Kinetics and mechanism of trichloroisocyanuric acid/NaNO2-triggered nitration of aromatic compounds under acid-free and Vilsmeier-Haack conditions

Kinetics and mechanism of nitration of aromatic compounds using trichloroisocyanuric acid (TCCA)/NaNO₂, TCCA-N,N-dimethyl formamide (TCCA-DMF)/NaNO₂, and TCCA-N,N-dimethyl acetamide (TCCA-DMA)/NaNO₂ under acid-free and Vilsmeier-Haack conditions. Reactions followed second-order kinetics with a first-order dependence on [Phenol] and [Nitrating agent] ([TCCA], [(TCCA-DMF)], or [(TCCA-DMA)] >> [NaNO₂]). Reaction rates accelerated with the introduction of electron-donating groups and retarded with electron-withdrawing groups, but did not fit well into the Hammett's theory of linear free energy relationship or its modified forms like Brown-Okamoto or Yukawa-Tsuno equations. Rate data were analyzed by Charton's multiple linear regression analysis. Isokinetic temperature (β) values, obtained from Exner's theory for different protocols, are 403.7 K (TCCA-NaNO₂), 365.8 K (TCCA-DMF)/NaNO₂, and 358 K (TCCA-DMA)/NaNO₂. These values are far above the experimental temperature range (303-323 K), indicating that the enthalpy factors are probably more important in controlling the reaction.     

Heat transfer and pressure drop studies in a circular tube fitted with straight full twist

Experimental investigation of heat transfer characteristics of circular tube fitted with straight full twist insert has been presented. The heat transfer coefficient increases with Reynolds number and decreasing spacer distance with maximum being 2 in. spacer distance for both the type of twist inserts. Also, there is no appreciable increase in heat transfer enhancement in straight full twist insert with 2 in. spacer distance. Experiments were carried out in turbulent flow using straight full twist insert with 4 in. spacer and similar trend of increasing Nusselt number with Reynolds number was observed. Performance evaluation analysis was made and the maximum performance ratio was obtained for each twist insert corresponding to the Reynolds number of 2550.     

Some Isoperimetric Inequalities in Electrochemistry and Hele Shaw Flows

Isoperimetric inequalities are applied to a moving-boundaryproblem for doubly-connected domains. This problem occurs forexample in electrochemistry, in which case the domains in questionare the electrolyte of an electrolytic cell. The two electrodessurrounding the electrolyte are assumed to grow or dissolve,at different rates in general, by electrochemical reaction.We obtain optimal estimates showing, for example, that the leastchange in volume of each electrode always occurs in sphericalsymmetry.     

Loss Reduction by Means of Two-Dimensional Roughness Elements on the Suction Surface of a Linear Turbine Rotor Cascade

This paper reports the results of experimental investigations carried out to reduce pressure losses by means of two-dimensional roughness elements (in the form of stainless steel tubes of different diameters). The roughness elements are fixed at various axial stations on the suction surface of 120° turning, 175 mm chord, impulse turbine rotor blades. Flow measurements are carried out at the exit of the cascade at five axial stations, using a five-hole probe operating in non-nulling mode. In addition, the blade surface static pressure distribution is measured. The data from the five-hole probe measurements are used to calculate pressure, velocity and flow angle distributions at the cascade exit and these results are used to calculate mass averaged values and integral parameters such as wake half-width, loss coefficient, etc. The static pressure distribution is altered very little except near the roughness element. The lift coefficient remains almost constant for all configurations and the drag coefficient is reduced for some configurations. The non-dimensional total pressure defects in the wake for all configurations followed Gaussian distribution. A two-dimensional roughness element of 0.6 mm diameter placed at 0.65 chord on the suction surface showed an appreciable reduction in pressure losses.     

l-Proline catalyzed efficient one-pot three-component aza-Diels–Alder reactions on nitrostyrylisoxazoles: a facile synthesis of new isoxazolyl tetrahydroquinolines and isoxazolo[2,3-a]pyrimidines

l-Proline acts as an efficient organocatalyst and found to promote one-pot three-component aza-Diels–Alder reaction of aryl or isoxazole imines formed in situ from aromatic or isoxazoleamines and aromatic aldehydes with nitrostyrylisoxazoles to afford the isoxazolyl tetrahydroquinolines or isoxazolo[2,3-a]pyrimidines, respectively, in excellent yields at ambient temperature under neutral conditions.     

