![]() Understand the criteria for spontaneity in terms of the properties of the Helmholtz energy and the Gibbs energy use the Gibbs energy to express the spontaneity of a process in terms of the properties of a system use the Gibbs energy to predict the maximum non-expansion work that a system can do use the fact that the Gibbs energy is a state function to find relations between system properties in terms of Maxwell relations.ĭescribe mixtures of substances in thermodynamic terms using the class of properties known as partial molar quantities describe the thermodynamics of mixing apply the concept of the chemical potential of a substance to describe the physical properties of liquid mixtures understand how Raoult’s and Henry’s laws may be used to express the chemical potential of a substance in terms of its mole fraction in a mixture understand the effect of a solute on the thermodynamic properties of a solution, e.g. Understand the dispersal of energy and the origin of the spontaneity of physical and chemical change define the property of entropy in thermodynamic terms and describe it from a statistical viewpoint understand that entropy is a state function Describe the entropy changes that accompany specific processes such as expansion, phase transition, and heating. Error estimates for the calculated entropies are given, and possible sources of systematic errors, and their importance for a reliable prediction of the absolute entropy, are discussed.By the end of this module, you should be able to:Įmploy statistical thermodynamics to understand the distribution of molecular states by considering configurations and weights derive the Boltzmann distribution and use it to predict the populations of states in systems at thermal equilibrium define what is meant by the molecular partition function, interpret it, and, in certain simple cases, calculate it describe how thermodynamic information, such as the internal energy or the statistical entropy of a system, may be extracted from the partition function employ the partition function to obtain any thermodynamic function, for example, the Helmholtz energy, the pressure, the enthalpy, the Gibbs energy, for a system factorize the molecular partition function into a product of translational, rotational, vibrational and electronic contributions. The application of a more efficient importance sampling technique developed here results in a substantial reduction of statistical errors in the evaluation of the configuration integral for a given number of Monte Carlo steps. Numerical tests are performed on a number of small n-alkanes (from ethane to octane), for which the absolute entropies calculated at three different temperatures are compared both with the experimental values and with the previous theoretical results. ![]() ![]() A multidimensional potential energy hypersurface is calculated with the MM3(2000) molecular mechanics force field. Importance sampling Monte Carlo based on the adaptive VEGAS algorithm to perform multidimensional integration is implemented within the TINKER program package. The internal rotor hindrance and all coupling arising from the external and internal rotational degrees of freedom are explicitly taken into account. ![]() The method of Pitzer and Gwinn is used to correct the classical partition function for quantum mechanical effects at low temperatures. The evaluation of the classical rotational partition function represented by a configuration integral over all external and internal rotational degrees of freedom of nonrigid chain polyatomic molecules is described.
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