Thermodynamic analyses system

It has long been known that the adsorption of a gas on a solid surface is always accompanied by the evolution of heat. Various attempts have been made to arrive at a satisfactory thermodynamic analysis of heat of adsorption data, and within the past few years broad agreement has been achieved in setting up a general system of adsorption thermodynamics. Here we are not concerned with the derivation of the various thermodynamic functions but only with the more relevant definitions and the principles involved in the thermodynamic analysis of adsorption data. For more detailed treatments, appropriate texts should be consulted. " ... 

The combination of properties U - TS occurs so frequently in thermodynamic analysis that it is given a special name and symbol, namely A, the work fimction or maximum luork (because it represents the maximum work per unit mass, obtainable during any isothermal reversible change in any given system). Therefore, it is seen that... 

The decomposition process can be significantly intensified by the mechanical activation of the material prior to chemical decomposition. Based on a thermodynamic analysis of the system, Akimov and Chernyak [452] showed that the mechanical activation initiates dislocations mostly on the surface of the grains, and that heterogeneities in the surface cause the predominant migration of iron and manganese to the grain boundaries. It is noted that this phenomenon is more pronounced for manganese than it is for iron. 

The thermodynamic analysis of the selectivity of ion exchange with the participation of ions of quaternary ammonium bases [56--58] has shown that an increase in bonding selectivity, when metal ions are replaced by organic ions, which is usually accompanied by an increase in entropy of the system (Table 5). It follows from Table 5 that a drastic increase in bonding selectivity upon passing to a triethylbenzylammonium counterion (the most complex ion) is due to a considerable increase in the entropy of the system. 

The thermodynamic analysis of these systems played an important role in the interpretation of these data and of the high selectivity. It was found that selective sorption of complex organic ions is accompanied by an increase in the entropy of the system (Table 6). 

Chemical vapor deposition processes are complex. Chemical thermodynamics, mass transfer, reaction kinetics and crystal growth all play important roles. Equilibrium thermodynamic analysis is the first step in understanding any CVD process. Thermodynamic calculations are useful in predicting limiting deposition rates and condensed phases in the systems which can deposit under the limiting equilibrium state. These calculations are made for CVD of titanium - - and tantalum diborides, but in dynamic CVD systems equilibrium is rarely achieved and kinetic factors often govern the deposition rate behavior. 

A combination of thermodynamic analysis and experimental data on the deposition rates, efficiencies and deposit morphologies as a function of CVD variables may be used to develop models for the deposition processes. In the case of CVD of borides such a predictive model has been created so far only for a CVD system in which TiBj is obtained by reduction of TiCl4 and BCI3 with... 

Experimental studies, combined with thermodynamic analysis, indicate that the CTA hydropurification process is a complex reaction system including both parallel and tandem reactions wherein 4-CBA hydrogenation is exothermic and its paralleled decarbonylation is endothermic. 

Consider the following thermodynamic analysis for a reaction of the type A + B C + D conducted in a two-phase system (aqueous/organic). The equilibrium constants in the separate phases are ... 

A method of thermodynamic analysis for site steam systems will next be developed to allow the thermal loads and levels on a complete site to be studied. For this, a temperature-enthalpy picture for the whole site is needed, analogous to the grand composite curve for an individual process, as developed in Chapter 16. There are two ways in which such curves can be developed. The first relates to a new design situation. 

For cases where the standard state pressure for the various species is chosen as that of the system under investigation, changes in this variable will alter the values of AG° and AH0. In such cases thermodynamic analysis indicates that... 

Ultrafast ESPT from the neutral form readily explains why excitation into the A and B bands of AvGFP leads to a similar green anionic fluorescence emission [84], Simplistic thermodynamic analysis, by way of the Forster cycle, indicates that the excited state protonation pK.J of the chromophore is lowered by about 9 units as compared to its ground state. However, because the green anionic emission is slightly different when it arises from excitation into band A or band B (Fig. 5) and because these differences are even more pronounced at low temperatures [81, 118], fluorescence after excitation of the neutral A state must occur from an intermediate anionic form I not exactly equivalent to B. State I is usually viewed as an excited anionic chromophore surrounded by an unrelaxed, neutral-like protein conformation. The kinetic and thermodynamic system formed by the respective ground and excited states of A, B, and I is sometimes called the three state model (Fig. 7). 

