Thermodynamics and the Free Energy of Chemical Substances

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The scope of thermodynamics. Definitions; the concept of equilibrium. Conventions and mathematical methods. Solutions. The first law of thermodynamics and the concept of energy. The fugacity. Application of the second law to solutions. The perfect solution. The laws of the dilute solution. Systems involving variables other than pressure, temperature and composition. A useful function, called the activity, and its application to solutions. Change of activity with the temperature, and the calculation of activity from freezing points. The standard change of free energy; the equilibrium constant. Solutions of electrolytes. The activity of strong electrolytes. The activity of electrolytes from freezing point data, and tables of activity coefficients. Activity coefficient in mixed electrolytes; the principle of the ionic strength; the activity of individual ions. The galvanic cell. Single potentials; standard electrode potentials of the elements. The third law of thermodynamics. The entropy of monatomic gases and a table of atomic entropies. Introduction to systematic free energy calculations: the free energy of elementary hydrogen and metallic hydrides. Oxygen and its compouns with hydrogen and with some metals. Chlorine and its compouns. Bromine and its compounds. Iodine and its compounds. Nitrogen compounds. Carbon and some of its compounds. Compounds of carbon and nitrogen. Table of free energies; and examples illustrating its use. Conversion table for mol fractions, mol ratios and molities. Some useful numerical factors. Coefficients employed in converting activity, equilibrium constant and free energy from one temperature to another. Publications by the authrs, pertaining to thermodynamics.

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Page 109 - Clausius. • Die Energie der Welt ist konstant • Die Entropie der Welt strebt einem Maximum zu...
Page 448 - If the entropy of each element in some crystalline state be taken as zero at the absolute zero of temperature, every substance has a finite positive entropy; but at the absolute zero of temperature the entropy may become zero, and does so become in the case of perfect crystalline substances.
Page 109 - What is this entropy, which such masters have placed in a position of coordinate importance with energy, but which has proved a bugbear to so many a student of thermodynamics?
Page vii - The labor of generations of architects and artisans has been forgotten, the scaffolding erected for their toil has long since been removed, their mistakes have been erased, or have become hidden by the dust of centuries. Seeing only the perfection of the completed whole, we are impressed as by some superhuman agency. But sometimes we enter such an edifice that is still partly under construction; then the sound of hammers, the reek of tobacco, the trivial jests bandied from workman to workman, enable...
Page 126 - ... two parts into which it has once been divided, after these have once been mixed. In other words, the impossibility of an uncompensated decrease of entropy seems to be reduced to improbability.
Page 112 - The essential content of the second law might be given by the statement that when any actual process occurs it is impossible to invent a means of restoring every system concerned to its original condition.
Page 110 - ... that every system left to itself changes, rapidly or slowly, in such a way as to approach a definite final state of rest. This state of rest (defined in a statistical way) we also call a state of equilibrium.
Page 3 - SCO,, but the gas leaving the chimney contains a considerable proportion of carbon monoxide, which thus carries away an important quantity of unutilized heat. Because this incomplete reaction was thought to be due to an insufficiently prolonged contact between carbon monoxide and the iron ore, the dimensions of the furnaces have been increased. In England they have been made as high as thirty meters.
Page 111 - This state of rest (defined in a statistical way) we also called the state of equilibrium. Now, since it is a universal postulate of all natural science that a system, under given circumstances, will behave in one and only one way, it is a corollary that no system, except through the influence of external agencies, will change in the opposite direction, ie, away from the state of equilibrium.
Page 26 - Mathematics offers a wonderful shorthand for the precise formulation of well standardized ideas. On the other hand, the expressions of mathematics are lacking in humor, which is to say that they are no suitable medium for those finer shades of thought which are often necessary in the exposition of ideas which are on the way towards standardization. The formal severity of a mathematical treatment has its disadvantages. Indeed in our opinion absolute mathematical rigor is a sort of ignis fatuus...

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