On the coexistence of spin and lattice polarons in the La0.67−xEuxCa0.33MnO3 CMR system

The electrical and magnetic transport properties of the La_0.67−xEu_xCa_0.33MnO₃ system exhibit lowering of insulator to metal and paramagnetic to ferromagnetic transition temperature (T_C) with the increase of Eu concentration in addition to possessing CMR property. The temperature variation of electrical resistivity and magnetic susceptibility for x=0.21 is found to have two distinct regions in the paramagnetic state for T>T_P; one with the localization of lattice polaron in the high-temperature region (T>1.5T_P) satisfying the dynamics of variable range hopping (VRH) model and the other being the combination of the spin and lattice polarons in the region T_P<T<1.5T_P. The resistivity variation with temperature and magnetic field, the cusp in the resistivity peak and CMR phenomenon are interpreted in terms of coexistence of spin and lattice small polarons in the intermediate region (T_P<T<1.5T_P). The spin polaron energy in the La_0.46Eu_0.21Ca_0.33MnO₃ system is estimated to be 106.73±0.90 meV and this energy decreases with the increase of external magnetic field. The MR ratio is maximal with a value of 99.99% around the transition temperature and this maximum persists till T→0 K, at the field of 8 T.     

MODELING CLIMATE CHANGE AND THE EFFECT ON THE NORWEGIAN SALMON FARMING INDUSTRY

Abstract Global warming is expected to affect the ecosystem in the Northeast Atlantic, and substantial changes will also affect the aquaculture industry. Farming of salmon and trout is the biggest aquaculture industry in Norway, with an export value of about 3 billion US dollars in 2007. The objective of the paper is to analyze the potential economic effect a general increase in sea temperature can have on the Norwegian salmon aquaculture industry. The assessment of the economic impact of global warming is made possible by estimating a growth function, which explicitly includes sea water temperature. The analysis compares the economic effect of a climate change on fish farming plants in the south and the north of Norway. The scenarios are based on a model with monthly seasonal variation in temperature.     

N,N’-dimethyl formamide (DMF) mediated Vilsmeier–Haack adducts with 1,3,5-triazine compounds as efficient catalysts for the transesterification of β-ketoesters

Abstract

N, N’-dimethyl formamide (DMF) mediated Vilsmeier–Haack (VH) adducts with 1,3,5-triazine compunds such as trichloroisocyanuric acid (TCCA) and trichlorotriazine (TCTA) were prepared by replacing classical oxy chlorides POCl₃, and SOCl₂, which were explored as efficient catalysts for the transesterification of β-ketoesters. The prepared (TCCA/DMF) and (TCTA/DMF) adducts improved greenery of the classical Vilsmeier–Haack reagents (POCl₃/DMF), and (SOCl₂/DMF), and demonstrated their better efficient catalytic ativity. Reaction times were in the range: 3.5 to 6.5?hr (SOCl₂/DMF); 2.8–5.2?hr (POCl₃/DMF); 2.5–5.2?hr (TCCA/DMF) and 2.5–5.0?hr (TCTA/DMF) catalytic systems. Ultrasonically (US) assisted protocols with these reagents further reduced the reaction times (two to three times), while microwave assisted (MW) protocols with these reagents were much more effective. The reactions could be completed in only few seconds (less than a minute) in MWassisted protocols as compared to US assited reactions, followed by good product yields.     

The effect of end conditions on the vortex-induced vibration of cylinders

In the present investigation we study the effect of end conditions on the vortex-induced vibration of an elastically mounted rigid cylinder. This work was triggered by some initial controlled vibration experiments which showed that spanwise end conditions can have a large effect on measured fluid forces on a cylinder, and this suggested that some of the disparity amongst previous free vibration studies may possibly be attributed to differences in end conditions. In the principal experiments here, we are concerned with a vertical cylinder piercing the clean free surface of a water channel, and attached to a carriage system mounted atop the channel. The upper end of the submerged cylinder is thus the free surface, while the lower end is manipulated to yield three different conditions, namely: an attached endplate; an unattached endplate fixed to the channel floor (with a variable gap between cylinder and plate); and a condition of no endplate at all. Interestingly, we find that the free vibration response for the attached and unattached endplate cases were nearly identical. One expectation was that the case without an endplate would lead to a flow around the end of the body, modifying the vortex dynamics, and thereby reducing the correlation of the induced fluid forces on the body. Surprisingly, over the entire response plot, the vibration amplitude is markedly higher in the absence of an endplate, with the exception of the peak amplitude, which remains nearly unchanged. Unexpectedly, the vibrations become much more steady at flow velocities in the vicinity of the peak response, if the endplate is removed. In a further set of experiments, we undertake controlled vibration, where we vary the gap between cylinder and endplate. We discover a large discontinuous jump in the magnitude of fluid excitation, when the gap exceeds 15% of a diameter. For larger gaps, the fluid excitation becomes independent of the gap size, effectively equivalent to having no plate at all. This study is consistent with some of the disparity between the character of vibration response plots in previous studies, if one takes into account the particular end conditions chosen in those studies.     

Zirconium(IV) chloride catalyzed new and efficient protocol for the selective cleavage of p-methoxybenzyl ethers

A highly selective and efficient method for the unmasking of p-methoxybenzyl (PMB) ethers and esters has been developed by use of 20 mol % of zirconium(IV) chloride as Lewis acid in acetonitrile. The present method is very fast, and the conditions are tolerable to a variety of acid/base-sensitive protecting groups and substrates such as carbohydrates, terpenes, and amino acids. The products are obtained in good to high yields.