Studies on Energy Exchange and Upper Ocean Thermat Structure in Arabian Sea and Heat Transport in Northern Indian Ocean

The thesis focused Studies on Energy Exchange and Upper Ocean Thermal Structure in Arabian Sea and Heat Transport in Northern Indian Ocean. The present thesis is an attempt to understand the upper ocean thermal characteristics at selected areas in the western and eastern Arabian Sea in relation to surface energy exchange and dynamics, on a climatological basis. It is also aimed to examine, the relative importance of different processes in the evolution of SST at the western and eastern Arabian Sea. Short-term variations of energy exchange and upper ocean thermal structure are also investigated. Climatological studies of upper ocean thermal structure and surface energy exchange in the western and eastern parts of Arabian Sea bring out the similarities/differences and the causative factors for the observed features. Annual variation of zonally averaged heat advection in north Indian Ocean shows that maximum export of about 100 W/m2 occurs around 15ON during southwest monsoon season. This is due to large negative heat storage caused by intense upwelling in several parts of northern Indian Ocean. By and large, northern Indian Ocean is an area of heat export

The simulation of the opposing fluxes of latent heat and CO2 over various land-use types: coupling a gas exchange model to a mesoscale atmospheric model

A mesoscale meteorological model (FOOT3DK) is coupled with a gas exchange model to simulate surface fluxes of CO2 and H2O under field conditions. The gas exchange model consists of a C3 single leaf photosynthesis sub-model and an extended big leaf (sun/shade) sub-model that divides the canopy into sunlit and shaded fractions. Simulated CO2 fluxes of the stand-alone version of the gas exchange model correspond well to eddy-covariance measurements at a test site in a rural area in the west of Germany. The coupled FOOT3DK/gas exchange model is validated for the diurnal cycle at singular grid points, and delivers realistic fluxes with respect to their order of magnitude and to the general daily course. Compared to the Jarvis-based big leaf scheme, simulations of latent heat fluxes with a photosynthesis-based scheme for stomatal conductance are more realistic. As expected, flux averages are strongly influenced by the underlying land cover. While the simulated net ecosystem exchange is highly correlated with leaf area index, this correlation is much weaker for the latent heat flux. Photosynthetic CO2 uptake is associated with transpirational water loss via the stomata, and the resulting opposing surface fluxes of CO2 and H2O are reproduced with the model approach. Over vegetated surfaces it is shown that the coupling of a photosynthesis-based gas exchange model with the land-surface scheme of a mesoscale model results in more realistic simulated latent heat fluxes.

Simultaneous synthesis of work exchange networks with heat integration

The optimal integration of work and its interaction with heat can represent large energy savings in industrial plants. This paper introduces a new optimization model for the simultaneous synthesis of work exchange networks (WENs), with heat integration for the optimal pressure recovery of process gaseous streams. The proposed approach for the WEN synthesis is analogous to the well-known problem of synthesis of heat exchanger networks (HENs). Thus, there is work exchange between high-pressure (HP) and low-pressure (LP) streams, achieved by pressure manipulation equipment running on common axes. The model allows the use of several units of single-shaft-turbine-compressor (SSTC), as well as stand-alone compressors, turbines and valves. Helper motors and generators are used to respond to any demand and excess of energy. Moreover, between the WEN stages the streams are sent to the HEN to promote thermal recovery, aiming to enhance the work integration. A multi-stage superstructure is proposed to represent the process. The WEN superstructure is optimized in a mixed-integer nonlinear programming (MINLP) formulation and solved with the GAMS software, with the goal of minimizing the total annualized cost. Three examples are conducted to verify the accuracy of the proposed method. In all case studies, the heat integration between WEN stages is essential to improve the pressure recovery, and to reduce the total costs involved in the process.

