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Such calculations carried out for more-realistic potential functions, though of greater complexity, also lead to values for molecular parameters For example, experimental volumetric data for many gases have been regressed to yield values of a and E for the Lennard-Jones potential [Eq (161)] Values from several potential functions are given by R L ~ o w l e ~ ~ This is an essential source of values, because theory does not provide the means for their prediction One must remember, however, that potential functions are empirical models, and as such are approximations The deficiency of a model is reflected by the values of the molecular parameters regressed from the model, and they must therefore be regarded as effective values of the parameters Different effective values result from the use of different potential functions Since transport properties, such as viscosity and diffusivity, are also related to these same potential functions, data for the transport properties, particularly viscosity, are also used to provide values for E and a Note, however, that any deficiency in the potential function influences the calculation of values in different ways, and the same molecular parameters obtained from different data sources are rarely in exact agreement

The above equation has an equilibrium constant that is less than 1 What are the relative strengths of the acids and bases

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Thermodynamic properties such as internal energy and enthalpy are manifestations on a gross scale of the positions, motions, and interactions of the countless molecules comprising a macroscopic system The two theories that relate the behavior of molecules to macroscopic properties are kinetic theory and statistical mechanics These theories together represent a very large body of extra-thermodynamic knowledge, well beyond the scope of this text Our purpose here is to indicate in a very elementary fashion how the energy associated with the individual molecules of an ideal gas relates to the macroscopic internal energy of the ideal-gas state A fundamental postulate of quantum theory is that energy is quantized, that energy on the microscopic scale comes in very small discrete units Thus a macroscopic system has associated with it an enormous number of quanta of energy, which sum to determine its energy level Quantum theory specifies that the set of energy levels "allowed" to a closed system is determined by its volume This does not mean that fixing the volume of a system fixes its energy; it just determines the discrete set of energy levels permitted to it When a system is isolated (constrained from exchanging either mass or energy with its surroundings), it exists at one of the energy levels allowed to it Each energy level of a system has associated with it a number of quantum states This number g is known as the degeneracy of the level Although an isolated system exists at a particular energy level, it passes over time through all of the g quantum states characterized by this same energy A large number of quantum states is accessible to a system of given volume in equilibrium with surroundings at fixed temperature From the thermodynamic point of view, fixing T and V establishes the state of the system, including its internal energy However, macroscopic equilibrium does not imply a static situation on the microscopic scale The ceaseless motion of the molecules and their collisions with the walls of the container result in exchanges of energy with the surroundings, which cause momentary fluctuations in the energy of the system Thus the internal energy of thermodynamics is an average over the discrete set of energy levels of.

'R L Rowley, Statistical Mechanics for Thermophysical Property Calculations, app 5, PTR Prentice Hall, Englewood Cliffs, NJ, 1994

As shown above, malonic acid is a diprotic acid The successive equilibrium constants are 15 3 6 10 (Ka1) and 20 10 (Ka2) What is the equilibrium constant for the above reaction 14 (A) 10 10 (B) 20 10 6 (C) 40 10 12 (D) 30 10 9 (E) 15 10 3 24 C(s) + H2O(g) CO(g) + H2O(g) endothermic

W H AT I T TA K E S T O B E # 1

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