Polarisation studies on the Raman spectra of cubic crystals - Part II: Calcium fluoride and potassium aluminium sulphate

Polarisation characters of the Raman lines of calcium fluoride (fluorspar) and potassium aluminium sulphate (alum) were investigated under the following conditions. Unpolarised light was incident normally on a face of the crystal making an angle 22.5° with a cubic face and the light scattered transversely along a cubic axis was analysed by a double image prism kept with its principal axes inclined at 45° to the vertical. Under these conditions the depolarisation factors of the Raman lines belonging to the totally symmetric (A), the doubly degenerate (E) and the triply degenerate (F) modes should be respectively =1, >1 and <1. The characteristic Raman line of CaF2 at 322 cm-1 exhibited a depolarisation value less than 1, showing thereby that the corresponding mode is a triply degenerate one (F). The Raman lines observed in the spectrum of K-alum were also classified and the results were compared with those given by previous investigators using standard crystal orientations.

Polarographic and redox potential studies on copper(I) and copper(II) and their complexes. Part III. Copper (I and II)-ethylene diamine and edta complexes and theory of formation of step reduction waves in cupric copper systems

Polarographic and redox potential measurements on the cupric and cuprous complexes of ethylenediamine and EDTA have been carried out. From the ratio of the stability constants of the cupric and cuprous complexes, and the stability constant of the cupric complex, the stability constant of the cuprous-ethylenediamine complex is obtained. In the case of the EDTA complex it has been possible to obtain only βic/β2ous from the equilibrium concentrations of the cuprous and cupric complexes and the disproportionation constant. The inequalities for the appearance of step reduction waves have been given. The values of the stability constants of the cupric and cuprous complexes determined by the polarographic-redox potential method have been used to explain the appearance of step reduction waves in some systems and the non-appearance in other systems.

Polarographic and redox potential studies on copper(I) and copper(II) and their complexes. Part I. Copper(I and II)-ammonia and methylamine complexes

The equilibrium between cuprous ion, cupric ion and metallic copper has been studied using polarographic and redox potential measurements, by reducing cupric ion with copper gauze until equilibrium. Using the well-defined anodic diffusion current plateau, an amperometric method for estimating cuprous copper based on the titration of cuprous ion with dichromate or permanganate has been developed. The diffusion current constant and the disproportionation constant of cuprous ion and the standard potential for the reduction reaction of Cu2+ → Cu+ have been determined. Polarograms have been taken after reducing cupric complexes of ammonia and methylamine with copper until equilibrium. In the case of the copper-ammonia system, reduction to the cuprous state is practically complete while in the case of the cupric-methylamine system, the first cathodic wave occurs to some extent. A new method, called the polarographic-redox potential method, for determining the stability constants of cuprous and cupric complexes has been developed. The method depends upon the determination of the concentration of complexes by polarographic wave heights, and free cupric anc cuprous ions by redox potentials. The stability constants of the following complexes have been obtained: Cu(NH3)2+4, Cu(NH3)+2, Cu(CH3NH2)2(OH)2, Cu(CH3NH2)+2. The stability constants determined by the new method and the half-wave potential shift method agree and the value for the cupric-ammonia complex is in good agreement with Bjerrum method, indicating the reliability of this method.

Free convection heat transfer from vertical cylinders part I: Power law surface temperature variation

This paper reports on the investigations of laminar free convection heat transfer from vertical cylinders and wires whose surface temperature varies along the height according to the relation TW - T∞ = Nxn. The set of boundary layer partial differential equations and the boundary conditions are transformed to a more amenable form and solved by the process of successive substitution. Numerical solutions of the first approximated equations (two-point nonlinear boundary value type of ordinary differential equations) bring about the major contribution to the problem (about 95%), as seen from the solutions of higher approximations. The results reduce to those for the isothermal case when n=0. Criteria for classifying the cylinders into three broad categories, viz., short cylinders, long cylinders and wires, have been developed. For all values of n the same criteria hold. Heat transfer correlations obtained for short cylinders (which coincide with those of flat plates) are checked with those available in the literature. Heat transfer and fluid flow correlations are developed for all the regimes.

Free convection heat transfer from vertical cylinders part II: Exponential surface temperature variation

Investigation on laminar free convection heat transfer from vertical cylinders and wires having a surface temperature variation of the form TW - T∞ = M emx are presented. As in Part I for power law surface temperature variation, the axisymmetric boundary layer equations of mass, momentum and energy are transformed to more convenient forms and solved numerically. The second approximation refines the results of the first upto a maximum of only 2%. Analysis of the results indicates that cylinders can be classified into the same three categories as in Part I, namely, short cylinders, long cylinders, and wires, heat transfer and fluid flow correlations being developed for each case.

