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configurational energy, before its adoption and systematic use for evaluating thermodynamic and solutions properties. 7.3.1 Experimental Configurational Energy The internal energy data for the single component CO2 were obtained from the NIST database (2006). The NIST database uses the Span-Wagner equation of state, which is the current standard for CO2 and it is accepted as essentially equivalent to experimental data. In order to calculate the ideal part of the internal energy, we assume the classical approximation of statistical mechanics where one hypothesises that the energy for a system can be written as sum of energies, each comes from a different property of the system. Within this approximation, the ideal partition function can be written as a product of the partition functions pertaining to the different types of energy. In the case, of a polyatomic gas like CO2 the ideal partition function is a product of electronic, nuclear, rotational, translational and vibrational partition functions (McQuarrie and Simon, 1999). In that case the ideal part of the internal energy is given by the equation (Van P.Carey, 1999) U 5 3n5vib,j /T vib,j /T D /T e (7.1) NkBT 2 j1 2T evib,j 1 kBT The experimental potential energy is obtained from the total experimental potential energy (NIST database) by subtracting the ideal part, which calculated through equation (7.1). The potential energy for the single component CO2 was calculated through three methods: 1) Monte Carlo simulations in NVT ensemble conditions, where temperature and volume remain constant. 98PDF Image | MOLECULAR SIMULATION STUDIES IN THE SUPERCRITICAL REGION
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