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.

Thermodynamic and kinetic analysis of carbohydrate binding to the basic lectin from winged bean (Psophocarpus tetragonolobus)

A basic lectin (pI approximately 10.0) was purified to homogeneity from the seeds of winged bean (Psophocarpus tetragonolobus) by affinity chromatography on Sepharose 6-aminocaproyl-D-galactosamine. The lectin agglutinated trypsinized rabbit erythrocytes and had a relative molecular mass of 58,000 consisting of two subunits of Mr 29,000. The lectin binds to N-dansylgalactosamine, leading to a 15-fold increase in dansyl fluorescence with a concomitant 25-nm blue shift in the emission maximum. The lectin has two binding sites/dimer for this sugar and an association constant of 4.17 X 10(5) M-1 at 25 degrees C. The strong binding to N-dansylgalactosamine is due to a relatively positive entropic contribution as revealed by the thermodynamic parameters: delta H = -33.62 kJ mol-1 and delta S0 = -5.24 J mol-1 K-1. Binding of this sugar to the lectin shows that it can accommodate a large hydrophobic substituent on the C-2 carbon of D-galactose. Studies with other sugars indicate that a hydrophobic substituent in alpha- conformation at the anomeric position increases the affinity of binding. The C-4 and C-6 hydroxyl groups are critical for sugar binding to this lectin. Lectin difference absorption spectra in the presence of N-acetylgalactosamine indicate perturbation of tryptophan residues on sugar binding. The results of stopped flow kinetics with N- dansylgalactosamine and the lectin are consistent with a simple one- step mechanism for which k+1 = 1.33 X 10(4) M-1 s-1 and k-1 = 3.2 X 10(- 2) s-1 at 25 degrees C. This k-1 is slower than any reported for a lectin-monosaccharide complex so far. The activation parameters indicate an enthalpically controlled association process.

Dosage consistency is the key factor in avoiding evolution of resistance to phosphine and population increase in stored-grain pests

BACKGROUND Control of pests in stored grain and the evolution of resistance to pesticides are serious problems worldwide. A stochastic individual-based two-locus model was used to investigate the impact of two important issues, the consistency of pesticide dosage through the storage facility and the immigration rate of the adult pest, on overall population control and avoidance of evolution of resistance to the fumigant phosphine in an important pest of stored grain, the lesser grain borer. RESULTS A very consistent dosage maintained good control for all immigration rates, while an inconsistent dosage failed to maintain control in all cases. At intermediate dosage consistency, immigration rate became a critical factor in whether control was maintained or resistance emerged. CONCLUSION Achieving a consistent fumigant dosage is a key factor in avoiding evolution of resistance to phosphine and maintaining control of populations of stored-grain pests; when the dosage achieved is very inconsistent, there is likely to be a problem regardless of immigration rate. © 2012 Society of Chemical Industry

Thermodynamic implication of the special relativistic postulate

Abstract is not available.

Using old concepts to gain new insights: Addressing the issue of consistency

Purpose – This paper aims to go beyond a bookkeeping approach to evolutionary analysis whereby surviving firms are better adapted and extinct firms were less adapted. From discussion of the preliminary findings of research into the Hobart pizza industry, evidence is presented of the need to adopt a more traditional approach to applying evolutionary theories with organizational research. Design/methodology/approach – After a brief review of the relevant literature, the preliminary findings of research into the Hobart pizza industry are presented. Then, several evolutionary concepts that are commonplace in ecological research are introduced to help explain the emergent findings. The paper concludes with consideration given to advancing a more consistent approach to employing evolutionary theories within organizational research. Findings – The paper finds that the process of selection cannot be assumed to occur evenly across time and/or space. Within geographically small markets different forms of selection operate in different ways and degrees requiring the use of more traditional evolutionary theories to highlight the causal process associated with population change. Research limitations/implications – The paper concludes by highlighting Geoffrey Hodgson’s Principle of Consistency. It is demonstrated that a failure to truly understand how and why theory is used in one domain will likely result in its misuse in another domain. That, at present, too few evolutionary concepts are employed in organisational research to ensure an appreciation of any underlying causal processes through which social change occurs. Originality/value – The concepts introduced throughout this paper, whilst not new, provide new entry points for organizational researchers intent on employing an evolutionary approach to understand the process of social change.