Electron paramagnetic resonance evidence for Jahn-Teller glasses

Single crystal E.P.R. studies of copper as a dopant in lithium potassium sulphate, lithium ammonium sulphate and lithium sodium sulphate have been carried out from room temperature down to 77K. The three Jahn-Teller (JT) systems behave very similarly to one another. The room temperature dynamic JT spectra with giso = 2·19 ± 0·01 and Aiso = ±(33 ± 4) times 10-4 cm-1 transform around 247 K to spectra characterized by randomly frozen-in axial strains with g‖ = 2·4307 ± 0·0005, g⊥ = 2·083 ± 0·001, A‖ = ±(116 ± 2) times 10-4 cm-1 and A⊥ = ∓(14 ± 4) times 10-4 cm-1. We proposed that the low temperature phase (below 247 K) of each of these systems provides an example of a Jahn-Teller glass.

Interannual Variations of Sea Surface Temperature over the Arabian Sea and the Indian Monsoon: A New Perspective

The interannual variation of surface fields over the Arabian Sea and Bay of Bengal are studied using data between 1900 and 1979. It is emphasized that the monthly mean sea surface temperature (SST) over the north Indian Ocean and monsoon rainfall are significantly affected by synoptic systems and other intraseasonal variations. To highlight the interannual signals it is important to remove the large-amplitude high-frequency noise and very low frequency long-term trends, if any. By suitable spatial and temporal averaging of the SST and the rainfall data and by removing the long-term trend from the SST data, we have been able to show that there exists a homogeneous region in the southeastern Arabian Sea over which the March�April (MA) SST anomalies are significantly correlated with the seasonal (June�September) rainfall over India. A potential of this premonsoon signal for predicting the seasonal rainfall over India is indicated. It is shown that the correlation between the SST and the seasonal monsoon rainfall goes through a change of sign from significantly positive with premonsoon SST to very small values with SST during the monsoon season and to significantly negative with SST during the post-monsoon months. For the first time, we have demonstrated that heavy or deficient rainfall years are associated with large-scale coherent changes in the SST (although perhaps of small amplitude) over the north Indian 0cean. We also indicate possible reasons for the apparent lack of persistence of the premonsoon SST anomalies.

Two-dimensional fuzzy fault tree analysis for chlorine release from a chlor-alkali industry using expert elicitation

The hazards associated with major accident hazard (MAN) industries are fire, explosion and toxic gas releases. Of these, toxic gas release is the worst as it has the potential to cause extensive fatalities. Qualitative and quantitative hazard analyses are essential for the identification and quantification of these hazards related to chemical industries. Fault tree analysis (FTA) is an established technique in hazard identification. This technique has the advantage of being both qualitative and quantitative, if the probabilities and frequencies of the basic events are known. This paper outlines the estimation of the probability of release of chlorine from storage and filling facility of chlor-alkali industry using FTA. An attempt has also been made to arrive at the probability of chlorine release using expert elicitation and proven fuzzy logic technique for Indian conditions. Sensitivity analysis has been done to evaluate the percentage contribution of each basic event that could lead to chlorine release. Two-dimensional fuzzy fault tree analysis (TDFFTA) has been proposed for balancing the hesitation factor involved in expert elicitation. (C) 2010 Elsevier B.V. All rights reserved.

Studies on the biosynthesis of cytochrome P-450 in rat liver—A probe with phenobarbital

Cytochrome P-450 has been purified from phenobarbital-treated rat livers to a specific content of 17 nmol/mg protein. The major species purified has a molecular weight of 48,000. Using the purified antibody for the cytochrome P-450 preparation it has been shown that the major product synthesized in vivo and in the homologous cell-free system in vitro is the 48,000 molecular weight species. Poly(A)-containing RNA isolated from phenobarbital-treated animals codes for the synthesis of the 48,000 molecular weight species in the wheat germ and reticulocyte lysate cell-free systems. It is concluded that cytochrome P-450 synthesis does not involve processing of a polyprotein precursor, although certain minor modifications including glycosylation of the primary translation product are not ruled out. Phenobarbital treatment of the animal results in a significant increase in the cytochrome P-450 messenger activity as measured in the wheat germ cell-free system.

Kinetics of propellant decomposition

Equations for solid-state decompositions which are controlled by the phase-boundary movement and nucleation have been examined using ammonium perchlorate/polystyrene propellant decomposition at 503 K and 533 K. It was found that 3 different equations governed by the nucleation process show a good fit of data at these temperatures. However, the best fit was obtained for the following Avrami-Erofeev equation, [-In (1 - α]1/4=kt.