MINLP Optimization Algorithm for the Synthesis of Heat and Work Exchange Networks

This paper introduces a new optimization model for the simultaneous synthesis of heat and work exchange networks. The work integration is performed in the work exchange network (WEN), while the heat integration is carried out in the heat exchanger network (HEN). In the WEN synthesis, streams at high-pressure (HP) and low-pressure (LP) are subjected to pressure manipulation stages, via turbines and compressors running on common shafts and stand-alone equipment. The model allows the use of several units of single-shaft-turbine-compressor (SSTC), as well as helper motors and generators to respond to any shortage and/or excess of energy, respectively, in the SSTC axes. The heat integration of the streams occurs in the HEN between each WEN stage. Thus, as the inlet and outlet streams temperatures in the HEN are dependent of the WEN design, they must be considered as optimization variables. The proposed multi-stage superstructure is formulated in mixed-integer nonlinear programming (MINLP), in order to minimize the total annualized cost composed by capital and operational expenses. A case study is conducted to verify the accuracy of the proposed approach. The results indicate that the heat integration between the WEN stages is essential to enhance the work integration, and to reduce the total cost of process due the need of a smaller amount of hot and cold utilities.

DEVELOPMENT OF A MICRO-HEAT EXCHANGER WITH STACKED PLATES USING LTCC TECHNOLOGY

A green ceramic tape micro-heat exchanger was developed using Low Temperature Co-fired Ceramics technology (LTCC). The device was designed by using Computational Aided Design software and simulations were made using a Computational Fluid Dynamics package (COMSOL Multiphysics) to evaluate the homogeneity of fluid distribution in the microchannels. Four geometries were proposed and simulated in two and three dimensions to show that geometric details directly affect the distribution of velocity in the micro-heat exchanger channels. The simulation results were quite useful for the design of the microfluidic device. The micro-heat exchanger was then constructed using the LTCC technology and is composed of five thermal exchange plates in cross-flow arrangement and two connecting plates, with all plates stacked to form a device with external dimensions of 26 x 26 x 6 mm(3).

Free-Surface Aeration and Momentum Exchange at a Bottom Outlet

This study aims to provide some new understanding of the air-water flow properties in high-velocity water jets discharging past an abrupt drop. Such a setup has been little studied to date despite the relevance to bottom outlets. Downstream of the step brink, the free-jet entrains air at both upper and lower air-water interfaces, as well as along the sides. An air-water shear layer develops at the lower nappe interface. At the lower nappe, the velocity redistribution was successfully modelled and the velocity field was found to be similar to that in two-dimensional wake flow. The results highlighted further two distinct flow regions. Close to the brink (Wex < 5000), the flow was dominated by momentum transfer. Further downstream (Wex > 5000), a strong competition between air bubble diffusion and momentum exchanges took place.

Catecholamine release in heat-stressed Antarctic fish causes proton extrusion by the red cells

Two species of Antarctic fish were stressed by moving them from seawater at -1 degrees C to seawater at 10 degrees C and holding them for a period of 10 min. The active cryopelagic species Pagothenia borchgrevinki maintained heart rate while in the benthic species Trematomus bernacchii there was an increase in heart rate. Blood pressure did not change in either species. Both species released catecholamines into the circulation as a consequence of the stress. P. borchgrevinki released the greater amounts, having mean plasma concentrations of 177 +/- 54 nmol.l(-1) noradrenaline and 263 +/- 131 nmol.l(-1) adrenaline at 10 min. Pla.sma noradrenaline concentrations rose to 47 +/- 14 nmol.l(-1) and adrenaline to 73 +/- 28 nmol.l(-1) in T. bernacchii. Blood from P. borchgrevinki was tonometered in the presence of isoprenaline. A fall in extracellular pH suggests the presence of a Na+/H+ antiporter on the red cell membrane, the first demonstration of this in an Antarctic fish. Treatment with the beta-adrenergic antagonist drug sotalol inhibited swelling of red blood cells taken from temperature-stressed P. borchgrevinki, suggesting that the antiporter responds to endogenous catecholamines.

