Study of cyclohexanol decomposition reaction over the ferrospinels, A1−xCuxFe2O4 (A=Ni or Co and x=0, 0.3, 0.5, 0.7 and 1), prepared by ‘soft’ chemical methods

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.

Influence of surface and acid properties of vanadia supported on ceria promoted with rice husk silica on cyclohexanol decomposition

Cyclohexanol decomposition activity of supported vanadia catalysts is ascribed to the high surface area, total acidity and interaction between supported vanadia and the amorphous support. Among the supported catalysts, the effect of vanadia over various wt% V2O5 (2–10) loading indicates that the catalyst comprising of 6 wt% V2O5 exhibits higher acidity and decomposition activity. Structural characterization of the catalysts has been done by techniques like energy dispersive X-ray analysis, X-ray diffraction and BET surface area. Acidity of the catalysts has been measured by temperature programmed desorption using ammonia as a probe molecule and the results have been correlated with the activity of catalysts.

Alkylation of phenol with methanol over mixed oxides of tin with some rare earth elements

Alkylation of phenol with methanol has been carried out over Sn-La and Sn-Sm mixed oxides of varying compositions at 623 K in a vapour phase flow reactor. It is found that the product selectivity is greatly influenced by the acid-base properties of the catalysts. Ortho-cresol formation is favoured over catalysts with weak acid sites whereas formation of 2,6-xylenol occurs in the presence of stronger acid sites. The cyclohexanol decomposition reaction and titrimetric method using Hammett indicators have been employed to elucidate the acid-base properties of the catalysts.

Effect of vanadia on physico-chemical and catalytic characteristics of dysprosia

Physico-chemical characterization of DY203/V2O5 systems prepared through wet impregnation method has been carried out using various techniques like EDX, XRD, FTIR. thermal studies, BET surface area, pore volume and pore size distribution analysis. The amount of vanadia incorporated has been found to influence the surface properties of dysprosia. The spectroscopic results combining with X-ray analysis reveal that vanadia species exist predominantly as isolated amorphous vanadyl units along with crystalline dysprosium orthovanadate. Basicity studies have been conducted by adsorption of electron acceptors and acidity and acid strength distribution by temperature programmed desorption of ammonia. Cyclohexanol decomposition has been employed as a chemical probe reaction to examine the effect of vanadia on the acid base property of Dy2O3. Incorporation of vanadia titrates thc Lewis acid and base sites of Dy2O3, while an enhancement of Bronsted acid sites has been noticed. Data have been correlated with the catalytic activity of these oxides towards the vapour phase methylation of phenol

Oxidative dehydrogenation of ethylbenzene over La and Dy supported vanadia

A series of supported vanadia systems have been prepared by excess solvent technique using La203 and DY203 as supports. Physical characterization has been carried out using XRD, FTIR, TG studies, BET surface area measurement, pore volume analysis etc. Cyclohexanol decomposition has been used as a test reaction for evaluating the acid base properties of the supported system. The oxidative dehydrogenation of ethylbenzene has been employed as a chemical probe reaction to examine the catalytic activity. The active species correspond to amorphous and crystalline tetrahedral vanadyl units in the supported system.

Surface Properties and Catalytic Activity of Ferrospinels Containing Cobalt, Nickel and Copper

The present study describes the surface properties and catalytic activities of ferrospinels containing Co, Ni and Cu prepared by the low temperature route. Various physico-chemical methods have been adopted to characterise the systems. The reactions carried out are the Friedel-Crafts benzoylation of aromatics and the cyclohexanol decomposition. We have attempted the sulphate modification of the ferrites and have studied the surface and catalytic properties of the sulphated analogues.The work is presented in six chapters, the last chapter giving the summary and conclusions of the results presented earlier. Our samples prove as potential catalysts for the benzoylation of aromatics , for which truly heterogeneous catalysts are rare. Again , the materials show remarkable dehydration/dehydrogenation activities during cyclohexanol decomposition. There is plenty of scope for research in this field, especially in the development of environmentally benign catalysts for acylation reactions.