Removal of hexavalent chromium using coffee husk

The potential to remove chromium(VI) from aqueous solutions through biosorption using coffee husk was investigated. The effects of pH, contact time, initial concentration and adsorbent dosage on the adsorption of Cr(VI) were studied. The data obeyed Langmuir and Freundlich adsorption isotherms. The Langmuir adsorption capacity was found to be 44.95 mg/g. The Freundlich constants K-f and n were 1.027 mg/g (litre/mg)(n)] and 1.493, respectively. Desorption studies indicated the removal of 60% of the hexavalent chromium. Infrared spectral studies revealed the presence of functional groups, such as hydroxyl and carboxyl groups, on the surface of the biomass, which facilitates biosorption of Cr(VI).

Analysis of Compressibility of Sensitive Soils

Sensitive soils, in general, are prone to mechanical disturbances while sampling, handling, and testing. This necessitates the prediction of true field behavior. The compressibility response of such soils is typical of having three zones, mechanistically explained as nonparticulate, transitional, and particulate. Such zoning has enabled the development of a simple method to predict the field compressibility response of the sample. The field compression curve with sigmact act as the most probable yield stress is considered to reflect 0% disturbance. By a comparison of experimentally determined sigmac and sigmact, it is possible to estimate the degree of sample disturbance. When the value of sigmac is closer to sigmact, the sampling disturbance approaches zero. As the value of sigmac reduces, the degree of sampling disturbance increases. The possibility of using this degree of sample disturbance from compressibility data to obtain other true properties from laboratory results of the sampled specimens has been examined.

Ultimate Strength of RC Wall Panels with Openings

Test results of 12 reinforced concrete (RC) wall panels with openings are presented. The panels have been subjected to in-plane vertical loads applied at an eccentricity to represent possible accidental eccentricity that occurs in practice due to constructional imperfections. The 12 specimens consist of two identical groups of six panels each. One group of panels is tested in one-way in-plane action (i.e., supported at top and bottom edges against lateral displacement). The second group of panels is tested in two-way in-plane action (i.e., supported on all the four edges against lateral displacement). Openings in the panels represent typical door and window openings. Cracking loads, ultimate loads, crack patterns, and lateral deflections of the panels are studied. Empirical methods have been developed for the prediction of ultimate load. Also, lateral deflections, cracking loads, and ultimate loads of identical loads tested under one-way and two-way action are compared.

Ultimate Strength of R.C. Wall Panels in Two-Way In-Plane Action

Test results of 24 reinforced concrete wall panels in two-way action (i.e., supported on all the four sides) and subjected to in-plane vertical load are presented. The load is applied at an eccentricity to represent possible accidental eccentricity that occurs in practice due to constructional imperfections. Influences of aspect ratio, thinness ratio, slendemess ratio, vertical steel, and horizontal steel on the ultimate load are studied. Two equations are proposed to predict the ultimate load carried by the panels. The first equation is empirical and is arrived at from trial and error fitting with test data. The second equation is semi-empirical and is developed from a modification of the buckling strength of thin rectangular plates. Both the equations are formulated so as to give a safe prediction of a large portion of ultimate strength test results. Also, ultimate load cracking load and lateral deflections of identical panels in two-way action (all four sides supported) and oneway action (top and bottom sides only supported) are compared.

Stiffness Coefficients of Layered Soil Systems

One of the most important dynamic properties required in the design of machine foundations is the stiffness or spring constant of the supporting soil. For a layered soil system, the stiffness obtained from an idealization of soils underneath as springs in series gives the same value of stiffness regardless of the location and extent of individual soil layers with respect to the base of the foundation. This paper aims to develop the importance of the relative positioning of soil layers and their thickness beneath the foundation. A simple and approximate procedure called the weighted average method has been proposed to obtain the equivalent stiffness of a layered soil system knowing the individual values of the layers, their relative position with respect to foundation base, and their thicknesses. The theoretically estimated values from the weighted average method are compared with those obtained by conducting field vibration tests using a square footing over different two- and three-layered systems and are found to be very good. The tests were conducted over a range of static and dynamic loads using three different materials. The results are also compared with the existing methods available in the literature.

Improved Inverted V-Notch or Chimney Weir

This paper is devoted to the improvement of the measuring range of inverted V-notch (IVN) weir, a practical linear sharp-crested weir, designed earlier by the writers. The range of linearity of IVN can be considerably enhanced (by more than 200%) by the addition of a retangular weir of width 0.265W (W = half crest width) at a depth of 0.735d (d = altitude of IVN), above the crest of the weir, which is equivalent to providing at this depth two vertical straight lines to the IVN, resulting in a chimney-shaped profile; hence, the modified weir is named chimney weir. The design parameters of the weir, that is, the linearity range, base flow depth, and datum constant, which fixes the reference plane of the weir, are estimated by solving the nonlinear programming problem using a numerical optimization procedure. For flows through this weir above a depth of 0.22d, the discharges are proportional to the depth of flow measured above a reference plane situated at 0.08d above the weir crest for all heads in the range 0.22d <= h <= 2.43d, within a maximum percentage deviation of ±1.5 from the theoretical discharge. A significant result of the analysis is that the same linear head-discharge relationship governing the flow through the IVN is also valid for the extended chimney weir. Experiments with three different chimney weirs show excellent agreement with the theory by giving a constant average coefficient of discharge for each weir.

