Photoinduced oxidation of benzhydrol over lanthana modified sol-gel titania

Lanthana modified sol-gel titania is prepared through particulate sol-gel route and the physico-chemical characterizations of the prepared systems were done using X-Ray diffration, EDX, BET surface area-pore volume measurements and TG-DTG analysis. Benzophenone was observed to be the sole product in the TiO2 photocatalyzed oxidation of benzhydrol in oxygen purged acetonitrile. The influence of various parameters, like irradiation time, amount of catalyst, concentration of the catalyst and other factors on the photocatalytic oxidation has been investigated. The proposed mechanism envisages the involvement of a superoxide radical anion.

Wet peroxide oxidation of phenol over mixed pillared montmorillonites

Wet peroxide oxidation (WPO) of phenol is an effective means for the production of diphenols, which are of great industrial importance. An added advantage of this method is the removal of phenol from wastewater effluents. Hydroxylation of phenol occurs efficiently over mixed iron aluminium pillared montmorillonites. An initial induction period is noticed in all cases. A thorough study on the reaction variables suggests free radical mechanism for the reaction.

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.

Liquid phase benzoylation of arenes over iron promoted sulphated zirconia

The present work undertakes the preparation and physico-chemical characterisation of iron promoted sulphated zirconia (SZ) with different amounts of iron loading and their application to Friedel-Crafts benzoylation of benzene, toluene and xylene under different experimental conditions, XRD and laser Raman techniques reveal the stabilisation of the tetragonal phase of zirconia and the existence of iron in highly dispersed form as Fe203 on the catalyst surface. The surface acidic properties were determined by ammonia temperature programmed desorption (TPD) and perylene adsorption, The results were supported by the TGA studies after adsorption of pyridine and 2,6-dimethylpyridine (2,6-DMP), Strong Lewis acid sites on the surface, which are evident from TPD and perylene adsorption studies. explain the high catalytic activity of the systems towards benzoylation. The experimental results provide evidence for the truly heterogeneous nature of the reaction. The studies also establish the resistance to deactivation in the metal incorporated sulphated systems.

Catalytic oxidation of cyclohexane over Cu-Zn-Cr ternary spinel systems

Spinel systems with the composition of Cu 1−x Zn x Cr 2 O 4 [x = 0 CCr, x = 0.25 CZCr-1, x = 0.5 CZCr-2, x = 0.75 CZCr-3 and x = 1 ZCr] were prepared by homogeneous co-precipitation method and were characterized by X-ray diffraction (XRD) and FT-IR spectroscopy. Elemental analysis was done by EDX, and surface area measurements by the BET method. The redox behavior of these catalysts in cyclohexane oxidation at 243 K using TBHP as oxidant was examined. Cyclohexanone was the major product over all catalysts with some cyclohexanol. 69.2% selectivity to cyclohexanol and cyclohexanone at 23% conversion of cyclohexane was realized over zinc chromite spinels in 10 h.

Influence of residual cations (Na+, K+ and Mg2+) in the alkylation activity of benzene with 1-octene over rare earth metal ion exchanged FAU–Y zeolite

The effect of residual cations in rare earth metal modified faujasite–Y zeolite has been monitored using magic angle spinning NMR spectral analysis and catalytic activity studies. The second metal ions being used are Na+, K+ and Mg+. From a comparison of the spectra of different samples, it is concluded that potassium and magnesium exchange causes a greater downfield shift in the 29Si NMR peaks. Also, lanthanum exchanged samples show migration behavior from large cages to small cages, which causes the redistribution of second counter cations. It is also observed that Mg2+ causes the most effective migration of lanthanum ions due to its greater charge. The prepared systems were effectively employed for the alkylation of benzene with 1-octene in the vapor phase. From the deactivation studies it is observed that the as-exchanged zeolites possess better stability towards reaction condition over the pure HFAU zeolite.