Characterisation of the acid-base properties of pillared montmorillonites

Iron and mixed iron aluminium pillared montrnorillonites prepared by partial hydrolysis method were subjected to room temperature exchange with transition metals of the first series. The resulting materials were characterised by different spectroscopic techniques and surface area measurements. About 1-3% transition metals were incorporated into the porous network. The structural stability of the porous network was not affected by exchange. XRD and AI NMR spectroscopy evidenced the presence of iron substituted Al13 like polymers in FeAl pillared systems. Acidity and basicity benefited much as a result of metal exchange. Acidity and basicity were quantified by model reactions, viz., cumene cracking and cyclohexanol decomposition respectively. The presence of basic sites in otherwise acidic pillared clays, though diminutive in amount can be of much importance in acid base catalysed reactions.

Catalysis by Transition Metal Modified Ceria and Ceria-Zirconia Mixed Oxides Prepared via Sol-Gel Route

The aim of catalysis research is to apply the catalyst successfully in economically important reactions in an environmentally friendly way. The present work focuses on the modification of structural and surface properties of ceria and ceria-zirconia catalysts by the incorporation of transition metals. The applications of these catalysts in industrially important reactions like ethylbenzene oxidation, alkylation of aromatics are also investigated.Sol-gel method is effective for the preparation of transition metal modified ceria and ceria-zirconia mixed oxide since it produces catalyst with highly dispersed incorporated metal. Unlike that of impregnation method plugging of pores is not prominent for sol-gel derived catalyst materials. This prevents loss of surface area on metal modification as evident for BET surface area measurements.The powder X-ray diffraction analysis confirms the cubic structure of transition metal modified ceria and ceria-zirconia catalysts. The thermal stability is evident from TGA/DTA analysis. DR UV-vis spectra provide information on the coordination environment of the incorporated metal. EPR analysis ofCr, Mn and Cu modified ceria and a ceria-zirconia catalyst reveals the presence of different oxidation states of incorporated metal.Temperature programmed desorption of ammonia and thermogravimetric desorption of 2,6-dimethyl pyridine confirms the enhancement of acidity on metal incorporation. High a-methyl styrene selectivity in cumene cracking reaction implies the presence of comparatively more number of Lewis acid sites with some amount of Bronsted acid sites. The formation of cyclohexanone during cyclohexanol decomposition confirms the presence of basic sites on the catalyst surface.Mn and Cr modified catalysts show better activity towards ethylbenzene oxidation. A redox mechanism through oxometal pathway is suggested.All the catalysts were found to be active towards benzylation of toluene and a-xylene. The selectivity towards monoalkylated products remains almost 100%. The catalytic activity is correlated with the Lewis acidity of the prepared systems.The activity of the catalysts towards methylation of phenols depends on the strength acid sites as well as the redox properties of the catalysts. A strong dependence of methylation activity on the total acidity is illustrated.

Studies on Some Simple and Zeolite-Y Encapsulated 3d-Transition Metal Complexes of Schiff Bases Derived From 2-Aminobenzothiazole

In this regard Schiff base complexes have attracted wide attention. Furthermore, such complexes are found to play important role in analytical chemistry, organic synthesis, metallurgy, refining of metals, electroplating and photography. Many Schiff base complexes are reported in literature. Their properties depend on the nature of the metal ion as well as on the nature of the ligand. By altering the ligands it is possible to obtain desired electronic environment around the metal ion. Thus there is a continuing interest in the synthesis of simple and zeolite encapsulated Schiff base complexes of metal ions. Zeolites have a number of striking structural similarities to the protein portion of natural enzymes. Zeolite based catalysts are known for their remarkable ability of mimicking the chemistry of biological systems. In view of the importance of catalysts in all the areas of modern chemical industries, an effort has been made to synthesize some simple Schiff base complexes, heterogenize them by encapsulating within the supercages of zeoliteY cavities and to study their applications. The thesis deals with studies on the synthesis and characterization of some simple and zeoliteY encapsulated Mn(II), Fe(III), Co(II), Ni(II) and Cu(II) complexes and on the catalytic activity of these complexes on some oxidation reactions. Simple complexes were prepared from the Schiff base ligands SBT derived from 2-aminobenzothiazole and salicylaldehyde and the ligand VBT derived from 2-aminobenzothiazole and vanillin (4-hydroxy-3- methoxybenzaldehyde). ZeoliteY encapsulated Mn(II), Fe(III), Co(II), Ni(II) and Cu(II) complexes of Schiff base ligands SBT and VBT and also of 2-aminobenzothiazole were synthesized. All the prepared complexes were characterized using the physico-chemical techniques such as chemical analysis (employing AAS and CHN analyses), magnetic moment studies, conductance measurements and electronic and FTIR spectra. EPR spectra of the Cu(II) complexes were also carried out to know the probable structures and nature of Cu(II) complexes. Thermogravimetric analyses were carried out to obtain the information regarding the thermal stability of various complexes. The successful encapsulations of the complexes within the cavities of zeoliteY were ascertained by XRD, surface area and pore volume analysis. Assignments of geometries of simple and zeoliteY encapsulated complexes are given in all the cases. Both simple and zeoliteY encapsulated complexes were screened for catalytic activity towards oxidation reactions such as decomposition of hydrogen peroxide, oxidation of benzaldehyde, benzyl alcohol, 1-propanol, 2-propanol and cyclohexanol.

