follows the elementary rate law
when the stoichiometry equation shows first order with respect to ethylene dichloride and
vinyl chloride. So, which mean that the overall order for the equation is one.

Figure 3.1: Stoichiometry equation, frequency factor, and activation energy (Karasek et al.,
2016).

From figure 3.1, the rate constant, k can be calculated from the given information. In order to
calculate the rate constant, k, formula of Arhenius equation can be applied as shown in
below.

k = A exp (-Ea / RT)

Table 3.1: Important values and parameters for furnace reactor.
Activation Energy, Ea 58000 cal/ mol
(Karasek et al., 2016)
Frequency factor, A 1.14 x 1014 s-1
1,2 dicloroethane Phase Gas
Temperature 500oC = 773K
(WD. Seider, et al., 1965)
Conversion 0.6
Pressure 26 atm
Gas Constant, R 1.987 cal/mol.K

From information obtain in figure 3.2, the value of rate constant is calculated below.
Rate Constant, k Calculation
k1 = A exp (-Ea / RT)
k1 = 1.14 x 1014 s-1 exp (-58000 cal/ mol / 1.987 cal/mol.K x 773K)
k1 = 4.54 x 10-3 s-1

Concentration Calculation
YAO = 1.0 CAO = YAOPO/RTO
PO = 26 atm CAO = 1x26 atm/0.0821 L.atm/K.mol x 773K
R = 0.0821 L.atm/K.mol CAO = 0.4097 mol/L
TO = 773K

C AO (1−X )
C A=
(1+ εX )

mol
0.4097 (1−0.6)
L
C A=
[1+ (1 ×0.6 ) ]

mol
C A=0.1024
L

Rate of Reaction, -rA Calculation

-rA = kCA
-rA = 4.54 x 10-3 s-1 x 0.1024 mol/L
-rA = 4.65 x 10-4 mol/L. s
Effect of Changing Temperature (Increase and Decrease by 10OC)
Temperature: 763K
K2 = K1 exp [(Ea/R) (1/T1 – 1/T2)]
K2 = 4.54 x 10-3 s-1 exp [(58000 / 1.987) (1/773 – 1/763)]
K2 = 2.77 x 10-3 s-1
YAO = 1.0 CAO = YAOPO/RTO
PO = 26 atm CAO = 1x26 atm/0.0821 L.atm/K.mol x 763K
R = 0.0821 L.atm/K.mol CAO = 0.4151 mol/L
TO = 763K
C AO (1−X )
C A=
(1+ εX )

mol
0.4151 ( 1−0.6)
L
C A=
[1+ ( 1 ×0.6 ) ]

mol
C A=0.1038
L

Rate of Reaction, -rA Calculation

-rA = kCA
-rA = 2.77 x 10-3 x 0.1038 mol/L
-rA = 2.88 x 10-4 mol/L. s
 Temperature: 783K
K3 = K1 exp [(Ea/R) (1/T1 – 1/T2)]
K3 = 4.54 x 10-3 s-1 exp [(58000 / 1.987) (1/773 – 1/783)]
K3 = 7.35 x 10-3 s-1
YAO = 1.0 CAO = YAOPO/RTO
PO = 26 atm CAO = 1x26 atm/0.0821 L.atm/K.mol x 783K
R = 0.0821 L.atm/K.mol CAO = 0.4045 mol/L
TO = 783K
C AO (1−X )
C A=
(1+ εX )

mol
0.4045 (1−0.6)
L
C A=
[1+ ( 1 ×0.6 ) ]

mol
C A=0.1011
L

Rate of Reaction, -rA Calculation

-rA = kCA
-rA = 7.35 x 10-3 s-1 x 0.1011 mol/L
-rA = 7.43 x 10-4 mol/L. s

Table 3.2: Different temperature for rate of reaction, -rA

Temperature(K) Rate of Reaction, -rA (mol/L. s)
763 2.88 x 10-4
773 4.65 x 10-4
783 7.43 x 10-4
Referring on table 3.2, the rate of reaction, -r A shows increasing in pattern. As the
temperature increase, so the rate of reaction also increase. Thus it shows that the
temperature affect the value of rate of reaction. All chemical processes are affected by the
temperature at which the process is occurring, although the exact change in reaction rate
with temperature is unique for any process. However, many reaction rates will approximately
double for each 103C increase in temperature, and this rule of thumb can be a helpful guide
in understanding the effects of temperature changes (Bicking, 2000).
Effect of Changing Pressure (Increase and Decrease by 2MPa=19.74atm)
Pressure: 6.26 atm
Rate Constant, k Calculation
k1 = A exp (-Ea / RT)
k1 = 1.14 x 1014 s-1 exp (-58000 cal/ mol / 1.987 cal/mol.K x 773K)
k1 = 4.54 x 10-3 s-1

Concentration Calculation
YAO = 1.0 CAO = YAOPO/RTO
PO = 6.26 atm CAO = 1x6.26atm/0.0821 L.atm/K.mol x
R = 0.0821 L.atm/K.mol 773K
TO = 773K CAO = 0.0986 mol/L