Gas gap heat switch for CryoFree project

Cryogen-free superconducting magnet systems have become popular during the last two decades for the simple reason that with the use of liquid helium is rather cumbersome and is a scarce resource. Some available CFMS uses a mechanical cryocooler as cold source of the superconductor magnet. However, the cooling of the sample holder is still made through an open circuit of helium. A thermal management of a completely cryogen-free system is possible to be implemented by using a controlled gas gap heat switch (GGHS) between the cryocooler and the variable temperature insert (VTI). This way it would eliminate the helium open circuit. Heat switches are devices that allow to toggle between two distinct thermal states (ON and OFF state). Several cryogenic applications need good thermal contact and a good thermal insulation at different stages of operation. A versatile GGHS was designed and built with a 100 mm gap and tested with helium as exchange gas. An analytic thermal model was developed and a good agreement with the experimental data was obtained. The device was tested on a crycooler at 4 to 80 K ranges. A 285 mW/K thermal conductance was measured at ON state and 0.09 mW/K at OFF. 3000 ON/OFF thermal conductance ratio was obtained at 4 K with helium.

Building a thinner gap in a gas-gap heat switch

25th International Cryogenic Engineering Conference and the International Cryogenic Materials Conference in 2014, ICEC 25–ICMC 2014

On problems of calculating energy expenditure and substrate utilization from respiratory exchange data.

Indirect calorimetry based on respiratory exchange measurement has been successfully used from the beginning of the century to obtain an estimate of heat production (energy expenditure) in human subjects and animals. The errors inherent to this classical technique can stem from various sources: 1) model of calculation and assumptions, 2) calorimetric factors used, 3) technical factors and 4) human factors. The physiological and biochemical factors influencing the interpretation of calorimetric data include a change in the size of the bicarbonate and urea pools and the accumulation or loss (via breath, urine or sweat) of intermediary metabolites (gluconeogenesis, ketogenesis). More recently, respiratory gas exchange data have been used to estimate substrate utilization rates in various physiological and metabolic situations (fasting, post-prandial state, etc.). It should be recalled that indirect calorimetry provides an index of overall substrate disappearance rates. This is incorrectly assumed to be equivalent to substrate "oxidation" rates. Unfortunately, there is no adequate golden standard to validate whole body substrate "oxidation" rates, and this contrasts to the "validation" of heat production by indirect calorimetry, through use of direct calorimetry under strict thermal equilibrium conditions. Tracer techniques using stable (or radioactive) isotopes, represent an independent way of assessing substrate utilization rates. When carbohydrate metabolism is measured with both techniques, indirect calorimetry generally provides consistent glucose "oxidation" rates as compared to isotopic tracers, but only when certain metabolic processes (such as gluconeogenesis and lipogenesis) are minimal or / and when the respiratory quotients are not at the extreme of the physiological range. However, it is believed that the tracer techniques underestimate true glucose "oxidation" rates due to the failure to account for glycogenolysis in the tissue storing glucose, since this escapes the systemic circulation. A major advantage of isotopic techniques is that they are able to estimate (given certain assumptions) various metabolic processes (such as gluconeogenesis) in a noninvasive way. Furthermore when, in addition to the 3 macronutrients, a fourth substrate is administered (such as ethanol), isotopic quantification of substrate "oxidation" allows one to eliminate the inherent assumptions made by indirect calorimetry. In conclusion, isotopic tracers techniques and indirect calorimetry should be considered as complementary techniques, in particular since the tracer techniques require the measurement of carbon dioxide production obtained by indirect calorimetry. However, it should be kept in mind that the assessment of substrate oxidation by indirect calorimetry may involve large errors in particular over a short period of time. By indirect calorimetry, energy expenditure (heat production) is calculated with substantially less error than substrate oxidation rates.