A Study on the Transport and Distribution of Atmospheric Aerosols and its Influence on Regional Meteorological Parameters over the Indian Subcontinent

This doctoral thesis addresses the growing concern about the significant changes in the climatic and weather patterns due to the aerosol loading that have taken place in the Indo Gangetic Plain(IGP)which includes most of the Northern Indian region. The study region comprises of major industrial cities in India (New Delhi, Kanpur, Allahabad, Jamshedpur and Kolkata). Northern and central parts of India are one of the most thickly populated areas in the world and have the most intensely farmed areas. Rapid increase in population and urbanization has resulted in an abrupt increase in aerosol concentrations in recent years. The IGP has a major source of coal; therefore most of the industries including numerous thermal power plants that run on coal are located around this region. They inject copious amount of aerosols into the atmosphere. Moreover, the transport of dust aerosols from arid locations is prevalent during the dry months which increase the aerosol loading in theatmosphere. The topography of the place is also ideal for the congregation of aerosols. It is bounded by the Himalayas in the north, Thar Desert in the west, the Vindhyan range in the south and Brahmaputra ridge in the east. During the non‐monsoon months (October to May) the weather in the location is dry with very little rainfall. Surface winds are weak during most of the time in this dry season. The aerosols that reach the location by means of long distance transport and from regional sources get accumulated under these favourable conditions. The increase in aerosol concentration due to the complex combination of aerosol transport and anthropogenic factors mixed with the contribution from the natural sources alters the optical properties and the life time of clouds in the region. The associated perturbations in radiative balance have a significant impact on the meteorological parameters and this in turn determines the precipitation forming process. Therefore, any change in weather which disturbs the normal hydrological pattern is alarming in the socio‐economic point of view. Hence, the main focus of this work is to determine the variation in transport and distribution of aerosols in the region and to understand the interaction of these aerosols with meteorological parameters and cloud properties.

A Study on Aerosol Transport Dynamics over the Indian Landmass and the Adjoining Oceanic Regions Using Satellite Data

The present study brings out the influence of transport dynamics on the aerosol distribution over the Indian region at a few selected geographically distinct locations. Over the Bay of Bengal the dominant pathway of aerosol transport during the pre-monsoon period is through higher altitudes (~ 3 km); directed from the Indian main land. In contrast, the aerosol pathways over the Arabian Sea during the same period are quite complex. They are directed from geographically different environments around the ocean through different altitudes. However in general, the day-to-day variability of AOD at both these regions is significantly influenced by the features of atmospheric circulation especially, the wind convergence at higher altitudes (around 3 km). Over the Ganga Basin during the winter period, the wind convergence at lower altitudes (< I km) govems the shon term variations in AOD, while the mean AOD distribution at this location is mainly governed by the local anthropogenic sources.

Studies on the paratial and temporal distribution of surface meteorological parameters over Indian subcontinent

The intention of the present thesis work is to understand the physical processes responsible for climatic variability and predictability of the Indian subcontinent. The study is expected to delineate and emphasize the various boundaries and areas of transition and bring out the regional and temporal characteristics of the meteorological distribution of the country. The results obtained from the study is expected to provide a better understanding the physics of Indian cl imate, which can be incorporated for numerical weather prediction. The results obtained from the present study can be incorporated for climate modelling and long-term prediction of the meteorological parameters over Indian subcontinent

