Process thermodynamic analysis

This chapter examines two industrial polymer processes. Thermodynamic analysis is used as a tool to locate, in a matter-of-fact fashion, process inefficiencies. Some sample process improvement options are discussed. 

Stem layer adsorption was involved in the discussion of the effect of ions on f potentials (Section V-6), electrocapillary behavior (Section V-7), and electrode potentials (Section V-8) and enters into the effect of electrolytes on charged monolayers (Section XV-6). More speciflcally, this type of behavior occurs in the adsorption of electrolytes by ionic crystals. A large amount of wotk of this type has been done, partly because of the importance of such effects on the purity of precipitates of analytical interest and partly because of the role of such adsorption in coagulation and other colloid chemical processes. Early studies include those by Weiser [157], by Paneth, Hahn, and Fajans [158], and by Kolthoff and co-workers [159], A recent calorimetric study of proton adsorption by Lyklema and co-workers [160] supports a new thermodynamic analysis of double-layer formation. A recent example of this is found in a study... 

B. Linnhoff, Thermodynamic Analysis in the Design of Process Networks, Ph.D. dissertation. University of Leeds, Leeds, U.K., 1979. 

Kelvin showed the interdependence of these phenomena by thermodynamic analysis, assuming that the irreversible processes were independent of the reversible ones. This approach was later proved theoretically sound using Onsager s concepts of irreversible thermodynamics (9). 

Real irreversible processes can be subjected to thermodynamic analysis. The goal is to calciilate the efficiency of energy use or production and to show how energy loss is apportioned among the steps of a process. The treatment here is limited to steady-state, steady-flow processes, because of their predominance in chemical technology. 

Although the T-s diagram is veiy useful for thermodynamic analysis, the pressure enthalpy diagram is used much more in refrigeration practice due to the fact that both evaporation and condensation are isobaric processes so that heat exchanged is equal to enthalpy difference A( = Ah. For the ideal, isentropic compression, the work could be also presented as enthalpy difference AW = Ah. The vapor compression cycle (Ranldne) is presented in Fig. H-73 in p-h coordinates. 

The protonation equilibria for nine hydroxamic acids in solutions have been studied pH-potentiometrically via a modified Irving and Rossotti technique. The dissociation constants (p/fa values) of hydroxamic acids and the thermodynamic functions (AG°, AH°, AS°, and 5) for the successive and overall protonation processes of hydroxamic acids have been derived at different temperatures in water and in three different mixtures of water and dioxane (the mole fractions of dioxane were 0.083, 0.174, and 0.33). Titrations were also carried out in water ionic strengths of (0.15, 0.20, and 0.25) mol dm NaNOg, and the resulting dissociation constants are reported. A detailed thermodynamic analysis of the effects of organic solvent (dioxane), temperature, and ionic strength on the protonation processes of hydroxamic acids is presented and discussed to determine the factors which control these processes. 

This expression shows that the maximum possible useful work (i.e., reversible work) that can be obtained from any process occurring at constant temperature and pressure is a function of the initial and final states only and is independent of the path. The combination of properties U + PV - TS or H - TS occurs so frequently in thermodynamic analysis that it is given a special name and symbol, F, the free energy (sometimes called the Gibbs Free Energy). Using this definition, Equation 2-143 is written... 

The synthesis of tantalum and niobium fluoride compounds is, above all, related to the fluorination of metals or oxides. Table 3 presents a thermodynamic analysis of fluorination processes at ambient temperature as performed by Rakov [51, 52]. It is obvious that the fluorination of both metals and oxides of niobium and tantalum can take place even at low temperatures, whereas fluorination using ammonium fluoride and ammonium hydrofluoride can be performed only at higher temperatures. 

The results of a thermodynamic analysis of the interactions in Equations (127) and (128), as presented in [452], show that a coherent shell of tantalum and niobium hydroxides is formed on the surface of the columbite or tantalite during the interaction with sulfuric acid. The formation of the shell drives the process towards a forced thermodynamic equilibrium between the initial components and the products of the interaction, making any further interaction thermodynamically disadvantageous. It was also shown that, from a thermodynamic standpoint, the formation of a pseudomorphic structure on the surface of columbite or tantalite components is preferable to the formation of tantalum and niobium oxysulfates. Hence, the formation of the pseudomorphic phases catalyzes the interaction described by Equation (127) while halting that described by Equation (128). 

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. 

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. 

Thus, the electrode processes occurring in zinc-carbon batteries with salt electrolytes are complicated, and their thermodynamic analysis is difficult. In a rough approximation disregarding secondary processes, the current-producing reaction can be described as... 

Parmon VN. 2007. Thermodynamic analysis of the effect of the nanopaiticle size of the active component on the adsorption equilibrium and the rate of heterogeneous catalytic processes. Dokl Phys Chem 413 42-48. 

Accessible work potential is called the exergy that is the maximum amount of work that may be performed theoretically by bringing a resource into equilibrium with its surrounding through a reversible process. Exergy analysis is essentially a TA, and utilizes the combined laws of thermodynamics to account the loss of available energy. Exergy is always destroyed by irreversibilities in a system, and expressed by... 

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. 

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