Nonideal Equations of State Texas Tech University德克萨斯理工大学非理想状态方程.pptVIP

Non-ideal Equations of State Review Real Fluids Gases do not always obey the ideal gas law. At modest temperatures but high pressures, the molecules get close enough together that intermolecular attractive forces become significant. Two things can happen – At low temperatures the gas can turn into a liquid At higher temperatures the gas stays a gas but behaves a lot like a liquid this state is called a supercritical fluid Review The temperature at which it becomes impossible to ever form a liquid regardless of the pressure is called the critical temperature. (Tc) The pressure at which there is just last both vapor and liquid is called the critical pressure. (Pc) Use of Tc and Pc The critical temperature and pressure are key parameters for calculating the relationship between P, V, and T for non-ideal fluids using empirical EOS’s. Empirical Equations Several empirical “cubic” equations have been invented to relate P to V and T for non-ideal gases. van der Waals Redlich Kwong Peng Robinson Redlich Kwong Suave van der Waals van der Waals The values of a and b are different for different chemicals, but they are related in the same way to each chemical’s Tc and Pc. Critical properties are tabulated. Peng-Robinson The vdW equation is Ok but other empirical EOS’s are more accurate (but more complicated) One that has a nice balance of accuracy vs complexity is the Peng-Robinson EOS. Peng-Robinson The a and b parameters are related empirically to the critical properties: Peng-Robinson The a parameter is temperature dependent and also depends on another tabulated,chemical specific, parameter called the “acentric factor” Peng-Robinson It is usually a good idea to program the more complex equations into a spreadsheet or Maple. Because of the way the equation is written, finding the volume when T and P are given or finding the temperature when P and V are given requires trial and error calculations (root finding) Beware Multiple Roots When the object is to find V with T