40
K. Kondamudi et al. / Journal of Molecular Catalysis A: Chemical 321 (2010) 34–41
Table 5
4. Conclusion
Estimated parameters in empirical Arrhenius equation with T0 = 70 ◦C.
Selective liquid phase tert-butylation of p-cresol with TBA in
room temperature ionic liquid has been systematically carried out
at different reaction conditions in a batch autoclave under auto-
geneous pressure. The SO3-H functionalized room temperature
Brønsted acidic ionic liquid, prepared in the laboratory, are inex-
pensive and contain no halogen atoms such as fluorine and chlorine.
These ILs are completely recoverable and recyclable in this alkyla-
tion reaction. The ILs can be directly reused after removal of water
under vacuum. Catalytic amount of the laboratory prepared IL-1
achieved high p-cresol conversion, complete alcohol conversion
and high product selectivity at low temperatures. Thus, these Bron-
sted acidic ionic liquid catalysts show promise for the development
of a continuous and environmentally benign, energy efficient and
economical process route for the production of TBC and BHT. The
kinetics of the reaction are well interpreted using the extended
Arrhenius equation. The experimental yields of the products match
well with model predicted yields suggesting that the reaction rate
model is appropriate.
Reaction rate constants
k1
k2
k3
A
−9.62
−9.86
−6.13
−10.7
B (103)
Ea, kcal/mol
ꢀH, kcal
ꢀS, cal
7.87
15.64
−10.61
−21.07
−21.77
−142.28
−12.18
−12.87
−14.95
−34.37
−115.94
Table 6
Estimated parameters in extended Arrhenius equation with T0 = 70 ◦C.
Reaction rate constant
k2
k3
Aꢀ
−11.18
−5.53
1.12
−11.2
−1.05
1.12
Bꢀ (×103)
Cꢀ (×108)
ꢀCp, kcal/K mol
ꢀH, kcal
ꢀS, cal
1.82
1.83
1.38
10.26
−51.34
−77.28
to heat and mass transfer resistances at low temperature and also
the solvolysis effect in the reaction [39–41]. In order to interpret
these effects on the reaction, a modified empirical form of Arrhenius
equation is applied as given below
Acknowledgements
ꢀ
ꢁ
Sreedevi Upadhyayula thanks the Department of Science and
Technology, India, for a research grant. Kishore Kondamudi thanks
Honeywell International India Private Limited, India, for a research
fellowship.
1
T
ꢁ
1
T0
ln k = A + B
−
−
+ ε
(7)
(8)
ꢀ
kT
h
ꢀH
RT
ꢀS
R
ln k = ln
+
Ea = −RB
(9a)
(9b)
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ꢀ
ꢁ
ꢀ
ꢁ
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−
+ Cꢀ
−
2 + ε
(10)
1
T
1
T0
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T
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− 1
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(11b)
(11c)
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+
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