Thermodynamic chemistry

But probably the most serious barrier has been the paralysis that overtakes the inexperienced mind when it is faced with an explosion. This prevents many from recognizing an explosion as the orderly process it is. Like any orderly process, an explosive shock can be investigated, its effects recorded, understood, and used. The rapidity and violence of an explosion do not vitiate Newton s laws, nor those of thermodynamics, chemistry, or quantum mechanics. They do, however, force matter into new states quite different from those we customarily deal with. These provide stringent tests for some of our favorite assumptions about matter s bulk properties. 

Frank EU, Weingartner H. Supercritical water. In Letcher TM, ed. Chemical Thermodynamics (Chemistry for the 21st Century Monograph). Oxford Blackwell Science, 1999. 

In the branch of science called thermodynamic chemistry a more detailed consideration is given to the relative effects of energy and probability. It has been found that the effect of probability can be described quantitatively by a new property of substances. This new property, which represents the probability of a substance in various states, is called entropy. 

A.V. Suvorov, Termodynamicheskaya chimia paroobraznogo sostoyania (Thermodynamic chemistry of vapour state). Leningrad Chimia. 1970. 208 p. 

S.I. Sandler, in Chemical Thermodynamics - Chemistry for the 21st Century (T.M. Letcher, ed.), Blackwell Science, Oxford, 1999 (Chapter 2). 

Lewis, G. N. 1907. Outline of a new system of thermodynamic chemistry. Proceedings of the American Academy of Arts and Sciences 43 259-293. 

Zwolinski (Executive Officer) "International Data Series Selected Data on Mixtures," Thermodynamics Research Center, Chemistry Department, Texas A M University, College Station, Texas 77843 (continuing since 1973). ... 

Zwolinski, B. J., and R. C. Wilhoit "Vapor Pressures and Heats of Vaporization of Hydrocarbons and Related Compounds," Thermodynamic Research Center, Dept, of Chemistry, Texas A M University, College Station, Texas, 1971. 

Dislocation theory as a portion of the subject of solid-state physics is somewhat beyond the scope of this book, but it is desirable to examine the subject briefly in terms of its implications in surface chemistry. Perhaps the most elementary type of defect is that of an extra or interstitial atom—Frenkel defect [110]—or a missing atom or vacancy—Schottky defect [111]. Such point defects play an important role in the treatment of diffusion and electrical conductivities in solids and the solubility of a salt in the host lattice of another or different valence type [112]. Point defects have a thermodynamic basis for their existence in terms of the energy and entropy of their formation, the situation is similar to the formation of isolated holes and erratic atoms on a surface. Dislocations, on the other hand, may be viewed as an organized concentration of point defects they are lattice defects and play an important role in the mechanism of the plastic deformation of solids. Lattice defects or dislocations are not thermodynamic in the sense of the point defects their formation is intimately connected with the mechanism of nucleation and crystal growth (see Section IX-4), and they constitute an important source of surface imperfection. 

While a thermodynamic treatment can be developed entirely in terms of f(P,T), to apply adsorption models, it is highly desirable to know on a per square centimeter basis rather than a per gram basis or, alternatively, to know B, the fraction of surface covered. In both the physical chemistry and the applied chemistry of the solid-gas interface, the specific surface area is thus of extreme importance. 

Oscarson J L and Izatt R M 1992 Calorimetry Physical Methods of Chemistry Determination of Thermodynamic Properties 2nd edn, vol VI, ed B W Rossiter and R C Baetzold (New York Wiley)... 

Okamoto Y and U H E Hansmann 1995. Thermodynamics of Helix-coil Transitions Studied 1 Multicanonical Algorithms. Journal of Physical Chemistry 99 11276-11287. 

Mitchell M J and J A McCammon 1991. Free Energy Difference Calculations by Thermodynamic Integration Difficulties in Obtaining a Precise Value. Journal of Computational Chemistry 12 271-275. 

The subject of entropy is introduced here to illustrate treatment of experimental data sets as distinct from continuous theoretical functions like Eq. (1-33). Thermodynamics and physical chemistry texts develop the equation... 

Thermodynamics is one of the most well-developed mathematical descriptions of chemistry. It is the held of thermodynamics that dehnes many of the concepts of energy, free energy and entropy. This is covered in physical chemistry text books. 

Computational results can be related to thermodynamics. The result of computations might be internal energies, free energies, and so on, depending on the computation done. Likewise, it is possible to compute various contributions to the entropy. One frustration is that computational software does not always make it obvious which energy is being listed due to the dilferences in terminology between computational chemistry and thermodynamics. Some of these differences will be noted at the appropriate point in this book. 

References D. D. Wagman, et ah, The NBS Tables of Chemical Thermodynamic Properties, in J. Phys. Chem. Ref. Data, 11 2,1982 M. W. Chase, et ah, JANAF Thermochemical Tables, 3rd ed., American Chemical Society and the American Institute of Physics, 1986 (supplements to JANAF appear in J. Phys. Chem. Ref. Data) Thermodynamic Research Center, TRC Thermodynamic Tables, Texas A M University, College Station, Texas I. Barin and O. Knacke, Thermochemical Properties of Inorganic Substances, Springer-Verlag, Berlin, 1973 J. B. Pedley, R. D. Naylor, and S. P. Kirby, Thermochemical Data of Organic Compounds, 2nd ed.. Chapman and Hall, London, 1986 V. Majer and V. Svoboda, Enthalpies of Vaporization of Organic Compounds, International Union of Pure and Applied Chemistry, Chemical Data Series No. 32, Blackwell, Oxford, 1985. 

Thermodynamics is the study of thermal, electrical, chemical, and mechanical forms of energy. The study of thermodynamics crosses many disciplines, including physics, engineering, and chemistry. Of the various branches of thermodynamics. 

Finally, a consideration of equilibrium chemistry can only help us decide what reactions are favorable. Knowing that a reaction is favorable does not guarantee that the reaction will occur. How fast a reaction approaches its equilibrium position does not depend on the magnitude of the equilibrium constant. The rate of a chemical reaction is a kinetic, not a thermodynamic, phenomenon. Kinetic effects and their application in analytical chemistry are discussed in Chapter 13. 

Analytical chemistry is more than a collection of techniques it is the application of chemistry to the analysis of samples. As you will see in later chapters, almost all analytical methods use chemical reactivity to accomplish one or more of the following—dissolve the sample, separate analytes and interferents, transform the analyte to a more useful form, or provide a signal. Equilibrium chemistry and thermodynamics provide us with a means for predicting which reactions are likely to be favorable. 

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