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First-order phase transitions exhibit a discontinuity in the first derivative of the free energy with respect to some thermodynamic variable. [6] The various solid/liquid/gas transitions are classified as first-order transitions because they involve a discontinuous change in density, which is the (inverse of the) first derivative of the free ...
Chemical thermodynamics is the study of the interrelation of heat and work with chemical reactions or with physical changes of state within the confines of the laws of thermodynamics. Chemical thermodynamics involves not only laboratory measurements of various thermodynamic properties, but also the application of mathematical methods to the ...
The easiest thermodynamic models, also known as equations of state, can come from simple correlations that relate different thermodynamic properties using a linear or second-order polynomial function of temperature and pressures. They are generally fitted using experimental data available for that specific properties.
In particular, the second-order contribution () has been calculated by Burnett. [17] In general circumstances, however, these higher-order corrections may not give reliable improvements to the first-order theory, due to the fact that the Chapman–Enskog expansion does not always converge. [ 18 ] (
The second law refers to a system of matter and radiation, initially with inhomogeneities in temperature, pressure, chemical potential, and other intensive properties, that are due to internal 'constraints', or impermeable rigid walls, within it, or to externally imposed forces.
The first established thermodynamic principle, which eventually became the second law of thermodynamics, was formulated by Sadi Carnot in 1824 in his book Reflections on the Motive Power of Fire. By 1860, as formalized in the works of scientists such as Rudolf Clausius and William Thomson , what are now known as the first and second laws were ...
Associative ionization is a gas phase reaction in which two atoms or molecules interact to form a single product ion. [4]+ + + where species A with excess internal energy (indicated by the asterisk) interacts with B to form the ion AB +.
After van 't Hoff, chemical kinetics dealt with the experimental determination of reaction rates from which rate laws and rate constants are derived. Relatively simple rate laws exist for zero order reactions (for which reaction rates are independent of concentration), first order reactions, and second order reactions, and can be derived for ...