Studies on the meteriological aspects of air pollution over Cochin

Pollutants that once enter into the earth’s atmosphere become part of the atmosphere and hence their dispersion, dilution, direction of transportation etc. are governed by the meteorological conditions. The thesis deals with the study of the atmospheric dispersion capacity, wind climatology, atmospheric stability, pollutant distribution by means of a model and the suggestions for a comprehensive planning for the industrially developing city, Cochin. The definition, sources, types and effects of air pollution have been dealt with briefly. The influence of various meteorological parameters such as vector wind, temperature and its vertical structure and atmospheric stability in relation to pollutant dispersal have been studied. The importance of inversions, mixing heights, ventilation coefficients were brought out. The spatial variation of mixing heights studies for the first time on a microscale region, serves to delineate the regions of good and poor dispersal capacity. A study of wind direction fluctuation, σθ and its relation to stability and mixing heights were shown to be much useful. It was shown that there is a necessity to look into the method of σθ computation. The development of Gausssian Plume Model along with the application for multiple sources was presented. The pollutant chosen was sulphur dioxide and industrial sources alone were considered. The percentage frequency of occurrence of inversions and isothermals are found to be low in all months during the year. The spatial variation of mixing heights revealed that a single mixing height cannot be taken as a representative for the whole city have low mixing heights and monsoonal months showed lowest mixing heights. The study of ventilation co-efficients showed values less than the required optimum value 6000m2/5. However, the low values may be due to the consideration of surface wind alone instead of the vertically averaged wind. Relatively more calm conditions and light winds during night and strong winds during day time were observed. During the most of the year westerlies during day time and northeasterlies during night time are the dominant winds. Unstable conditions with high values of σθ during day time and stable conditions with lower values of σθ during night time are the prominent features. Monsoonal months showed neutral stability for most of the time. A study σθ of and Pasquill Stability category has revealed the difficulty in giving a unique value of for each stability category. For the first time regression equations have been developed relating mixing heights and σθ. A closer examination of σθ revealed that half of the range of wind direction fluctuations is to be taken, instead of one by sixth, to compute σθ. The spatial distribution of SO2 showed a more or less uniform distribution with a slight intrusion towards south. Winter months showed low concentrations contrary to the expectations. The variations of the concentration is found to be influenced more by the mixing height and the stack height rather than wind speed. In the densely populated areas the concentration is more than the threshold limit value. However, the values reported appear to be high, because no depletion of the material is assumed through dry or wet depositions and also because of the inclusion of calm conditions with a very light wind speed. A reduction of emission during night time with a consequent rise during day time would bring down the levels of pollution. The probable locations for the new industries could be the extreme southeast parts because the concentration towards the north falls off very quickly resulting low concentrations. In such a case pollutant spread would be towards south and west, thus keeping the city interior relatively free from pollution. A more detailed examination of the pollutant spread by means of models that would take the dry and wet depositions may be necessary. Nevertheless, the present model serves to give the trend of the distribution of pollutant concentration with which one can suggest the optimum locations for the new industries

Spatio-temporal Variability of Atmospheric Ozone over Indian Subcontinent and its Relation to Meteorological Parameters

Ozone present in the atmosphere not only absorbs the biologically harmful ultraviolet radiation but also is an important ingredient of the climate system. The radiative absorption properties of ozone make it a determining factor in the structure of the atmosphere. Ozone in the troposphere has many negative impacts on humans and other living beings. Another significant aspect is the absorption of outgoing infrared radiation by ozone thus acting as a greenhouse gas. The variability of ozone in the atmosphere involves many interconnections with the incoming and outgoing radiation, temperature circulation etc. Hence ozone forms an important part of chemistry-climate as well as radiative transfer models. This aspect also makes the quantification of ozone more important. The discovery of Antarctic ozone hole and the role of anthropogenic activities in causing it made it possible to plan and implement necessary preventive measures. Continuous monitoring of ozone is also necessary to identify the effect of these preventive steps. The reactions involving the formation and destruction of ozone are influenced significantly by the temperature fluctuations of the atmosphere. On the other hand the variations in ozone can change the temperature structure of the atmosphere. Indian subcontinent is a region having large weather and climate variability which is evident from the large interannual variability of monsoon system over the region. Nearly half of Indian region comprises the tropical region. Most of ozone is formed in the tropical region and transported to higher latitudes. The formation and transport of ozone can be influenced by changes in solar radiation and various atmospheric circulation features. Besides industrial activities and vehicular traffic is more due to its large population. This may give rise to an increase in the production of tropospheric ozone which is greenhouse gas. Hence it becomes necessary to monitor the atmospheric ozone over this region. This study probes into the spatial distribution and temporal evolution of ozone over Indian subcontinent and discusses the contributing atmospheric parameters.

