Thermodynamic modeling of ethanol fumigation in a diesel engine

Due to rapidly diminishing international supplies of fossil fuels, such as petroleum and diesel, the cost of fuel is constantly increasing, leading to higher costs of living, as a result of the significant reliance of many industries on motor vehicles. Many technologies have been developed to replace part or all of a fossil fuel with bio-fuels. One of the dual fuel technologies is fumigation of ethanol in diesel engines, which injects ethanol into the intake air stream of the engine. The advantage of this is that it avoids any costly modification of the engine high pressure diesel injection system, while reducing the volume of diesel required and potentially increasing the power output and efficiency. This paper investigates the performance of a diesel engine, converted to implement ethanol fumigation. The project will use both existing experimental data, along with generating computer modeled results using the program AVL Boost. The data from both experiments and the numerical simulation indicate desirable results for the peak pressure and the indicated mean effective pressure (IMEP). Increase in ethanol substitution resulted in elevated combustion pressure and an increase in the IMEP, while the variation of ethanol injection location resulted in negligible change. These increases in cylinder pressure led to a higher work output and total efficiency in the engine as the ethanol substitution was increased. In comparing the numerical and experimental results, the simulation showed a slight elevation, due to the inaccuracies in the heat release models. Future work is required to improve the combustion model and investigate the effect of the variation of the location of ethanol injection.

Optimisation methods for coupled thermodynamic and 1D design of radial-inflow turbines

Optimisation is a fundamental step in the turbine design process, especially in the development of non-classical designs of radial-inflow turbines working with high-density fluids in low-temperature Organic Rankine Cycles (ORCs). The present work discusses the simultaneous optimisation of the thermodynamic cycle and the one-dimensional design of radial-inflow turbines. In particular, the work describes the integration between a 1D meanline preliminary design code adapted to real gases and the performance estimation approach for radial-inflow turbines in an established ORC cycle analysis procedure. The optimisation approach is split in two distinct loops; the inner operates on the 1D design based on the parameters received from the outer loop, which optimises the thermodynamic cycle. The method uses parameters including brine flow rate, temperature and working fluid, shifting assumptions such as head and flow coefficients into the optimisation routine. The discussed design and optimisation method is then validated against published benchmark cases. Finally, using the same conditions, the coupled optimisation procedure is extended to the preliminary design of a radial-inflow turbine with R143a as working fluid in realistic geothermal conditions and compared against results from commercially-available software RITAL from Concepts-NREC.

Thermodynamic characterization of the conformational stability of the homodimeric protein, pea lectin

The conformational stability of the homodimeric pea lectin was determined by both isothermal urea-induced and thermal denaturation in the absence and presence of urea. The denaturation profiles were analyzed to obtain the thermodynamic parameters associated with the unfolding of the protein. The data not only conform to the simple A(2) double left right arrow 2U model of unfolding but also are well described by the linear extrapolation model for the nature of denaturant-protein interactions. In addition, both the conformational stability (Delta G(s)) and the Delta C-p for the protein unfolding is quite high, at about 18.79 kcal/ mol and 5.32 kcal/(mol K), respectively, which may be a reflection of the relatively larger size of the dimeric molecule (M-r 49 000) and, perhaps, a consequent larger buried hydrophobic core in the folded protein. The simple two-state (A(2) double left right arrow 2U) nature of the unfolding process, with the absence of any monomeric intermediate, suggests that the quaternary interactions alone may contribute significantly to the conformational stability of the oligomer-a point that may be general to many oligomeric proteins.

Thermal reactivity of poly(styrene peroxide): a thermodynamic approach

Abstract is not available.

Size-dependent melting of nanoparticles: Hundred years of thermodynamic model

Thermodynamic model first published in 1909, is being used extensively to understand the size-dependent melting of nanoparticles. Pawlow deduced an expression for the size-dependent melting temperature of small particles based on the thermodynamic model which was then modified and applied to different nanostructures such as nanowires, prism-shaped nanoparticles, etc. The model has also been modified to understand the melting of supported nanoparticles and superheating of embedded nanoparticles. In this article, we have reviewed the melting behaviour of nanostructures reported in the literature since 1909.

