Theoretical and experimental characterisation of energy in an electrostatic discharge

Electrostatic discharges have been identified as the most likely cause in a number of incidents of fire and explosion with unexplained ignitions. The lack of data and suitable models for this ignition mechanism creates a void in the analysis to quantify the importance of static electricity as a credible ignition mechanism. Quantifiable hazard analysis of the risk of ignition by static discharge cannot, therefore, be entirely carried out with our current understanding of this phenomenon. The study of electrostatics has been ongoing for a long time. However, it was not until the wide spread use of electronics that research was developed for the protection of electronics from electrostatic discharges. Current experimental models for electrostatic discharge developed for intrinsic safety with electronics are inadequate for ignition analysis and typically are not supported by theoretical analysis. A preliminary simulation and experiment with low voltage was designed to investigate the characteristics of energy dissipation and provided a basis for a high voltage investigation. It was seen that for a low voltage the discharge energy represents about 10% of the initial capacitive energy available and that the energy dissipation was within 10 ns of the initial discharge. The potential difference is greatest at the initial break down when the largest amount of the energy is dissipated. The discharge pathway is then established and minimal energy is dissipated as energy dissipation becomes greatly influenced by other components and stray resistance in the discharge circuit. From the initial low voltage simulation work, the importance of the energy dissipation and the characteristic of the discharge were determined. After the preliminary low voltage work was completed, a high voltage discharge experiment was designed and fabricated. Voltage and current measurement were recorded on the discharge circuit allowing the discharge characteristic to be recorded and energy dissipation in the discharge circuit calculated. Discharge energy calculations show consistency with the low voltage work relating to discharge energy with about 30-40% of the total initial capacitive energy being discharged in the resulting high voltage arc. After the system was characterised and operation validated, high voltage ignition energy measurements were conducted on a solution of n-Pentane evaporating in a 250 cm3 chamber. A series of ignition experiments were conducted to determine the minimum ignition energy of n-Pentane. The data from the ignition work was analysed with standard statistical regression methods for tests that return binary (yes/no) data and found to be in agreement with recent publications. The research demonstrates that energy dissipation is heavily dependent on the circuit configuration and most especially by the discharge circuit's capacitance and resistance. The analysis established a discharge profile for the discharges studied and validates the application of this methodology for further research into different materials and atmospheres; by systematically looking at discharge profiles of test materials with various parameters (e.g., capacitance, inductance, and resistance). Systematic experiments looking at the discharge characteristics of the spark will also help understand the way energy is dissipated in an electrostatic discharge enabling a better understanding of the ignition characteristics of materials in terms of energy and the dissipation of that energy in an electrostatic discharge.

Gibbs Energy of Formation of Cobalt Divanadium Tetroxide

The Gibbs energy of formation of V2O3-saturated spinel CoV2O4 has been measured in the temperature range 900–1700 K using a solid state galvanic cell, which can be represented as Pt, Co + CoV2O4 + V2O3/(CaO) ZrO2/Co + CoO, Pt. The standard free energy of formation of cobalt vanadite from component oxides can be represented as CoO (rs) + V2O3 (cor) → CoV2O4 (sp), ΔG° = −30,125 − 5.06T (± 150) J mole−1. Cation mixing on crystallographically nonequivalent sites of the spinel is responsible for the decrease in free energy with increasing temperature. A correlation between “second law” entropies of formation of cubic 2–3 spinels from component oxides with rock salt and corundum structures and cation distribution is presented. Based on the information obtained in this study and trends in the stability of aluminate and chromite spinels, it can be deduced that copper vanadite is unstable.