Modification of Ca-Montmorillonite by Low-Temperature Heat Treatment, HR-106, 1964

Objectives of this investigation were to measure the effects of moderate heat treatments (below the dehydroxylation temperature) on physical and chemical properties of a calcium-montmorillonite clay. Previous workers have noted the reduction in cation exchange capacity and swelling property after heating in the range 200 to 400°C, and have suggested several possible explanations, such as hysteresis effect, increased inter-layer attractions due to removal of inter-layer water, or changes in the disposition of inter-layer or layer surface ions. The liquid limits of Ca-montmorillonite were steadily decreased with increased temperature of treatment, levelling at about 450°C. The plastic limit decreased slightly up to 350°C, above which samples could no longer be rolled into threads. The gradual change is in contrast with sudden major changes noted for weight loss (maximum rates of change at l00°C and 500°C), glycol retention surface area (520°C), and d001 diffraction peak intensity (17.7 A spacing) and breadth after glycolation (530°C). Other properties showing more gradual reductions with heat treatment were amount of exchangeable calcium (without water soaking), cation exchange capacity by NH4AC method, and d001 intensity (21 A spacing) after storing at 100% r.h. one month and re-wetting with water. Previous water soaking allowed much greater release of fixed Ca++ up to 450°C. Similar results were obtained with cation exchange capacities when samples were treated with N CaCl2 solution. The 21.0 A peak intensity curve showed close similarity to the liquid limit and plastic index curves in the low temperature range, and an explanation is suggested.

Pressure-assisted cold denaturation of hen egg white lysozyme: the influence of co-solvents probed by hydrogen exchange nuclear magnetic resonance

COSY proton nuclear magnetic resonance was used to measure the exchange rates of amide protons of hen egg white lysozyme (HEWL) in the pressure-assisted cold-denatured state and in the heat-denatured state. After dissolving lysozyme in deuterium oxide buffer, labile protons exchange for deuterons in such a way that exposed protons are substituted rapidly, whereas "protected" protons within structured parts of the protein are substituted slowly. The exchange rates k obs were determined for HEWL under heat treatment (80ºC) and under high pressure conditions at low temperature (3.75 kbar, -13ºC). Moreover, the influence of co-solvents (sorbitol, urea) on the exchange rate was examined under pressure-assisted cold denaturation conditions, and the corresponding protection factors, P, were determined. The exchange kinetics upon heat treatment was found to be a two-step process with initial slow exchange followed by a fast one, showing residual protection in the slow-exchange state and P-factors in the random-coil-like range for the final temperature-denatured state. Addition of sorbitol (500 mM) led to an increase of P-factors for the pressure-assisted cold denatured state, but not for the heat-denatured state. The presence of 2 M urea resulted in a drastic decrease of the P-factors of the pressure-assisted cold denatured state. For both types of co-solvents, the effect they exert appears to be cooperative, i.e., no particular regions within the protein can be identified with significantly diverse changes of P-factors.

Thermodynamic evaluation and modeling of proton and water exchange associated with benzamidine and berenil binding to ß-trypsin

Serine-proteases are involved in vital processes in virtually all species. They are important targets for researchers studying the relationships between protein structure and activity, for the rational design of new pharmaceuticals. Trypsin was used as a model to assess a possible differential contribution of hydration water to the binding of two synthetic inhibitors. Thermodynamic parameters for the association of bovine ß-trypsin (homogeneous material, observed 23,294.4 ± 0.2 Da, theoretical 23,292.5 Da) with the inhibitors benzamidine and berenil at pH 8.0, 25ºC and with 25 mM CaCl2, were determined using isothermal titration calorimetry and the osmotic stress method. The association constant for berenil was about 12 times higher compared to the one for benzamidine (binding constants are K = 596,599 ± 25,057 and 49,513 ± 2,732 M-1, respectively; the number of binding sites is the same for both ligands, N = 0.99 ± 0.05). Apparently the driving force responsible for this large difference of affinity is not due to hydrophobic interactions because the variation in heat capacity (DCp), a characteristic signature of these interactions, was similar in both systems tested (-464.7 ± 23.9 and -477.1 ± 86.8 J K-1 mol-1 for berenil and benzamidine, respectively). The results also indicated that the enzyme has a net gain of about 21 water molecules regardless of the inhibitor tested. It was shown that the difference in affinity could be due to a larger number of interactions between berenil and the enzyme based on computational modeling. The data support the view that pharmaceuticals derived from benzamidine that enable hydrogen bond formation outside the catalytic binding pocket of ß-trypsin may result in more effective inhibitors.