Catalysis of C-alkylation of phenol using V2O5-La2O3 system

Vapour phase methylation of phenol is carried out over La2O3 supported vanadia systems of various composition. The structural features and physico chemical characterisation of the catalysts are investigated. Orthovanadates are formed in addition to surface vanadyl species on the metal oxide support. No V2O5 crystallites are detected. The acid base properties of the oxides are studied by Hammett indicator method and decomposition of cyclohexanol.The data are correlated with the catalytic activity and selectivity of the products. Ring alkylation is found to be predominant over these catalysts.

Surface properties and catalytic activity of vanadia supported on samaria

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

Studies on the Surface Properties and Catalytic Activity of Metal Chromites on Thermal Decomposition of Ammonium Perchlorate

Department of Applied Chemistry, Cochin University of Science and Technology

Studies on Simple and Encapsulated Transition Metal Complexes of Schiff Bases Derived from Diaminonaphthalene

Schiff base complexes of transition metal ions have played a significant role in coordination chemistry.In the present study we have synthesized some new Mn(II),Co(II) and Cu(II) complexes of Schiff bases derived from 1,8-diaminonaphthalene.Even though we could not isolate theses Schiff bases (as they readily cyclise to form the perimidine compounds),we were able to characterize unequivacally the complexes synthesized from these compounds as complexes of Schiff Bases. We Synthesized three perimidine derivatives ,2-(quinoxalin-2-yl)-2,3-dihydro-1H-perimidine,2-(2,3-dihydro-1H-perimidin-2-yl)-6-methoxyphenol and 4-(2,3-dihyro-1H-perimidin-2-yl)-2-methoxyphenol by the condensation of 1,8-diaminonaphthalene with quinoxaline-2-carboxaldehyde,2- hydroxy-3-methoxybenzaldehyde or 4-hydroxy-3-methoxybenzaldehyde respectively.Theses compounds were used as precursor ligands for the preparation of Schiff base complexes.The complexes were characterized by using elemental analysis ,conductance and magnetic susceptibility measuremets ,infrared and UV-Visible spectroscopy ,thermogravimetric analysis and EPR spectroscopy .We also encapsulated the complexes in zeolite Y matrix and these encapsulated complexes were also characterized. We have also tried theses complexes as catalysts in the oxidation of cyclohexanol and decomposition of hydrogen peroxide.

Feature Extraction Methods Based on Linear Predictive Coding and Wavelet Packet Decomposition for Recognizing Spoken Words in Malayalam

Speech signals are one of the most important means of communication among the human beings. In this paper, a comparative study of two feature extraction techniques are carried out for recognizing speaker independent spoken isolated words. First one is a hybrid approach with Linear Predictive Coding (LPC) and Artificial Neural Networks (ANN) and the second method uses a combination of Wavelet Packet Decomposition (WPD) and Artificial Neural Networks. Voice signals are sampled directly from the microphone and then they are processed using these two techniques for extracting the features. Words from Malayalam, one of the four major Dravidian languages of southern India are chosen for recognition. Training, testing and pattern recognition are performed using Artificial Neural Networks. Back propagation method is used to train the ANN. The proposed method is implemented for 50 speakers uttering 20 isolated words each. Both the methods produce good recognition accuracy. But Wavelet Packet Decomposition is found to be more suitable for recognizing speech because of its multi-resolution characteristics and efficient time frequency localizations