Photo-induced double-strand DNA and site-specific protein cleavage activity of L-histidine (mu-oxo)diiron(III) complexes of heterocyclic bases

Three oxo-bridged diiron(III) complexes of L-histidine and heterocyclic bases [Fe-2(mu-O)(L-his)(2)(B)(2)](ClO4)(2) (1-3), where B is 2,2'-bipyridine (bpy),1,10-phenanthroline (phen), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq), were prepared and characterized. The bpy complex 1 was structurally characterized by X-ray crystallography. The molecular structure showed a {Fe-2(mu-O)} core in which iron(III) in a FeN4O2 coordination is bound to tridentate monoanionic L-histidine and bidentate bpy ligands. The Fe center dot center dot center dot Fe distance is similar to 3.5 angstrom. The Fe-O-Fe unit is essentially linear, giving a bond angle of similar to 172 degrees. The complexes showed irreversible cyclic voltammetric cathodic response near -0.1 V vs. SCE in H2O-0.1 M KCl. The binuclear units displayed antiferromagnetic interaction between two high-spin (S = 5/2) iron(III) centers giving a -J value of -110 cm(-1). The complexes showed good DNA binding propensity giving a binding constant value of similar to 10(5) M-1. Isothermal titration calorimetric data indicated single binding mode to the DNA. The binding was found to be driven by negative free energy change and enthalpy. The dpq complex 3 showed oxidative double-strand DNA cleavage on exposure to UV-A and visible light. The phen complex 2 displayed single-strand photocleavage of DNA. The DNA double-strand breaks were rationalized from theoretical molecular docking calculations. Mechanistic investigations showed formation of hydroxyl radicals as the reactive species through photodecarboxylation of the L-histidine ligand. The complexes exhibited good binding propensity to bovine serum albumin (BSA) protein in Tris-HCl/NaCl buffer medium. The dpq complex 3 showed UV-A light-induced site-specific oxidative BSA cleavage forming fragments of similar to 45 kDa and similar to 20 kDa molecular weights via SOH pathway.

Molecular modeling of Bt Cry1Ac (DI–DII)–ASAL (Allium sativum lectin)–fusion protein and its interaction with aminopeptidase N (APN) receptor of Manduca sexta

Genetic engineering of Bacillus thuringiensis (Bt) Cry proteins has resulted in the synthesis of various novel toxin proteins with enhanced insecticidal activity and specificity towards different insect pests. In this study, a fusion protein consisting of the DI–DII domains of Cry1Ac and garlic lectin (ASAL) has been designed in silico by replacing the DIII domain of Cry1Ac with ASAL. The binding interface between the DI–DII domains of Cry1Ac and lectin has been identified using protein–protein docking studies. Free energy of binding calculations and interaction profiles between the Cry1Ac and lectin domains confirmed the stability of fusion protein. A total of 18 hydrogen bonds was observed in the DI–DII–lectin fusion protein compared to 11 hydrogen bonds in the Cry1Ac (DI–DII–DIII) protein. Molecular mechanics/Poisson–Boltzmann (generalized-Born) surface area [MM/PB (GB) SA] methods were used for predicting free energy of interactions of the fusion proteins. Protein–protein docking studies based on the number of hydrogen bonds, hydrophobic interactions, aromatic–aromatic, aromatic–sulphur, cation–pi interactions and binding energy of Cry1Ac/fusion proteins with the aminopeptidase N (APN) of Manduca sexta rationalised the higher binding affinity of the fusion protein with the APN receptor compared to that of the Cry1Ac–APN complex, as predicted by ZDOCK, Rosetta and ClusPro analysis. The molecular binding interface between the fusion protein and the APN receptor is well packed, analogously to that of the Cry1Ac–APN complex. These findings offer scope for the design and development of customized fusion molecules for improved pest management in crop plants.