Calciothermic reduction of TiO2: A diagrammatic assessment of the thermodynamic limit of deoxidation

Calciothermic reduction of TiO2 provides a potentially low-cost route to titanium production. Presented in this article is a suitably designed diagram, useful for assessing the degree of reduction of TiO2 and residual oxygen contamination in metal as a function of reduction temperature and other process parameters. The oxygen chemical potential diagram à la Ellingham-Richardson-Jeffes is useful for visualization of the thermodynamics of reduction reactions at high temperatures. Although traditionally the diagram depicts oxygen potentials corresponding to the oxidation of different metals to their corresponding oxides or of lower oxides to higher oxides, oxygen potentials associated with solution phases at constant composition can be readily superimposed. The usefulness of the diagram for an insightful analysis of calciothermic reduction, either direct or through an electrochemical process, is discussed. Identified are possible process variations, modeling and optimization strategies.

Determination of the thermodynamic properties of xMgO + (1 x)MnO (s, sln) from a solid-electrolyte galvanic cell in the temperature range 1163 to 1318 K

The thermodynamic activities of MgO in the NaCl-type solid solutions which can exist in xMgO + (1 x)MnO have been determined in the temperature range 1163 to 1318 K from a solid-state galvanic cell incorporating MgF2 as the solid electrolyte. The activities of MnO have been calculated by a graphical Gibbs-Duhem integration method. The activities of both the components exhibit positive deviations from ideality over the entire composition range. The excess molar enthalpies are found to be positive. Further, xMgO + (1 - x)MnO does not conform to regular-solution behaviour. The origin of the excess thermodynamic properties is discussed in relation to the cationic size disparity and the crystal-field effects.

Phase relations in the system Ta-Rh-O and thermodynamic properties of TaRhO4

Phase relations in the system Ta-Rh-O were determined by analysis of quenched samples corresponding to thirteen compositions inside the ternary triangle after equilibration at 1273 K. All the Ta-Rh alloys were found to be in equilibrium with Ta2O5. Only one ternary oxide TaRhO4 was detected. Based on phase relations in the ternary system, a solid-state electrochemical cell, incorporating calcia-stabilized zirconia as the electrolyte, was designed to measure the standard Gibbs energy of formation (Delta G degrees, J mol(-1)) of TaRhO4 in the temperature range from 900 to 1300 K. For the reaction, 1/2 beta-Ta2O5 + 1/2 Rh2O3(ortho) -> TaRhO4 Delta G degrees = -42993 + 5.676T (+/- 85) The calculated decomposition temperatures of TaRhO4 are 1644 +/- 5K in pure O-2 and 1543 +/- 5K in air at a total pressure p(o) = 0.1 MPa. Thermodynamic properties of TaRhO4 at 298.15K have been evaluated from the results. The limited experimental thermodynamic data for Rh-rich alloys available in the literature are in fair accord with Miedema's model. The Gibbs energies of formation of the different phases in the binary system Ta-Rh were estimated based on these inputs, consistent with the binary phase diagram. Based on the thermodynamic information on the stability of various phases, an oxygen potential diagram for the system Ta-Rh-O at 1273K was constructed. Also presented are temperature-composition diagrams for the ternary system at constant oxygen partial pressures (po(2)/p(o) = 0.212 and 10(-6)) calculated form the basic data.

Thermodynamic scaling theory for impurities in metals

A perturbative scaling theory for calculating static thermodynamic properties of arbitrary local impurity degrees of freedom interacting with the conduction electrons of a metal is presented. The basic features are developments of the ideas of Anderson and Wilson, but the precise formulation is new and is capable of taking into account band-edge effects which cannot be neglected in certain problems. Recursion relations are derived for arbitrary interaction Hamiltonians up to third order in perturbation theory. A generalized impurity Hamiltonian is defined and its scaling equations are derived up to third order. The strategy of using such perturbative scaling equations is delineated and the renormalization-group aspects are discussed. The method is illustrated by applying it to the single-impurity Kondo problem whose static properties are well understood.

A new formalism for representation of binary thermodynamic data

The applicability of a formalism involving an exponential function of composition x1 in interpreting the thermodynamic properties of alloys has been studied. The excess integral and partial molar free energies of mixing are expressed as: $$\begin{gathered} \Delta F^{xs} = a_o x_1 (1 - x_1 )e^{bx_1 } \hfill \\ RTln\gamma _1 = a_o (1 - x_1 )^2 (1 + bx_1 )e^{bx_1 } \hfill \\ RTln\gamma _2 = a_o x_1^2 (1 - b + bx_1 )e^{bx_1 } \hfill \\ \end{gathered} $$ The equations are used in interpreting experimental data for several relatively weakly interacting binary systems. For the purpose of comparison, activity coefficients obtained by the subregular model and Krupkowski’s formalism have also been computed. The present equations may be considered to be convenient in describing the thermodynamic behavior of metallic solutions.

