Nature of thermodynamics

H. Poincare, Science and Hypothesis, reprinted by Dover, New York, 1952 P. W. Bridgman, The Logic of Modem Physics, MacmiUan, New York, 1927 P. W. Bridgman, The Nature of Thermodynamics, Harvard University Press, Cambridge, MA, 1941 P. Duhem, The Aim and Structure of Physical Theory, Princeton University Press, Princeton, NJ, 1954. 

Looking at thermodynamics from the physical chemistry perspective, students at the high school and college levels experience difficulties with fundamental concepts in chemical equilibrium and thermodynamics (61). Thomas and Schwenz (62) found that physical chemistry students still have difficulties with the above concepts, which may continue through their professional careers. Both students and lecturers in the SOzbilir study (52) (see above) assumed the abstract nature of thermodynamics concepts as a cause of learning difficulties. 

Once an emulsion has been formed, its stability with respect to depletion flocculation is determined primarily by the nature of thermodynamically unfavourable interactions (Ay > 0) between the biopolymers which influences the osmotic pressure in the aqueous phase according to equation (3.9) (see also equation (3.19)). That is, the value of A, influences the depth of the minimum in the depletion potential, AGdep (see equation (3.41) and Figure 3.6). 

Bridgman, P.W. The Nature of Thermodynamics. Harvard University Press, Cambridge, MA. 1941. 

In a matter of personal experience, it is appropriate to acknowledge several meaningful discussions with my father, the late Richard M. Honig, who was an expert in jurisprudence and who readily saw the parallels between scientific methodology and the codification of law. He persisted with questions concerning the nature of thermodynamics that I could not readily answer and was thereby indirectly responsible for the tenor of the present volume. 

In his usual elegant style, Jaynes uses this situation to clarify not only the macroscopic nature of thermodynamics, but the role of information, reversible and irreversible mixing and the work available. Particularly interesting is his use of this example to emphasize the importance of defining the constraints (which he calls macrovariables) defining a system. When we know about Arl and Ar2 and are able to separate them by doing work on the system, we have an extra constraint in the sense of 4.9.2. 

FIGURE 3.1 The dual nature of thermodynamics. Half of the subject (upper panel) focuses on heat and work exchanges between a system and its surroundings. The other half (lower panel) attends to the relationships between state quantities. A property such as enthalpy is related to temperature, heat capacity, and more. The equivalent statement can be made about every quantity in the lower panel. 

The question whether the law of the conservation of energy is soundly based on experiment or whether it is really an act of faith has been discussed in detail by Meyerson, Identity and Reality transl. Loewenberg (London, Allen and Unwin, 1930) and by Bridgman, The Nature of Thermodynamics (Harvard, 1941). 

In order that the reader may appreciate the nature of thermodynamic quantities, thermodynamic data, and their uses, it is necessary for him to know the present state of thermodynamic theory and be aware of sources of information on the fundamental background of classical and statistical thermodynamics. This Chapter does not aim to give a short course in thermodynamics nor does it review in detail the history of the foundation of the subject with which such names as Joseph Black (1728—-99), Count Rumford (1753—1814), Sadi Carnot (1796—1832), James Joule (1818—89), and Lord Kelvin (1824—1907) are associated. 

Anybody would be foolhardy to claim that it is possible to list all the currently available books on chemical thermodynamics that are likely to be used by English-speaking chemists. Nevertheless, if the full significance of the nature of thermodynamic quantities and data is to be appreciated,... 

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