Enthalpy-entropy compensation based on isotherms of mango

Dados de equilíbrio da umidade da polpa de manga foram determinados utilizando-se o método estático gravimétrico. As isotermas de adsorção e dessorção foram obtidas na faixa de 30-70 ºC e as atividades de água (a w) de 0,02 a 0,97. A utilização do modelo de GAB nos resultados experimentais, através da análise de regressão não linear, proporcionou um bom ajuste entre os dados experimentais e os valores calculados. O calor isostérico de sorção foi estimado a partir dos dados de equilíbrio de sorção, utilizando-se a equação de Clausius-Clayperon. Notou-se que os calores isostéricos de sorção crescem com o aumento da temperatura e pode ser bem ajustado através de uma relação exponencial. A teoria da compensação entalpia-entropia foi aplicada às isotermas de sorção e gráficos deltaH versus deltaS forneceram as temperaturas isocinéticas, indicando um processo de sorção entalpicamente controlado.

Effect of drying method on the adsorption isotherms and isosteric heat of passion fruit pulp powder

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Thermodynamic and quality properties of lemon juice powder as affected by maltodextrin and Arabic gum

Sorption isotherms of lemon juice (LE) powders with and without additives-18% maltodextrin (MA) or 18% gum Arabic (GA) were determined at 20-50 degrees C. Addition of additives was shown to affect the isotherms in such a way that, at the same water activity, samples LE + GA and LE + MA presented lower equilibrium moisture content and were not so affected by varying temperature. The net isosteric heats of sorption of juice powders with additives were higher (less negative) than those of lemon juice powders, suggesting that there are more active polar sites in the product without addition of GA or MA. In general, the quality properties decreased with the addition of maltodextrin and gum arabic and it was obtained similar values for LE + GA and LE + MA.

Thermodynamic properties applied to the sorption isotherms of kiwifruit

The net isosteric heat and entropy of water sorption were calculated for kiwifruit, based on sorption isotherms obtained by the static gravimetric method at different temperatures (20 to 70 degreesC). The Guggenheim-Anderson-deBoer equation was fitted to the experimental data, using direct non-linear regression analysis; the agreement between experimental and calculated values was satisfactory. The net isosteric heat of sorption was estimated from equilibrium sorption data, using the Clausius-Clapeyron equation. Isosteric heats of sorption were found to increase with increasing temperature and could be well adjusted by an exponential relationship. The enthalpy-entropy compensation theory was applied to sorption isotherms and plots of DeltaH versus DeltaS provided the isokinetic temperature, T-B = 450.9 +/- 7.7 K, indicating an enthalpy-controlled desorption process over the whole range of moisture content considered.

Effect of maltodextrin and arabic gum in water vapor sorption thermodynamic properties of vacuum dried pineapple pulp powder

Moisture equilibrium data of pineapple pulp (PP) powders with and without additives - 18% maltodextrin (MD) or 18% gum Arabic (GA) - were determined at 20, 30, 40 and 50 degrees C by using the static gravimetric method in a water activity range of 0.06-0.90. The obtained isotherms were sigmoid, typical type 111, and the Guggenhein-Anderson-de Boer (GAB) model was fitted to the experimental data of equilibrium moisture content versus water activity. Addition of additives was shown to affect the isotherms in such a way that, at the same water activity, samples PP + GA and PP + MD presented lower equilibrium moisture content and were not so affected by varying temperature. The net isosteric heats of sorption of pulp powders with additives were higher (less negative) than those of pineapple pulp powders, suggesting that there are more active polar sites in the product without addition of GA or MD. An empirical exponential relationship could describe the heat of sorption dependence on the material moisture content. (C) 2007 Elsevier Ltd. All rights reserved.

Sorption isotherms of alligator's meat (Caiman crocodilus yacare)

Sorption isotherms were determined for salted alligator's meat at four different temperatures (10degreesC, 15degreesC, 25degreesC and 35degreesC), using a standard gravimetric method. The goodness of fit of five sorption models to experimental data was determined. Five models, namely the GAB, the BET, the Halsey, the Henderson and the Hailwood and Horrobin, were evaluated to determine the best fit for the experimental data. The GAB was the best fitted model for the data of salted alligator's meat with an average error less than 10% for temperature of 10degreesC and less than 5% for the others temperatures. The coefficients of determination (r(2)) were 0.99 for all temperatures considered. The monolayer values decreased as temperature increased. The other four models were not appropriated to fit the data because of the high error values, although the r(2) were also similar to the GAB model. The net isosteric heat of sorption was estimated from equilibrium sorption data, using the Clausis-Clapeyron equation. Isosteric heats of sorption were found to increase with increasing temperature and could be well adjusted by an exponential relationship. (C) 2002 Elsevier B.V. Ltd. All rights reserved.