Surface-mediated selective photocatalytic aerobic oxidation reactions on TiO2 nanofibres

N-doped TiO2 nanofibres were observed to possess lower aerobic oxidation activity than undoped TiO2 nanofibres in the selective photocatalytic aerobic oxidation of enzylamine and 4-methoxybenzyl alcohol. This was attributed to the reduction free energy of O2 adsorption in the vicinity of nitrogen dopant sites, as indicated by density functional theory (DFT) calculations when three-coordinated oxygen atoms are substituted by nitrogen atoms. It was found that the activity recovered following a controlled calcination of the N-doped NFs in air. The dependence of the conversion of benzylamine and 4-methoxybenzyl alcohol on the intensity of light irradiation confirmed that these reactions were driven by light. Action spectra showed that the two oxidation reactions are responsive to light from the UV region through to the visible light irradiation range. The extended light absorption wavelength range in these systems compared to pure TiO2 materials was found to result from the formation of surface complex species following adsorption of reactants onto the catalysts' surface, evidenced by the in situ IR experiment. Both catalytic and in situ IR results reveal that benzaldehyde is the intermediate in the aerobic oxidation of benzylamine to N-benzylidenebenzylamine process.

Density-wave theory of dislocations in crystals

The density-wave theory of Ramakrishnan and Yussouff is extended to provide a scheme for describing dislocations and other topological defects in crystals. Quantitative calculations are presented for the order-parameter profiles, the atomic configuration, and the free energy of a screw dislocation with Burgers vector b=(a/2, a/2, a/2) in a bcc solid. These calculations are done using a simple parametrization of the direct correlation function and a gradient expansion. It is conventional to express the free energy of the dislocation in a crystal of size R as (λb2/4π)ln(αR/‖b‖), where λ is the shear elastic constant, and α is a measure of the core energy. Our results yield for Na the value α≃1.94a/(‖c1’’‖)1/2 (≃1.85) at the freezing temperature (371 K) and α≃2.48a/(‖c1’’‖)1/2 at 271 K, where c1’’ is the curvature of the first peak of the direct correlation function c(q). Detailed results for the density distribution in the dislocation, particularly the core region, are also presented. These show that the dislocation core has a columnar character. To our knowledge, this study represents the first calculation of dislocation structure, including the core, within the framework of an order-parameter theory and incorporating thermal effects.

Theoretical Treatment of Interaction Parameters in Multicomponent Metallic Solutions

A new theoretical equation for interaction parameter in multicomponent metallic solutions is developed using the pseudopotential formalism coupled with the free energy of the hard sphere system. The approximate expression for the pseudopotential term is given in terms of the heat of solution at infinite dilution, to allow easy evaluation of the interaction parameter in various multicomponent systems. This theory has been applied to 23 non-ferrous alloys based on Pb, Sn, Bi and indium. Comparison with the results of previous theoretical calculations using only the hard sphere model suggests that the inclusion of the pseudopotential term yields a quantitatively more correct prediction of interaction parameters in multicomponent metallic solutions. Numerical calculations were also made for 320 Fe-base solutions relevant to steelmaking and the agreement between calculation and experimental data appears reasonable, with 90% reliability in predicting the correct sign.

Topological defects in crystals: A density-wave theory

A new approach for describing dislocations and other topological defects in crystals, based on the density wave theory of Ramakrishnan and Yussouff is presented. Quantitative calculations are discussed in brief for the order parameter profiles, the atomic configuration and the free energy of a screw dislocation with Burgers vector b = (a/2, a/2,a/2 ) in a bcc solid. Our results for the free energy of the dislocation in a crystal of sizeR, when expressed as (λb 2/4π) ln (αR/|b|) whereλ is the shear elastic constant, yield, for example, the valueα ⋍ 1·85 for sodium at its freezing temperature (371°K). The density distribution in the presence of the dislocation shows that the dislocation core has a columnar character. To our knowledge, this study represents the first calculation of dislocation structure, including the core, within the framework of an order parameter theory incorporating thermal effects.