Thermodynamic properties of Pb2PtO4 and PbPt2O4 and phase equilibria in the system Pb–Pt–O

The compounds Pb2PtO4 and PbPt2O4 were synthesized from an intimate mixture of yellow PbO and Pt metal powders by heating under pure oxygen gas at 973 K for periods up to 600 ks with intermediate grinding and recompacting. Both compounds were found to decompose on heating in pure oxygen to PbO and Pt, apparently in conflict with the requirements for equilibrium phase relations in the ternary system Pb–Pt–O. The oxygen chemical potential corresponding to the three-phase mixtures, Pb2PtO4 + PbO + Pt and PbPt2O4 + PbO + Pt were measured as a function of temperature using solid-state electrochemical cells incorporating yttria-stabilized zirconia as the solid electrolyte and pure oxygen gas at 0.1 MPa pressure as the reference electrode. The standard Gibbs free energies of formation of the ternary oxides were derived from the measurements. Analysis of the results indicated that the equilibrium involving three condensed phases Pb2PtO4 + PbO + Pt is metastable. Under equilibrium conditions, Pb2PtO4 should have decomposed to a mixture of PbO and PbPt2O4. Measurement of the oxygen potential corresponding to this equilibrium decomposition as a function of temperature indicated that decomposition temperature in pure oxygen is 1014(±2) K. This was further confirmed by direct determination of phase relations in the ternary Pb–Pt–O by equilibrating several compositions at 1023 K for periods up to 850 ks and phase identification of quenched samples using X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). Only one ternary oxide PbPt2O4 was stable at 1023 K under equilibrium conditions. Alloys and intermetallic compounds along the Pb–Pt binary were in equilibrium with PbO.

Thermodynamic and kinetic studies on saccharide binding to soya-bean agglutinin.

The fluorescence of N-dansylgalactosamine [N-(5-dimethylaminonaphthalene-1-sulphonyl)galactosamine] was enhanced 11-fold with a 25 nm blue-shift in the emission maximum upon binding to soya-bean agglutinin (SBA). This change was used to determine the association constants and thermodynamic parameters for this interaction. The association constant of 1.51 X 10(6) M-1 at 20 degrees C indicated a very strong binding, which is mainly due to a relatively small entropy value, as revealed by the thermodynamic parameters: delta G = -34.7 kJ X mol-1, delta H = -37.9 kJ X mol-1 and delta S = -10.9 J X mol-1 X K-1. The specific binding of this sugar to SBA shows that the lectin can accommodate a large hydrophobic substituent on the C-2 of galactose. Binding of non-fluorescent ligands, studied by monitoring the fluorescence changes when they are added to a mixture of SBA and N-dansylgalactosamine, indicates that a hydrophobic substituent at the anomeric position increases the affinity of the interaction. The C-6 hydroxy group also stabilizes the binding considerably. Kinetics of binding of N-dansylgalactosamine to SBA studied by stopped-flow spectrofluorimetry are consistent with a single-step mechanism and yielded k+1 = 2.4 X 10(5) M-1 X s-1 and k-1 = 0.2 s-1 at 20 degrees C. The activation parameters indicate an enthalpicly controlled association process.

Thermodynamic scaling theory for the two-impurity Anderson model

We present results of a study of the two-impurity Anderson model using a thermodynamic scaling theory developed recently. The model is characterized by the Coulomb energy U, the orbital energy epsilond, the d-level width Gamma, and the separation between impurities R. If Gamma<<−epsilond<~Gamma. Here we find that the single-impurity physics dominates the low-temperature behavior, and impurity-impurity interactions are perturbative. The qualitative features of the temperature-dependent susceptibility are discussed. Journal of Applied Physics is copyrighted by The American Institute of Physics.

Oxidation of alkaline earth sulfides to sulfates: Thermodynamic aspects

The emf of the galvanic cell, Pt, Ni + NiO/(CaO) ZrO2/MS + MSO4, Ir, Pt, where M is calcium, strontium, or barium, has been measured in the temperature range 850 to 1100 K. From these measurements the Gibbs’ energy changes for the oxidation of sulfides of alkaline earth metals to their respective sulfates have been calculated. The results are compared with available thermodynamic data in the literature. The agreement varies from ±2 kJ for the strontium system to ±20 kJ in the case of barium. Trends in the stabilities of alkaline earth sulfates are discussed in relation to the properties of the cationic species involved.