Production and heat treatment of cast graphitic steels with additions of niobium

The optimal combination of the mechanical characteristics of austempered spheroidal graphitic cast steel together with modern casting techniques yielded an economically promising product. The maximum potential of the usage of these steels is related to fabrication and characterization techniques, among which, one of the most important is the cooling diagram (TTT curve). In this work, 3 heats of graphitic steels with the following nominal compositions were cast: 1.0 % C, 2.3 % Si, 0.4 % Mn, and with niobium contents of. 0.0 %, 0.5 % and 1.0 %. TTT curves were determined by dilatometric testing and test specimens of these steels were austempered. The samples were then characterized by hardness testing and optical and SEM microscopy. Tensile, impact (no notch) and wear testing were also performed. The addition of niobium produced significant alterations in the TTT diagrams. Increasing niobium content moves the pearlite transformation nose to the right and the bainitic transformation nose to the left. Tensile strength of these alloys was high, in the range of 1700 MPa and impact values were around of 45 Joules for alloy with 1 % Nb, 49 Joules for alloy with 0.5 % Nb and fracture did not occur for the alloy without the addition of Nb.

Production and heat treatment of cast graphitic steels with additions of niobium

The optimal combination of the mechanical characteristics of austempered spheroidal graphitic cast steel together with modern casting techniques yielded an economically promising product. The maximum potentiality of the usage of these steels is related to fabrication and characterization techniques, among which, one of the most important is the cooling diagram (TTT curve). In this work, 3 heats of graphitic steels with the following nominal compositions were cast: 1.0%C, 2.3%Si, 0.4% Mn, and with niobium contents of 0.0%, 0.5% and 1.0%. TTT curves were determined by dilatometric testing and test specimens of these steels were austempered. The samples were then characterized by hardness testing and optical and SEM microscopy. Tensile, impact (no notch) and wear testing were also performed. The addition of niobium produced significant alterations in the TTT diagrams. Increasing niobium content moves the pearlite transformation nose to the right and the bainitic transformation nose to the left. Tensile strength of these alloys was high, in the range of 1700 MPa and impact values were around of 45 Joules for alloy with 1% Nb, 49 Joules for alloy with 0.5% Nb and fracture did not occur for the alloy without the addition of Nb.

AM1 and PM3 Calculations of the Potential Energy Surfaces for CH2OH Reactions with NO and NO2

The AM1 and PM3 molecular orbital methods have been utilized to investigate the reactions of CH20H with NO and NO2 PM3 and AM1 calculated heats of formation differ from experimental values by 8.6 and 18.8 kcal mol-', respectively. The dominant reaction of CH20H with NO is predicted to produce the adduct HOCH2N0, supporting the hypothesis of Pagsberg, Munk, Anastasi, and Simpson. Calculated activation energies for the NO2 system predict the formation of the adducts HOCH2N02 and HOCH20N0. In addition, the PM3 calculations predict that the abstraction reaction producing CH20 and HN02 is more likely than one producing CH20 and HONO from reactions of CH20H with NO2.

Sensitivity of charge transfer reactions to hydrocarbon ion structures

Charge transfer reactivities of hydrocarbon ions have been measured with time-of-flight techniques, and results correlated with theoretical structures computed by self-consistent field molecular orbital methods. Recombination energies, ion structures, heats of formation, reaction energetics and relative charge transfer cross-sections are presented for molecular and fragment ions produced by electron bombardment ionization of CH4, C2H4, C2H6, C3H8 and C4H10 molecules. Even-electron bridged cations have low ion recombination energies and relatively low charge transfer cross-sections as compared with odd-electron hydrocarbon cations.

Proceedings of the 10th Annual Biochemical Engineering Symposium

This the tenth in a series of symposia devoted to talks by students on their biochemical engineering research. The first, third, fifth, and ninth were at Kansas State University in Manhattan, the second and fourth were at the University of Nebraska–Lincoln, the sixth was in Kansas City in conjunction with the 81st American Institute of Chemical Engineers National Meeting, the seventh was at Iowa State University in Ames, and the eighth was held at the University of Missouri–Columbia. Contents"Combined Autohydrolysis-Organosolv Pretreatment of Lignocellulosic Materials," Robert A. Lewis, Colorado State University "An Investigation of Cellulase Activity Assays," Minhhuong Nguyen, University of Missouri–Columbia "Action Pattern of a Xylobiohydrolase from Aspergillus niger," Mary M. Frederick, Iowa State University "Estimation of Heats of Combustion of Biomass from Elemental Analysis Using Available Electron Concepts," Snehal A. Patel, Kansas State University "Design of a Wheat Straw to Ethanol Conversion Facility," Michael M. Meagher, Colorado State University "Effects of Salt, Heat, and Physical Form on the Fermentation of Bananas," Carl Drewel, University of Missouri–Columbia "Gas Hold-up in the Downflow Section of a Split Cylinder Airlift Column," Vasanti Deshpande, Kansas State University "Measurement of Michaelis Constants for Soluble and Immobilized Glucoamylase," Robert A. Lesch, Iowa State University "Kinetics of Alkaline Oxidation and Degradation of Sugars," Alfred R. Fratzke, Iowa State University "Stability of Cereal Protein During Microbial Growth on Grain Dust," Bamidele O. Solomon, Kansas State University

Progress toward chemical accuracy in the computer simulation of condensed phase reactions.