The Raman spectra of organic compounds -Part I. Methyl, ethyl, n-propyl and n-butyl alcohols

The Raman spectra of methyl alcohol, ethyl alcohol, n-propyl alcohol and n-butyl alcohol have been recorded using λ 2537 excitation. 35, 49, 45 and 51 Raman lines respectively have been identified in the spectra of these alcohols, in addition to the rotational 'wings'. In each case, a large number of additional lines have been recorded. The existence of Raman lines with frequency shifts greater than 3800 cm.-1, first reported by Bolla in the spectrum of ethyl alcohol, has been confirmed. Similar high-frequency shift Raman lines have also been recorded in the spectrum of methyl alcohol. They have been assigned as combinations. Proper assignments have been given for the prominent Raman lines appearing in the spectra of these alcohols.

Isomerisations of substituted β-keto-esters - Part II. Isomerisation of ethyl 1-ethoxycarbonyl 2oxocyclopentyl acetate into 2, 3-diethoxycarbonylcyclohexanone

A mechanism for the isomerisation of ethyl 1-ethoxycarbonyl-2-oxocyclopentylacetate (I) into a cyclohexane β-keto-ester as proceeding through an intermediate bicyclic /gb-diketone (VII) has been considered as an alternative mechanism to one earlier suggested.1 The determination of the structure of the isomerised β-keto-ester as 2, 3-diethoxycarbonylcyclohexanone (V) has provided support for the earlier mechanism.

Raman spectra of single crystals of dicarboxylic acids - Part I. β-malonic acid and β-succinic acid

Raman spectra of single crystals of β-malonic acid and β-succinic acid have been photographed using λ 2536·5 radiation. 32 Raman lines have been recorded in the case of β-malonic acid. Of these 21 lines have been recorded for the first time. The three intense lattice lines at 52, 90 and 144 cm.-1 have been attributed to rotational lattice oscillations. 29 Raman lines in the case of β-succinic acid have been recorded. The entire lattice spectrum and many internal frequencies have been recorded for the first time. The three intense lattice lines at 80, 135 and 160 cm.-1 have been assigned to the rotational oscillations of the two molecules of the succinic acid in the unit cell.

Studies on the hydrolysis of metal ions - Part II-Nickel

A detailed investigation of the hydrolysis of nickel in the lower concentration range has been made. The results have been analysed on the basis of 'Core + links' theory and on the assumption of the formation of one predominant complex. Evidence is obtained for the formation of Ni2 (OH)62- and its stability constant is calculated to be 1038.78

Spectrophotometric and potentiometric investigations of copper (II)-Ethanolamine complexes - Part III. diethanolamine (Gaussian analysis of electronic spectra in mono and diethanolamine systems)

Spectrophotometric and potentiometric investigations have been carried out on copper-diethanolamine system. Job plots at 900, 900 and 580 mμ have indicated the formation of CuD++, CuD2++ and CuD3++. The n- pA curves obtained indicate the formation of CuD++, CuD2++, CuD3++, CuDOH+, CuD2OH+ and CuD3OH+. The n- pA curves have been analyzed to obtain the stability constants of these complexes. Absorption curves of pure complexes have been computed by a graphical method. Gaussian analysis of the absorption curves of pure and hydroxy complexes show the presence of a second band, indicating that the structure is that of a distorted octahedron.

Polarisation studies on the Raman spectra of cubic crystals - Part I. Sodium chlorate

neral expressions have been derived for the intensities of the three classes of Raman lines namely totally symmetric A, doubly degenerate E and triply degenerate F, in the case of cubic crystals under the following conditions. The direction of the incident beam which is polarised with its electric vector inclined at an angle α to the normal to the scattering plane makes an angle Θ with one of the cubic axes of the crystal. The transversely scattered light is analysed by a double image prism with its principal axes inclined at angle β to the normal to the scattering plane, which is horizontal. For incident unpolarised light and Θ=22 1/2°, and the scattered light being analysed by a double image prism rotated through 45° from the position when its principal axes are vertical and horizontal ρ{variant} for A lines is equal to one, for E lines >1 and for F lines <1. This gives a method of classifying the Raman lines of a cubic crystal in a single setting. The results have been experimentally verified in sodium chlorate.