C AO (1−X )
C A=
(1+ εX )

mol
0.0986 (1−0.6)
L
C A=
[1+ (1 ×0.6 ) ]

mol
C A=0.0247
L

Rate of Reaction, -rA Calculation

-rA = kCA
-rA = 4.54 x 10-3 s-1 x 0.0247 mol/L
-rA = 1.12 x 10-4 mol/L. s
 Pressure: 45.74 atm
k1 = A exp (-Ea / RT)
k1 = 1.14 x 1014 s-1 exp (-58000 cal/ mol / 1.987 cal/mol.K x 773)
k1 = 4.54 x 10-3 s-1

Concentration Calculation
YAO = 1.0 CAO = YAOPO/RTO
PO = 45.74 atm CAO = 1x45.74atm/0.0821 L.atm/K.mol x
R = 0.0821 L.atm/K.mol 773K
TO = 773K CAO = 0.7207 mol/L

C AO (1−X )
C A=
(1+ εX )

mol
0.7207 (1−0.6)
L
C A=
[1+ (1 ×0.6 ) ]

mol
C A=0.1802
L

Rate of Reaction, -rA Calculation

-rA = kCA
-rA = 4.54 x 10-3 s-1 x 0.1802 mol/L
-rA = 8.18 x 10-4 mol/L. s

Table 3.3: Different pressure for rate of reaction, -rA

Pressure(atm) Rate of Reaction, -rA (mol/L. s)
6.26 1.12 x 10-4
26.00 4.65 x 10-4
45.74 8.18 x 10-4
From table 3.3, we can see that as the pressure increase, the rate of reaction also
increasing. Increasing the pressure on a reaction involving reacting gases increases the rate
of reaction (Brian, 2014). The molecules in smaller volume space will increase the frequency
of collision and the thus the rate increases.
Effect of Changing Conversion (Increase and Decrease by 10%)
Conversion: 0.5
Rate Constant, k Calculation
k1 = A exp (-Ea / RT)
k1 = 1.14 x 1014 s-1 exp (-58000 cal/ mol / 1.987 cal/mol.K x 773)
k1 = 4.54 x 10-3 s-1

Concentration Calculation
YAO = 1.0 CAO = YAOPO/RTO
PO = 26 atm CAO = 1x26 atm/0.0821 L.atm/K.mol x 773K
R = 0.0821 L.atm/K.mol CAO = 0.4097 mol/L
TO = 773K

C AO (1−X )
C A=
(1+ εX )

mol
0.4097 (1−0.5)
L
C A=
[1+ (1 ×0.5 ) ]

mol
C A=0.1366
L

Rate of Reaction, -rA Calculation

-rA = kCA
-rA = 4.54 x 10-3 s-1 x 0.1366 mol/L
-rA = 6.20 x 10-4 mol/L. s
 Conversion: 0.7
Rate Constant, k Calculation
k1 = A exp (-Ea / RT)
k1 = 1.14 x 1014 s-1 exp (-58000 cal/ mol / 1.987 cal/mol.K x 773)
k1 = 4.54 x 10-3 s-1

Concentration Calculation
YAO = 1.0 CAO = YAOPO/RTO
PO = 26 atm CAO = 1x26 atm/0.0821 L.atm/K.mol x 773K
R = 0.0821 L.atm/K.mol CAO = 0.4097 mol/L
TO = 773K

C AO (1−X )
C A=
(1+ εX )

mol
0.4097 (1−0.7)
L
C A=
[1+ (1 × 0.7 ) ]

mol
C A=0.0723
L

Rate of Reaction, -rA Calculation

-rA = kCA
-rA = 4.54 x 10-3 s-1 x 0.0723 mol/L
-rA = 3.28 x 10-4 mol/L. s

Table 3.4: Different conversion for rate of reaction, -rA

Conversion (%) Rate of Reaction, -rA (mol/L. s)
50 6.20 x 10-4
60 4.65 x 10-4
70 3.28 x 10-4

Effect of conversion on rate of reaction shows different trend compare to effect on

temperature and pressure. From table 3.4, it shows that the rate of reaction is decreasing
when the percentage of conversion decrease. From the rate law equation, when the
conversion increase, it is found that the reaction rate decrease.
References

Bicking, M. K. L. (2000). EXTRACTION | Analytical Extractions. Encyclopedia of Separation

Science, 1371–1382. https://doi.org/10.1016/B0-12-226770-2/02271-7

Karasek, L., Kirkpatrick, B., Lipsey, A., & Siahpush, K. (2016). Vinyl Chloride Production
CHEN 4520 Chemical Process Synthesis. 18. Retrieved from
https://static1.squarespace.com/static/58de9a70e6f2e1ff09408c52/t/594c7b95893fc0c612ba
36b1/1498184601846/BEK_MDP.pdf

Warren D. Seider, Seader, J. ., Lewin, D. R., & Widagdo, S. (1965). Product and Design
Process Principles. In The British Journal of Psychiatry (3rd ed., Vol. 111).
https://doi.org/10.1192/bjp.111.479.1009-a

Brian, M. (2014, 02 8). How do catalysts affect rates of reaction? Retrieved from Socratic:
https://socratic.org/questions/how-do-catalysts-affect-rates-of-reactions