We describe a procedure for the generation of chemically accurate computer-simulation models to study chemical reactions in the condensed phase. The process involves (i) the use of a coupled semiempirical quantum and classical molecular mechanics method to represent solutes and solvent, respectively; (ii) the optimization of semiempirical quantum mechanics (QM) parameters to produce a computationally efficient and chemically accurate QM model; (iii) the calibration of a quantum/classical microsolvation model using ab initio quantum theory; and (iv) the use of statistical mechanical principles and methods to simulate, on massively parallel computers, the thermodynamic properties of chemical reactions in aqueous solution. The utility of this process is demonstrated by the calculation of the enthalpy of reaction in vacuum and free energy change in aqueous solution for a proton transfer involving methanol, methoxide, imidazole, and imidazolium, which are functional groups involved with proton transfers in many biochemical systems. An optimized semiempirical QM model is produced, which results in the calculation of heats of formation of the above chemical species to within 1.0 kcal/mol (1 kcal = 4.18 kJ) of experimental values. The use of the calibrated QM and microsolvation QM/MM (molecular mechanics) models for the simulation of a proton transfer in aqueous solution gives a calculated free energy that is within 1.0 kcal/mol (12.2 calculated vs. 12.8 experimental) of a value estimated from experimental pKa values of the reacting species.

Study of hexane adsorption in nanoporous MCM-41 silica

We study here the adsorption of hexane on nanoporous MCM-41 silica at 303, 313, and 323 K, for various pore diameters between 2.40 and 4.24 nm. Adsorption equilibria, measured thermogravimetrically, show that all the isotherms, that are somewhat akin to those of type V, exhibit remarkably sharp capillary adsorption phase transition steps and are reversible. The position of the phase transition step gradually shifts from low to high relative pressure with an increase in the temperature as well as the pore sizes. The isosteric heats of adsorption derived from the equilibrium information using the Clapeyron equation reveal a gradual decrease with increasing adsorbed amount because of the surface heterogeneity but approach a constant value near the phase transition. A decrease in the pore size results in an increase in the isosteric heat of adsorption because of the increased dispersion forces. A simple strategy, based on the Broekhoff and De Boer adsorption theory, successfully interprets the hexane adsorption isotherms for the different pore size MCM-41 samples. The parameters of an empirical expression, used to represent the potential of interaction between the adsorbate and adsorbent, are obtained by fitting the monolayer region prior to capillary condensation and the experimental phase transition simultaneously, for some pore sizes. Subsequently, the parameters are used to predict the adsorption isotherm on other pore size samples, which showed good agreement with experimental data.

Formation and mechanical properties of Mg65Cu25Er10 and Mg65Cu15Ag10Er10 bulk amorphous alloys

Mg65Cu25Er10 and Mg65Cu15Ag10Er10 bulk amorphous alloys were produced by a copper mould casting method. The alloys have high glass-forming ability and good thermal stability. The maximum diameter of glass formation (D-c), glass transition temperature (T-g), crystallization onset temperature (T-x), temperature interval of the supercooled region (Delta T-x), melting temperature (T-m), liquidus temperature (T-1) as well as heats of crystallization (Delta H-x) and melting (Delta H-m) are reported for these alloys. Both alloys exhibit high hardness and high strength at room temperature. (c) 2005 Elsevier B.V. All rights reserved.

Simulation study of ammonia adsorption on graphitized carbon black

GCMC simulations are applied to the adsorption of sub-critical ammonia on graphitized carbon black at 240 K. The carbon black was modelled both with and without carbonyl functional groups. Large differences are seen between the amount adsorbed for different carbonyl configurations at low pressure (P < 10kPa). Once a single layer is formed on the carbon black, the adsorption behaviour is similar between the model surfaces with and without functional groups. Simulation isotherms are qualitatively similar to the few experimental isotherms available in the literature for ammonia on highly graphitized carbon black. The mode of adsorption up to monolayer coverage is exhaustively shown to be two-dimensional clustering using various techniques. A comparison between experiment and simulation isosteric heats shows that a surface without functional groups cannot reproduce the experimental isosteric heats of adsorption, even comparing with the experimental results of carbon black heat treated at 3373 K. The addition of carbonyls produces isosteric heats with similar features to those in the literature if the separation between the carbonyls is small.