In conclusion, we note that a cell is totally dependent on external supply of nutrients and energy and hence the states of coenzymes frequently depend on external conditions. They are also totally dependent on a central DNA code (see below). As coenzyme activity and DNA expression are concentration dependent, the treatment of them belongs with thermodynamic analysis of the whole controlled autocatalytic system. 

Further progress in the study of the Cu-Ni system awaited the preparation and careful characterization of alloy films of known bulk and surface composition. The essential step was taken by Sachtler and his co-workers 28, 88, 114) who prepared Cu-Ni alloy films by successive evaporation of the component metals in UHV. After evaporation the films were homogenized by heating in vacuum at 200°C. The bulk composition of the alloys was derived from X-ray diffraction, and the photoelectric work function of the films was also measured. A thermodynamic analysis, summarized by Fig. 13, indicated that alloy films sintered at 200°C should consist, at equilibrium, of two phases, viz., phase I containing 80% Cu and phase II containing 2% Cu. Evidence was presented that alloys within the... 

The observations on which thermodynamics is based refer to macroscopic properties only, and only those features of a system that appear to be temporally independent are therefore recorded. This limitation restricts a thermodynamic analysis to the static states of macrosystems. To facilitate the construction of a theoretical framework for thermodynamics [113] it is sufficient to consider only systems that are macroscopically homogeneous, isotropic, uncharged, and large enough so that surface effects can be neglected, and that are not acted on by electric, magnetic or gravitational fields. The only mechanical parameter to be retained is the volume V. For a mixed system the chemical composition is specified in terms of the mole numbers Ni, or the mole fractions [Ak — 1,2,..., r] of the chemically pure components of the system. The quantity V/(Y j=iNj) is called the molar... 

A thorough kinetic and thermodynamic analysis of this model system (small positive or negative enthalpies of formation are canceled by more negative entropies of formation) led Karlin s group to conclude that the stability of dioxygen binding is driven by favorable enthalpies, but unfavorable reaction entropies preclude observation of Cu2-02 at room temperatures.412... 

Sato et al.11 realized that for these lyotropic systems, whose phase boundaries have little temperature dependence, an investigation of the handedness in the widest possible temperature interval should be carried out. As the cholesteric handedness in a few cases is opposite at different temperatures, the data at a single temperature are meaningless. Using a simple thermodynamic analysis, they proposed a plot of the cholesteric wavenumber qc (the reciprocal pitch) as a function of the reciprocal temperature 1 IT [Eq. (1)]... 

There seems to be several mechanisms leading to the activity loss oxidation of cobalt metal, sintering of cobalt metal particles as well as sintering of the support and formation of stable cobalt-support metal oxides (silicates or aluminates). Oxidation by water is a key issue, possibly occurring on all supports and on unsupported cobalt. A thermodynamic analysis of this effect was reported by van Steen et al.,40 and they describe the FTS reaction system in terms of reactions (1) and (2) below ... 

Bird D. K. and Helgeson H. C. (1980). Chemical interaction of aqueous solution with epidolite-feldspar mineral assemblage in geologic systems, I Thermodynamic analysis of phase relations in the system Ca0-Fe0-Fe203-Al203-Si02-H20-C02. Amer. Jour. Set, 280 907-941. 

Newton R. C. (1987). Thermodynamic analysis of phase equilibria in simple mineral system. In Reviews in Mineralogy, vol. 17, P. H. Ribbe (series ed.), Mineralogical Society of America. 

The thermodynamic analysis of an actual Otto cycle is complicated. To simplify the analysis, we consider an ideal Otto cycle composed entirely of internally reversible processes. In the Otto cycle analysis, a closed piston-cylinder assembly is used as a control mass system. 

Wu, C., Finite-time thermodynamic analysis of a two-stage combined heat pump system. International Journal of Ambient Energy, 16(4), 205-208, 1995. 

Sturgill-Biltonen method, 64, 148 thermodynamic analysis, from graphs, 249, 557 V system, 64, 168. 

Miodownik et al. 1979, Watkin 1979). Irradiation can cause void-swelling, suppression of a formation in stainless steels and non-equilibrium precipitation of silicides. These phenomena are complex and occur by a combination of thermodynamic and kinetic effects. However, it was shown by Miodownik et al. (1979) that a thermodynamic analysis could be used to good effect to rationalise the effect of radiation on silicide formation. Although the work was done for a simple alloy system, it demonstrates how thermodynamics can be used in unusual cirounstances. 

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