Critical Reappraisal of Colloidal Activity of Clays

Soil properties and their behavior, apart from stress history, are influence markedly by physicochemical characteristics of the constituent clay and nonclay minerals and their relative proportions. Atterberg limits and Skempton's colloidal activity, which are simple quantitative parameters, reflect the composite effects of the soil constituents and their interactions with pore fluid. Micromechanistic interpretations of these parameters have been provided in this paper. It has been shown that, in general, the liquid limit of fine-grained soils reflects the physicochemical potential and that each of the factors of Skempton's colloidal activity are interdependent. It has been illustrated that property correlations with colloidal activity, as well as with Atterberg limits, result in involved interrelationships due to the interdependence of the parameters.

Crystal structures, spectral and magnetic properties of (µ-hydroxo)(µ-acetato)dicopper(II) complexes containing chelating amines

The reaction of [Cu2(O2CMe)4(H2O)2] with N, N, N′, N′-tetramethylethane- 1,2-diamine (tmen) in ethanol yielded the dicopper(II) complex [Cu2(OH)(O2CMe)(tmen)2][ClO4]21. A similar reaction with N, N- dimethylethane- 1,2-diamine (dmen) afforded a crystalline product 2 in which two dicopper(II) complexes, [Cu2(OH)(O2CMe)(dmen)2][ClO4]22a and [Cu2(OH)(O2CMe)(H2O)2(dmen)2][ClO4]22b, are cocrystallized in a 1 : 1 molar ratio along with 2NaClO4. The crystal structures of 1 and 2 have been determined. The complexes have an asymmetrically dibridged [Cu2(µ-OH)(µ-O2CMe)]2+ core. The co-ordination geometry of the metal is square planar (CuO2N2). The copper atoms in 2b have a square-pyramidal CuO3N2 co-ordination sphere. The Cu Cu distances and Cu–O–Cu angles in 1, 2a and 2b are 3.339(2), 3.368(3), 3.395(7)Å, 120.1(2), 116.4(1) and 123.6(2)°, respectively. Complex 1 exhibits an axial ESR spectrum in a methanol glass giving g∥= 2.26 (A∥= 164 × 10–4 cm–1) and g⊥= 2.04. The ESR spectra obtained from the bulk material of the dmen product are indicative of the presence of two dimers, viz. complex 2a(g∥= 2.25, A∥= 165 × 10–4 cm–1; g⊥= 2.03) and 2b(g∥= 2.19, A∥= 184 × 10–4 cm–1; g⊥= 2.0). Variable-temperature magnetic susceptibility measurements on these complexes show an intramolecular antiferromagnetic coupling in the dimeric core. The fitting parameters are J=–27.8 cm–1, g= 2.1 for complex 1 and J=–10.1 cm–1, g= 2.0 for 2. The magnetostructural properties of the complexes are discussed. There is a linear correlation of the –2J values with the Cu Cu distances among dibridged complexes having square-planar copper(II) centres.

Double Aromaticity in the 3,5-Dehydrophenyl Cation and in Cyclo[6]carbon

The presence of two (4n+2)-electron conjugated systems in perpendicular planes results in considerable aromatic stabilization. Despite having two fewer hydrogens, the 6 pi e-2 sigma e 3,5-dehydrophenyl cation (C6H3+, 1) is 32.7 (CCSD(T)/6-31G**) and 35.2 kcal/mol (RMP4sdtq/6-3iG*//RMP2(fu)/6-31G*) more stable than the phenyl cation (evaluated by an isodesmic reaction involving benzene and m-dehydrobenzene (4)). Cation 1, the global C6H3+ minimum, is 11.7,24.2, 11.8, and 30.4 kcal/mol lower in energy than the 2,6- (11) and 3,4-dehydrophenyl (12) cations as well as the open-chain isomers 13 and 14 (RMP4sdtq/6-31G*//RMP2(fu)/6-31G* + ZPE(RMP2(fu)/6-31G*)). The stability of 1 is increased hyperconjugatively by 2,4,6-trisilyl substitution. The double aromaticity of 1 is indicated by the computed magnetic susceptibility exaltations (IGLO/II//RMP2(fu)/6-31G*) of -5.2, -6.8, -15, and -23.2 relative to 11, 12, 13, and 14, respectively. Thus, 1 fulfills the geometric, energetic, and magnetic criteria of aromaticity. The double aromaticity of the D-6h cyclo[6]carbon is apparent from the same criteria