Phase Relations in the System Cu-Gd-O and Gibbs Energy of Formation of CuGd204

The phase relations in the system Cu-Gd-O have been determined at 1273 K by X-ray diffrac- tion, optical microscopy, and electron microprobe analysis of samples equilibrated in quartz ampules and in pure oxygen. Only one ternary compound, CuGd2O4, was found to be stable. The Gibbs free energy of formation of this compound has been measured using the solid-state cell Pt, Cu2O + CuGd2O4 + Gd2O3 // (Y2O3) ZrO2 // CuO + Cu2O, Pt in the temperature range of 900 to 1350 K. For the formation of CuGd2O4 from its binary component oxides, CuO (s) + Gd2O3 (s) → CuGd2O4 (s) ΔG° = 8230 - 11.2T (±50) J mol-1 Since the formation is endothermic, CuGd2O4 becomes thermodynamically unstable with respect to CuO and Gd2O3 below 735 K. When the oxygen partial pressure over CuGd2O4 is lowered, it decomposes according to the reaction 4CuGd2O4 (s) → 4Gd2O3 (s) + 2Cu2O (s) + O2 (g) for which the equilibrium oxygen potential is given by Δμo 2 = −227,970 + 143.2T (±500) J mol−1 An oxygen potential diagram for the system Cu-Gd-O at 1273 K is presented.

Gibbs energy of formation of orthorhombic CaZrO3

The Gibbs free energy of formation of the orthorhombic form of CaZrO3(o) from monoclinic ZrO2(m) and periclase CaO(p) has been determined as a function of temperature in the range 950-1225 K, using an electrochemical cell incorporating single-crystal CaF2 as the solid electrolyte. The results are corrected for the small solid solubility of CaO in ZrO2. For the reaction, ZrO2(m) + CaO(p) --> CaZrO3(o), DELTAG(phi) = -31590 -13.9T(+/- 180) J mol-1. The ''second-law'' enthalpy of formation of CaZrO3 obtained from the results of this study at a mean temperature of 1090 K is in excellent agreement with the high-temperature solution calorimetric measurements of Muromachi and Navrotsky at 1068 K (J. Solid State Chem., 72 (1988) 244), and the average value of the bomb and acid solution calorimetric studies of Lvova and Feodosev (Zh. Fiz. Khim., 38 (1964) 28), Korneev et al. (Izv. Akad. Nauk SSSR, Neorg. Mater., 7 (1971) 886) and Brown and Bennington (Thermochim. Acta, 106 (1986) 183). The standard entropy of CaZrO3(o) at 298.15 K from the free energy data is 96.4 (+/- 3.5) J K-1 mol-1. The results of this study are discussed in comparison with high-temperture e.m.f. measurements reported in the literature on cubic zirconia solid solutions.

A thermodynamic criterion for selection of gas compositions for diamond deposition

Isoactivity lines for carbon with respect to diamond as the standard state have been calculated in the ternary system C-H-O at 1223 K to identify the diamond deposition domain. The gas composition is calculated by suppressing the formation of all condensed forms of carbon using the SOLGASMIX free-energy minimization program. Thirty six gas species were included in the calculation. From the gas composition, isoactivity lines are computed using recent data on the Gibbs energy of diamond. Except for activities less than 0.1, the isoactivity lines are almost linear on the C-H-O ternary diagram. Gas compositions which generate activity of diamond ranging from 1 to 100 at 1223 K fall inside a narrow wedge originating from the point representing CO. This wedge is very similar to the revised lens-shaped diamond growth domain identified by Bachman et al., using inputs from experiment. The small difference between the calculated and observed domains may be attributed to variation in the supersaturation required for diamond deposition with gas composition. The diamond solubility in the gas phase along the isoactivity line for a(di)=100 and P=6.7 kPa exhibits a minimum at 1280 K, which is close to the optimum temperature found experimentally. At higher supersaturations, non-diamond forms of carbon, including amorphous varieties, are expected. The results suggest that thermodynamic calculations can be useful for locating diamond growth domains in more complex CVD systems containing halogens, for which very little experimental data is available.

