Nonequilibrium in Thermodynamic Formalism: The Second Law, Gases and Information Geometry

The relationship of the first and second laws of thermodynamics based on their energy nature is considered. It is noted that the processes described by the second law of thermodynamics often take place hidden within the system, which makes it difficult to detect them. Nevertheless, even with ideal mixing, an increase in the internal energy of the system occurs, numerically equal to an increase in free energy. The largest contribution to the change in the value of free energy is made by the entropy of mixing, which has energy significance. The entropy of mixing can do the job, which is confirmed in particular by osmotic processes.

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Reactions in solution

10.1093/oso/9780198782957.003.0016 ◽

2018 ◽

Author(s):

Dennis Sherwood ◽

Paul Dalby

Keyword(s):

Phase Equilibria ◽

Gas Phase ◽

First Principles ◽

Unique Feature ◽

Life Sciences ◽

Equilibrium Mixture ◽

Second Law ◽

Ideal Solution ◽

Coupled Reactions ◽

Definition Of

Another key chapter, examining reactions in solution. Starting with the definition of an ideal solution, and then introducing Raoult’s law and Henry’s law, this chapter then draws on the results of Chapter 14 (gas phase equilibria) to derive the corresponding results for equilibria in an ideal solution. A unique feature of this chapter is the analysis of coupled reactions, once again using first principles to show how the coupling of an endergonic reaction to a suitable exergonic reaction results in an equilibrium mixture in which the products of the endergonic reaction are present in much higher quantity. This demonstrates how coupled reactions can cause entropy-reducing events to take place without breaking the Second Law, so setting the scene for the future chapters on applications of thermodynamics to the life sciences, especially chapter 24 on bioenergetics.

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The Analogical Turn (1884–1887)

10.1093/oso/9780198816171.003.0006 ◽

2018 ◽

Author(s):

Olivier Darrigol

Keyword(s):

Boltzmann Equation ◽

Statistical Mechanics ◽

Mechanical System ◽

Thermal Equilibrium ◽

Special Kind ◽

Second Law Of Thermodynamics ◽

Second Law ◽

Equipartition Theorem ◽

Royal Road ◽

H Theorem

This chapter recounts how Boltzmann reacted to Hermann Helmholtz’s analogy between thermodynamic systems and a special kind of mechanical system (the “monocyclic systems”) by grouping all attempts to relate thermodynamics to mechanics, including the kinetic-molecular analogy, into a family of partial analogies all derivable from what we would now call a microcanonical ensemble. At that time, Boltzmann regarded ensemble-based statistical mechanics as the royal road to the laws of thermal equilibrium (as we now do). In the same period, he returned to the Boltzmann equation and the H theorem in reply to Peter Guthrie Tait’s attack on the equipartition theorem. He also made a non-technical survey of the second law of thermodynamics seen as a law of probability increase.

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Second law assessment of behavior differences in formation of several sulfur-oxygen compounds of lanthanum, cerium, and praseodymium

The Journal of Physical Chemistry ◽

10.1021/j100190a088 ◽

1992 ◽

Vol 96 (11) ◽

pp. 4620-4626

Author(s):

E. I. Onstott

Keyword(s):

Second Law

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Second-Law Analysis in a Steam Power Plant for Minimization of Avoidable Exergy Destruction

ASME 2010 4th International Conference on Energy Sustainability, Volume 1 ◽

10.1115/es2010-90144 ◽

2010 ◽

Cited By ~ 3

Author(s):

Tapan K. Ray ◽

Pankaj Ekbote ◽

Ranjan Ganguly ◽

Amitava Gupta

Keyword(s):

Work Performance ◽

Operating Conditions ◽

Performance Criteria ◽

Second Law ◽

Feed Water ◽

Exergy Destruction ◽

Actual Performance ◽

Time Operation ◽

Major Equipment ◽

Cycle Efficiency

Performance analysis of a 500 MWe steam turbine cycle is performed combining the thermodynamic first and second-law constraints to identify the potential avenues for significant enhancement in efficiency. The efficiency of certain plant components, e.g. condenser, feed water heaters etc., is not readily defined in the gamut of the first law, since their output do not involve any thermodynamic work. Performance criteria for such components are defined in a way which can easily be translated to the overall influence of the cycle input and output, and can be used to assess performances under different operating conditions. A performance calculation software has been developed that computes the energy and exergy flows using thermodynamic property values with the real time operation parameters at the terminal points of each system/equipment and evaluates the relevant rational performance parameters for them. Exergy-based analysis of the turbine cycle under different strategic conditions with different degrees of superheat and reheat sprays exhibit the extent of performance deterioration of the major equipment and its impact to the overall cycle efficiency. For example, during a unit operation with attemperation flow, a traditional energy analysis alone would wrongly indicate an improved thermal performance of HP heater 5, since the feed water temperature rise across it increases. However, the actual performance degradation is reflected as an exergy analysis indicates an increased exergy destruction within the HP heater 5 under reheat spray. These results corroborate to the deterioration of overall cycle efficiency and rightly assist operational optimization. The exergy-based analysis is found to offer a more direct tool for evaluating the commercial implication of the off-design operation of an individual component of a turbine cycle. The exergy destruction is also translated in terms of its environmental impact, since the irretrievable loss of useful work eventually leads to thermal pollution. The technique can be effectively used by practicing engineers in order to improve efficiency by reducing the avoidable exergy destruction, directly assisting the saving of energy resources and decreasing environmental pollution.

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