Studis on the climatological aspects of air pollution potential over trivandrum

The deteriorating air quality especially in urban environments is a cause of serious concern. In spite of being an effective sink, the atmosphere also has its own limitations in effectively dispersing the pollutants being dumped into it continuously by various sources, mainly industries. Many a time, it is not the higher emissions that cause alarming level of pollutants but the unfavourable atmospheric conditions under which the atmosphere is not able to disperse them effectively, leading to accumulation of pollutants near the ground. Hence, it is imperative to have an estimate of the atmospheric potential for dispersal of the substances emitted into it. This requires a knowledge of mixing height, ventilation coefficient, wind and stability of the region under study. Mere estimation of such pollution potential is not adequate, unless the probable distribution of concentration of pollutants is known. This can be obtained by means of mathematical models. The pollution potential coupled with the distribution of concentration provides a good basis for initiating steps to mitigate air pollution in any developing urban area. In this thesis, a fast developing industrial city, namely, Trivandrum is chosen for estimating the pollution potential and determining the spatial distribution of sulphur dioxide concentration. Each of the parameters required for pollution potential is discussed in detail separately. The thesis is divided into nine chapters.

Computational models for the prediction of severe thunderstorms over east indian region

Thunderstorm is one of the most spectacular weather phenomena in the atmosphere. Many parts over the Indian region experience thunderstorms at higher frequency during pre-monsoon months (March- May), when the atmosphere is highly unstable because of high temperatures prevailing at lower levels. Most dominant feature of the weather during the pre-monsoon season over the eastern Indo-Gangetic plain and northeast India is the outburst of severe local convective storms, commonly known as ‘Nor’wester’ or ‘Kalbaishakhi’. The severe thunderstorms associated with thunder, squall line, lightning and hail cause extensive losses in agriculture, damage to structure and also loss of life. The casualty due to lightning associated with thunderstorms in this region is the highest in the world. The highest numbers of aviation hazards are reported during occurrence of these thunderstorms. In India, 72% of tornadoes are associated with this thunderstorm.

Studies on the horizontal and vertical distribution of clouds and their impact on energetics of the Atmosphere over the Indian Region

Motivation for the present study is to improve the scienti c understanding on the prominent gap areas in the average three-dimensional distribution of clouds and their impact on the energetics of the earth-atmosphere system. This study is focused on the Indian subcontinent and the surrounding oceans bound within the latitude-longitude bands of 30 S to 30 N and 30 E to 110 E. Main objectives of this study are to : (i) estimate the monthly and seasonal mean vertical distributions of clouds and their spatial variations (which provide the monthly and seasonal mean 3-dimensional distributions of clouds) using multi-year satellite data and investigate their association with the general circulation of the atmosphere, (ii) investigate the characteristics of the `pool of inhibited cloudiness' that appear over the southwest Bay of Bengal during the Asian summer monsoon season (revealed by the 3-dimensional distribution of clouds) and identify the potential mechanisms for its genesis, (iii) investigate the role of SST and atmospheric thermo-dynamical parameters in regulating the vertical development and distribution of clouds, (iv) investigate the vertical distribution of tropical cirrus clouds and their descending nature using lidar observations at Thiruvananthapuram (8.5 N, 77 E), a tropical coastal station at the southwest Peninsular India, and (v) assessment of the impact of clouds on the energetics of the earth-atmosphere system, by estimating the regional seasonal mean cloud radiative forcing at top-of-the-atmosphere (TOA) and latent heating of the atmosphere by precipitating clouds using satellite data

Characteristics of SST over the Arabian Sea and Bay of Bengal

Evolution of mini warm pool in the Arabian Sea just before the onset of southwest monsoon and behavior of SST in the vicinity of weather systems formed during the premonsoon, southwest monsoon and post monsoon seasons were studied using TMI SST data. The Arabian Sea mini warm pool is formed about three weeks ahead of onset of southwest monsoon. Maximum SST is found about one week ahead of monsoon onset and then the warm pool gradually dissipated. Generally, a low-pressure system is formed when the SST exceeds a certain threshold value for the formation of the system. Daily SST values are examined both in Arabian sea and Bay of Bengal to bring out the quantity of increase in SST just before the formation of the system, quantity of rapid decrease in SST during the formation of the system and the number of days required for returning to normal SST. Many cases were examined for pre-monsoon, southwest monsoon and post monsoon seasons to understand the behavior of SST pattern. It is found that the SST increases about 3° C just before the formation of the system and decreases about 4° C during the formation within 2 to 3 days and takes about 4 to 6 days to return to normal SST pattern. However, the SST pattern depends on the weather system