Determination of the Gibbs energy of diamond using a solid state cell

he chemical potential of carbon in diamond, relative to its value in graphite, has been directly determined using a solid state electrochemical cell incorporating single crystal CaF2 as the solid electrolyte. The cell can be represented as Pt, C(graphite) + CaC2 + CaF2double vertical barCaF2double vertical barCaF2 + CaC2 + C(diamond), Pt The reversible emf of this cell is directly related by the Nernst equation to the Gibbs free energy change for the conversion of diamond to graphite. The difference in the chemical potential of carbon in the two crystal structures varies linearly with temperature in the range 940 to 1260 K ?C(diamond) ? ?C(graphite) = 1100 + 4.64T (±50) J mol?1 On the average, the values given by the equation are 320 J mol?1 less positive than the currently accepted ones based on calorimetric studies. The difference is primarily in the enthalpy term.

Absolute Entropy and Energy of Carbon Dioxide Using the Two-Phase Thermodynamic Model

The two-phase thermodynamic (2PT) model is used to determine the absolute entropy and energy of carbon dioxide over a wide range of conditions from molecular dynamics trajectories. The 2PT method determines the thermodynamic properties by applying the proper statistical mechanical partition function to the normal modes of a fluid. The vibrational density of state (DoS), obtained from the Fourier transform of the velocity autocorrelation function, converges quickly, allowing the free energy, entropy, and other thermodynamic properties to be determined from short 20-ps MD trajectories. The anharmonic effects in the vibrations are accounted for by the broadening of the normal modes into bands from sampling the velocities over the trajectory. The low frequency diffusive modes, which lead to finite DoS at zero frequency, are accounted for by considering the DoS as a superposition of gas-phase and solid-phase components (two phases). The analytical decomposition of the DoS allows for an evaluation of properties contributed by different types of molecular motions. We show that this 2PT analysis leads to accurate predictions of entropy and energy of CO2 over a wide range of conditions (from the triple point to the critical point of both the vapor and the liquid phases along the saturation line). This allows the equation of state of CO2 to be determined, which is limited only by the accuracy of the force field. We also validated that the 2PT entropy agrees with that determined from thermodynamic integration, but 2PT requires only a fraction of the time. A complication for CO2 is that its equilibrium configuration is linear, which would have only two rotational modes, but during the dynamics it is never exactly linear, so that there is a third mode from rotational about the axis. In this work, we show how to treat such linear molecules in the 2PT framework.

Thermodynamic investigation of the MOCVD of copper films from bis(2,2,6,6-tetramethyl-3,5-heptadionato)copper(II)

Equilibrium concentrations of various condensed and gaseous phases have been thermodynamically calculated, using the free energy minimization criterion, for the metalorganic chemical vapour deposition (MOCVD) of copper films using bis(2,2,6,6-tetramethyl-3,5-heptadionato)copper(II) as the precursor material. From among the many chemical species that may possibly result from the CVD process, only those expected on the basis of mass spectrometric analysis and chemical reasoning to be present at equilibrium, under different CVD conditions, are used in the thermodynamic calculations. The study predicts the deposition of pure, carbon-free copper in the inert atmosphere of argon as well as in the reactive hydrogen atmosphere, over a wide range of substrate temperatures and total reactor pressures. Thin films of copper, grown on SiO2/Si(100) substrates from this metalorganic precursor by low pressure CVD have been characterized by XRD and AES. The experimentally determined composition of CVD-grown copper films is in reasonable agreement with that predicted by thermodynamic analysis.

Gibbs free energies of formation of indium (III) oxide and sulphate

Emf measurements on the galvanic cell Pt, Ta, In + In,O, / Tho,-Y,03 / Cu + C+O, Pt were used to obtain the standard free energy of formation of 1%03fr om 600 to 900°C. Differential thermal analysis was used to detect the decomposition of In2(S0,), under controlled SO2 + O2 + Ar mixtures in thqtemperature range 640-8wC. X-ray diffraction analysis indicated that the decomposition product was 1%03 without an oxywlphate intermediate. The following equations were obtained for the variation of the standard free-energy change(Jlmole) with temperature: