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There exists a form of energy, known as internal energy U, which is an intrinsic property of a system, functionally related to the measurable coordinates which characterize the system For a closed system, not in motion, changes in this property are given by Eqs (25) and (26)

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The notation of Eqs (23) through (26) suggests that the terms on the left are different in kind from those on the right The internal-energy terms on the left reflect changes in the internal state or the thermodynamic state of the system It is this state that is reflected by its thermodynamic properties, among which are temperature, pressure, and density We know from experience that for a homogeneous pure substance fixing two of these properties automatically fixes all the others, and thus determines its thermodynamic state For example, nitrogen gas at a temperature of 300 K and a pressure of 10' kPa (1 bar) has a fixed specific volume or density and a fixed molar internal energy Indeed, it has an established set of intensive thermodynamic properties If this gas is heated or cooled, compressed or expanded, and then returned to its initial temperature and pressure, its intensive properties are restored to their initial values Such properties do not depend on the past history of the substance nor on the means by which it reaches a given state They depend only on present conditions, however reached Such quantities are known as state functions When two of them are held at fixed values for a homogeneous pure ~ubstance,~ the thermodynamic state of the substance is fully determined This means that a state function, such as specific internal energy, is a property that always has a value; it may therefore be expressed mathematically as a function of other thermodynamic properties, such as temperature and pressure, or temperature and density, and its values may be identified with points on a graph On the other hand, the terms on the right sides of Eqs (23) through (26), representing heat and work quantities, are not properties; they account for the energy changes that occur in the surroundings and appear only when changes occur in a system They depend on the nature of the process causing the change, and are associated with areas rather than points on a graph, as suggested by Fig 13 Although time is not a thermodynamic coordinate, the passage of time is inevitable whenever heat is transferred or work is accomplished The differential of a state function represents an infinitesimal change in its value Integration of such a differential results in a finite difference between two of its values, eg: and The differentials of heat and work are not changes, but are infinitesimal amounts When integrated, these differentials give not finite changes, but finite amounts Thus,.

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Solutions to some of the problems of this chapter require vapor pressures as a function of temperature for species which constitute systems in VLE Table 102 lists parameter values for tlle Antoine equation,

Acetone Acetonitrile Benzene Chlorobenzene I-Chlorobutane 1,4-Dioxane Ethanol Ethylbenzene ,d n-Heptane Methanol Methyl acetate \J n-Pentane 1-Propano1 Toluene Water

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