Rare earth metal ion exchanged (La3+, Ce3+, RE3+) KFAU-Y zeolites were prepared by simple ion-exchange methods and have
been characterized using different physico-chemical techniques. In this paper a novel application of solid acid catalysts in the dehydration/
Beckmann rearrangement of aldoximes; benzaldoxime and 4-methoxybenzaldoxime is reported. Dehydration/Beckmann
rearrangement reactions of benzaldoxime and 4-methoxybenzaldoxime is carried out in a continuous down flow reactor at
473K. 4-Methoxybenzaldoxime gave both Beckmann rearrangement product (4-methoxyphenylformamide) and dehydration product
(4-methoxybenzonitrile) in high overall yields. The difference in behavior of the aldoximes is explained in terms of electronic
effects. The production of benzonitrile was near quantitative under heterogeneous reaction conditions. The optimal protocol allows
nitriles to be synthesized in good yields through the dehydration of aldoximes. Time on stream studies show a fast decline in the
activity of the catalyst due to neutralization of acid sites by the basic reactant and product molecules.
Sugunan, S(Indian Journal of Chemistry, February , 1983)
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Abstract:
Solubilities of 4-nitrobenzoic acid at 25°, 35° and 42°C have
been determined in water and in the presence of several concentrations
of electrolytes. The free energies, enthalpies and entropies
of transfer are also reported. The data have been rationalized
by considering the structure-breaking effects of the ions of
the salts and the requirement of the localized hydrolysis model.
The theory of Symons is not satisfactory to rationalise the
experimental data.
Rice husk silica was utilized as the promoter of ceria for preparing supported vanadia catalysts. Effect of vanadium content was investigated with 2–10 wt.% V2O5 loading over the support. Structural characterization of the catalysts was done by various techniques like energy dispersive X-ray (EDX), X-ray diffraction (XRD), BET surface area, thermal analysis (TGA/DTA), FT-infrared spectroscopy (FT-IR), UV–vis diffused reflectance spectroscopy (DR UV–vis), electron paramagnetic spectroscopy (EPR) and solid state magnetic resonance spectroscopies (29Si and 51V MASNMR). Catalytic activity was studied towards liquid-phase oxidation of benzene. Surface area of ceria enhanced upon rice husk silica promotion, thus makes dispersion of the active sites of vanadia easier. Highly dispersed vanadia was found for low V2O5 loading and formation of cerium orthovanadate (CeVO4) occurs as the loading increases. Spectroscopic investigation clearly confirms the formation of CeVO4 phase at higher loadings of V2O5. The oxidation activity increases with vanadia loading up to 8 wt.% V2O5, and further increase reduces the conversion rate. Selective formation of phenol can be attributed to the presence of highly dispersed active sites of vanadia over the support.
Ramankutty, C G; Sugunan, S; Bejoy, Thomas(Elsevier, September 9, 2002)
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Abstract:
Preparation of simple and mixed ferrospinels of nickel, cobalt and copper and their sulphated analogues by the room temperature coprecipitation method yielded fine particles with high surface areas. Study of the vapour phase decomposition of cyclohexanol at 300 °C over all the ferrospinel systems showed very good conversions yielding cyclohexene by dehydration and/or cyclohexanone by dehydrogenation, as the major products. Sulphation very much enhanced the dehydration activity over all the samples. A good correlation was obtained between the dehydration activities of the simple ferrites and their weak plus medium strength acidities (usually of the Brφnsted type) determined independently by the n-butylamine adsorption and ammonia-TPD methods. Mixed ferrites containing copper showed a general decrease in acidities and a drastic decrease in dehydration activities. There was no general correlation between the basicity parameters obtained by electron donor studies and the ratio of dehydrogenation to dehydration activities. There was a leap in the dehydrogenation activities in the case of all the ferrospinel samples containing copper. Along with the basic properties, the redox properties of copper ion have been invoked to account for this added activity.