NMR studies of the exchange reactions of CH3CN.BX3 with excess CH3CN /|nJoseph Fogelman. -- 260 St. Catharines, Ont. : [s. n.],

Exchange reactions between molecular complexes and excess acid or base are well known and have been extensively surveyed in the literature(l). Since the exchange mechanism will, in some way involve the breaking of the labile donor-acceptor bond, it follows that a discussion of the factors relating to bonding in molecular complexes will be relevant. In general, a strong Lewis base and a strong Lewis acid form a stable adduct provided that certain stereochemical requirements are met. A strong Lewis base has the following characteristics (1),(2) (i) high electron density at the donor site. (ii) a non-bonded electron pair which has a low ionization potential (iii) electron donating substituents at the donor atom site. (iv) facile approach of the site of the Lewis base to the acceptor site as dictated by the steric hindrance of the substituents. Examples of typical Lewis bases are ethers, nitriles, ketones, alcohols, amines and phosphines. For a strong Lewis acid, the following properties are important:( i) low electron density at the acceptor site. (ii) electron withdrawing substituents. (iii) substituents which do not interfere with the close approach of the Lewis base. (iv) availability of a vacant orbital capable of accepting the lone electron pair of the donor atom. Examples of Lewis acids are the group III and IV halides such (M=B, AI, Ga, In) and MX4 - (M=Si, Ge, Sn, Pb). The relative bond strengths of molecular complexes have been investigated by:- (i) (ii) (iii) (iv) (v] (vi) dipole moment measurements (3). shifts of the carbonyl peaks in the IIIR. (4) ,(5), (6) .. NMR chemical shift data (4),(7),(8),(9). D.V. and visible spectrophotometric shifts (10),(11). equilibrium constant data (12), (13). heats of dissociation and heats of reactions (l~), (16), (17), (18), (19). Many experiments have bben carried out on boron trihalides in order to determine their relative acid strengths. Using pyridine, nitrobenzene, acetonitrile and trimethylamine as reference Lewis bases, it was found that the acid strength varied in order:RBx3 > BC1 3 >BF 3 • For the acetonitrile-boron trihalide and trimethylamine boron trihalide complexes in nitrobenzene, an-NMR study (7) showed that the shift to lower field was. greatest for the BB~3 adduct ~n~ smallest for the BF 3 which is in agreement with the acid strengths. If electronegativities of the substituents were the only important effect, and since c~ Br ,one would expect the electron density at the boron nucleus to vary as BF3heat of formation of ethyl acetate adducts and the shift in the carbonyl I.R. stretch, Drago (22) et al have proposed that the angular di~tortion of the X-B-X bonds from sp2 (12 ) to sp3 (10 hybridization is proportional to the amount of charge transferred, i.e. to the nature of the base, and they have rejected the earlier concept of reorganization energy in explaining the formation of the adduct bond (19).

The effect of free Ca2+ on the heat stability and other characteristics of low-heat skim milk powder

Low-heat skim milk powder (SMP), reconstituted to 25% total solids, was found to have poor heat stability. This could be improved by reducing the free Ca2+ concentration to 1.14 mm, or lower, by the addition of either Amberlite IR-120 ion-exchange resin in its sodium form or tri-sodium citrate in skim milk prior to evaporation and spray drying. Reduction in Ca2+ concentration was accompanied by increases in pH, particle size, and kinematic viscosity, and by a reduction in zeta-potential and changes in colour. In-container sterilisation of the reconstituted powder increased particle size, zeta-potential, kinematic viscosity and a* and b* values. However. Ca2+ concentration, pH and whiteness decreased. This study elucidated the importance of Ca2+ concentration and pH on heat stability of low-heat SMP, suggesting that Ca2+ concentration and pH in bulk milk are useful indicators for ensuring that spray dried milk powder has good heat stability. (C) 2009 Elsevier Ltd. All rights reserved.