Aspects of tautomerism. Part IV. A kinetic study of the dimerization reaction of pseudo-acid chlorides

The kinetics of dimerization of 4-substituted- and unsubstituted o-benzoylbenzoyl chlorides, with iodide ion can be described by the expression, rate =k2[acid chloride][iodide]. The value for the reaction in dimethylformamide solution is –0·38. The entropy of activation for the reaction is –34·2 cal mol–1 K–1 and the activation energy is 10·7 kcal mol–1. These results have been interpreted as evidence for the formation of pseudo-iodide in the rate-determining step and its fast decomposition to radicals which combine to give a mixture of stereoisomeric dilactones.

Aspects of tautomerism. Part V. Solvent, substituent, and steric effects on the ring–chain tautomerism of o-benzoylbenzamides

Ring-chain tautomeric equilibria of o-benzoylbenzamides in 95% ethanol, chloroform, dioxan, and acetonitrile have been estimated using u.v. spectroscopy. Unlike the case of acids, solvent polarity has only a small effect. In ethanol the cyclic form is favoured. Electron-withdrawing groups in the amide-bearing ring disfavour the cyclic form. Substitution of methyl, ethyl, and phenyl groups on the nitrogen atom of the amide function results in increase of the proportion of the cyclic form in the first two cases and decrease in the last.

Prosopis, an Alien among the Sacred Trees of South India

The problematic of invasive species in an alien environment has aroused the attention of scientists all over the world for quite some time. One of the exotic tree species that has provoked special attention in the tropical drylands is Prosopis juliflora. Originating in South America, prosopis (hereafter referred to as prosopis) has been introduced in the hot and semi-arid zones of the world particularly to provide fuelwood, to stabilize sand dunes and to combat desertification. The tree has become an essential source for fuelwood and a provider of several other products and services in areas where it has become established. However, despite the numerous benefits the tree provides to rural people, in several regions prosopis has become a noxious weed with a negative impact on the environment and to the economy of farmers and landowners. In India, prosopis was introduced in Andhra Pradesh in 1877. The tree was then proclaimed as the precious child of the plant world by scientists and local people alike. The purpose of this study was to investigate the overall impact of prosopis on local rural livelihoods in the drylands of South India. Of particular interest was the examination of the different usages of the tree, especially as fuelwood, and people s perceptions of it. Furthermore, the study examined the negative impacts of the uncontrolled invasion of prosopis on croplands, and its occupation of the banks of irrigation canals and other water sources. As another central theme, this study analysed the Hindu classification system for nature and for trees in particular. In India, several tree species are regarded as sacred. This study examined the position of the exotic prosopis among sacred trees, such as the bodhi, banyan and neem trees. The principle method for collecting the field data was by using individual and thematic group interviews. These interviews were semi-structured with open ended questions. Moreover, unstructured interviews as well as general observations provided complementary information. The data were gathered during two fieldwork periods in the states of Andhra Pradesh and Tamil Nadu, in South India. The results confirmed that prosopis both provides benefits and causes hazards to different stakeholders. Farmers and agriculturalists suffer economic losses in areas where prosopis has invaded crop fields and competes with other plants for water and nutrients. On the other hand, for a significant number of poor rural people, prosopis has become an important source of livelihood benefits. This tree, which grows on government wastelands, is commonly a free resource for all and has thus become a major local source of fuelwood. It also provides several other goods and services and cash income that contributes to improve livelihoods in rural communities. Prosopis ranked lowest in the tree classificatioin system of the Hindus of South India. Although it is appreciated for many benefits it provides for poor people, it has remained an outsider compared with the indigenous tree species. On the other hand, the most sacred trees, such as the bodhi or the banyan, are completely excluded from extraction and it is seen as a sacrilege to even cut branches from any of these trees. An unexpected finding was that, in a few cases, prosopis had also been elevated to the status of a sacred tree. Goods and services from prosopis are not utilized in the most beneficial way. Silvicultural management practices are suggested that would provide additional income and employment opportunities. Interventions are recommended to control further invasion of the tree that might cause serious negative effects in the future. For Hindus, the sacred always ranks highest, even above economic gain. The conservation of sacred groves and sacred trees is a tradition that has its roots in ancient history. These socio-religious practices need to be respected and continued. Successful management of tree and forest resources depends on the willingness of the local people to manage their natural resources, and this willingness exists and has always existed in South India. Keywords: South India, drylands, livelihood, fuelwood, invasive, resource, silviculture.