Sunajadevi, K R; Sugunan, S(Elsevier, September , 2005)
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Abstract:
Titania, sulfated titania and chromium loaded sulfated titania were prepared by sol–gel method and characterized using different technique. Phenol is nitrated regioselectively by nitric acid using chromium loaded sulfated titania catalysts. A remarkable ortho selectivity is observed in solid state nitration to yield exclusively ortho-nitrophenol. Compared to the conventional process, phenol nitration over solid acid catalyst is a clean and environment friendly process. Catalytic activity well correlates with the Brönsted acid sites of these catalysts.
Sugunan, S; Rahna, K S(Indian Journal of Chemistry, July , 2002)
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Abstract:
The incorporation of transition metal oxide pillars such as those of iron and chromium along with Al2O3, pillars within
the interlayers of a montmorillonite clay is investigated. The surface acidity of these catalysts has been evaluated for the first
time employing the equilibrium adsorption of an electron donor, perylene, and the results are compared with those obtained
by temperature programmed desorption of ammonia. The principle is based on the ability of a catalyst surface site to accept
a single electron from an electron donor like perylene to form charge transfer complexes and the amount of adsorbed species
is measured quantitatively by UV-vis spectroscopy. Fina1ly, an attempt has been made to correlate the acidity determined by
the two independcnt methods and the catalytic activity of present systems in the benzoylation of toluene with benzoyl
chloride. Incorporation of Fe and Cr has changed the properties of AI pitlared montmorillonite. Fe pillared systems have
been found to be vcry good catalysts for benzoylation reaction
Sugunan, S; Kumaree Seena, C R(Indian Journal of Chemistry, May , 1998)
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Abstract:
We have investigated the changes in surface acidity/basicity
and catalytic pro~erties of samarium oxide due to surface modification
by SO42- ion. The acidity/basicity of the catalysts is
determined by titration method using Hammett indicators.
Esterification of acetic acid by n-butanol is chosen as a test
reaction. Sm203, owing to its high basicity and low acidity, does
not catalyze the reaction. But sulphated Sm20J catalyzes the
esterification reaction effectively. Activation temperature does
not have much effect on the acidity of sulphated samaria.
Sugunan, S; Anto, Paul(Indian Journal of Chemistry, April , 1997)
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Abstract:
The surface acidity/basicity of binary oxides of Zr and La and the ternary oxides of Zr, La and Al are
reported. The data have been correlated with their catalytic activity towards liquid phase reduction of
cyclohexanone.
Sugunan, S; Bindhu, Jacob(Indian Journal of Engineering & Materials Sciences, June , 1997)
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Abstract:
The surface acidity and basicity of ternary oxides of
AI, Ce and Dy have been determined using a set of
Hammett indicators. The data have been correlated
with the catalytic activity of these oxides towards the
liquid phase reduction of cyclohexanone in 2-propanol.
The reaction is favoured by the higher basicity of
the ternary oxide.
Sugunan, S; Ampili, S; Bindhu, Jacob; Rani, Varghese(Indian Journal of Chemistry, February , 1996)
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Abstract:
The surface acidity and basicity of ternary oxides of
La, Ce and AI have been determined using a set of
Hammett indicators. The data have been correlated
with the catalytic activity of these oxides towards the
liquid phase reduction of cycIohexanone in 2-propanol.
Sugunan, S; Sunitha, Kurur; Anto, Paul(Indian Journal of Chemistry, December , 1994)
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Abstract:
The surface acidity and basicity of oxides of Sm and Zr
and their mixed oxides have been determined using a set of
Hammett indicators. The data have been correlated with
the catalytic activity of these oxides towards the liquid
phase reduction of cyclo-hexanone in 2-propanol.
Sugunan, S; Devika Rani, G; Unnikrishnan, P A(Indian Journal of Engineering & Materials Sciences, October , 1995)
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Abstract:
Acid/base strength distribution of Y2O3 and its mixed
oxides with alumina catalysts are measured on Hammett
acidity function scale and expressed in terms of H0max
value. Basicity of Y2O3 increases with increase in activation
temperature and for mixed oxides the basicity increases
with increase in concentration of Y2O3, in the catalyst.
Sugunan, S; Sherly, K B; Devika Rani, G(React. Kinet.Catal.Lett., 1993)
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Abstract:
The limit of electron transfer in electron affinity from
the oxide surface to the electron acceptor (EA) are reported
from the adsorption of EA on DY203, mixed oxides
of DY203 with alumina and mixed oxides of Y203 with y-alumina.
The extent of electron transfer is understood
from magnetic measurements.
Sugunan, S; Binsy, Varghese(Indian Journal of Chemistry, September , 1998)
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Abstract:
The electron donating properties, surface acidity/ basicity and catalytic activity of cerium - zirconium mixed
oxides at various compositions have been reported at an activation temperature of 500 degree C. The catalytic activity
for the esterification of acetic acid with n-butanol has heen correlated with electron donating properties and
surface acidity/basicity of the oxides.
The electron donating properties, surface acidity/basicity and catalytic activity of lanthana for various dopant concentrations of strontium are reported at two activation temperatures. The catalytic activity has been correlated with electron donating properties and surface acidity/basicity of the oxide.
Ferrospinels of nickel, cobalt and copper and their sulphated analogues were prepared by the room temperature coprecipitation
route to yield samples with high surface areas. The intrinsic acidity among the ferrites was found to decrease in
the order: cobalt> nickel> copper. Sulphation caused an increase in the number of weak and medium strong acid sites,
whereas the strong acid sites were left unaffected. Electron donor studies revealed that copper ferrite has both the highest
proportion of strong sites and the lowest proportion of weak basic sites. All the ferrite samples proved to be good catalysts
for the benzoy lation of toluene with benzoyl chloride. copper and cobalt ferrites being much more active than nickel ferrite.
The catalytic activity for benzoylation was not much influenced by sulphation, but it increased remarkably with calcination
temperature of the catalyst. Surface Lewis acid sites, provided by the octahedral cations on the spinel surface, are suggested
to be responsible for the catalytic activity for the benzoylation reaction.
Smitha, V K; Suja, H; Joyce, Jacob; Sugunan, S(Indian Journal of Chemistry, February , 2003)
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Abstract:
Preparation and physico-chemical characterization or
phosphate modified zirconia systems and their application to
Friedel-Crafts benzylation and benzoylation of toluene have been
reported. The influence of transition metals on the surface
properties and catalytic activity has also been discussed.
Sugunan, S; Renuka, N K(Indian Journal of Chemistry, February , 2002)
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Abstract:
Sm2O3 - vanadia catalysts have been prepared by wet
impregnation method using NH4VO3 solution. The surface
properties of the prepared catalysts have been studied using FTIR.
XRD. surface area and pore volume data. The acid-base properties
of the system have been investigated by titrimetric method using
Hammett indicators. adsorption of electron acceptors as well as
decomposition of cyclohexanol. Phenol alkylation reaction by
methanol has been carried out to investigate the catalytic activity.
It has been observed that the selectivity of the products depends
upon the composition of the supported system
Iron pillared Montmorillonite has been synthesised and it is then wet impregnated with vanadia with different vanadia
composition. These catalysts are characterised using conventional techniques such as XRD analysis,FTIR analysis and
surface area and pore volume measurements. Acidity is measured using spectrophotometric monitoring of adsorption of
perylene, thermogravimetric desorption of 2.6 dimethylpyridine and temperature programmed desorption of ammonia.
Activity studies are done in the liquid phase. It has been concluded that Lewis acidic sites are responsible for the benzylation
of toluene when the benzylating agent is benzyl chloride while Bronsted acidic sites are responsible when the reagent is
benzyl alcohol.