srs0n019 Equations of State - Wik Educator Equations of State From WikiEducator < Thermodynamics Thermodynai (4) Introduction ‘What is this thing called Thermodynamics??? | Definitions | ‘Thermal Equilibrium and Zeroth Law | Limitations First Law ‘Work, Heat, Energy, and the First Law | Work, Heat, Energy, and the First Law (simplied) | Derivatives | Derivatives Exercise | Reversibility, Enthalpy, and Heat Capacity Second Law Third Law ‘Things to Think About | Observations and Second Law of Thermodynamics | ‘Alternative Approach - the Clausis Inequality | Consequences of the Second Law | Consequences of the Second Law (simplified) | Camot Principle - motivation and examples | Equivalence of Second Law Statements* ‘Third Law of Thermodynamics | Consequences of Third Law* ‘Development of Thermodynamics |The Thermodynamic Network | Network Exercise | Equations of State | ‘Thermochemistry * Optional Section Objectives state Learn how to develop the relationship between pressure, volume, and temperature through the use of eqations of Contents ‘= Introduction and Motivation = 2 Definitions = 2.2 Critical Point = 2.3 Critical Constants = 2.4 Reduced Properties 3 Phase Rule = 3.1 Phase Rule = 3.2 Example 4 Real Gases 5 Generalized Correlations 6A Third Parameter 7 Analytical Equations = 7.2 Cubie Equations 3 Other Equations = 7.4 Recommendations = 8 Notes = 2.1 Compressibility Factor ‘= 5.1 Theory of Corresponding States = 7.1 van der Waals Equation = 7.2.1 Redlich-Kwong Equation = 7.2.2 Soave and Peng-Robinson Equations = 7.3.1 Viral Equation = 7.3.2 Benedict-Webb-Rubin Equation hips: Wikieducatororg/Thermodynamics/Equalions_of State wrsrs0n019 Equations of State - Wik Educator Introduction and Motivation In the last two sections we looked at the thermodynamics network. We said that we needed two things to determine relations between properties: 1. Pressure-Volume-Temperature (PVT) Data 2. Heat Capacity Data This section will look at PVT data, We will look at heat capacity data later Definition &4 Equation of State The relationship between pressure, volume, and temperature for a given substance There are three ways of expressing PVT data: 1, Experimental Data (usually given in tables) 2. Generalized Correlations 3. Analytical Equations Definitions Compressibility Factor The Compressibility Factor, Z is given by, Pv RT Zz where R = gas constant = 8,314 Jimol K = 83.14 em’ bar/mol K TWwo important notes about compressibility factors: = Zis dimensionless = Zis nota constant, Students often forget this, Critical Point The Critical Point is the point above which there exists no phase boundaries. A gas above the critical point will not form a liquid if itis isothermally compressed. Critical Constants The Critical Constants are the values of properties at the critical points (for example, critical temperature). We use a subscript C to denote a critical constant, For example, Tc, Pe. Reduced Properties Reduced Properties are the value of a property divided by its corresponding critical constant, We use a subscript of R to denote a reduced property. hips: Wikieducatororg/Thermodynamics/Equalions_of State 2srs0n019 Equations of State - Wik Educator For example, T Te - a= Fe P p,- 2 2= Be Phase Rule Phas diagram showing the critical point To understand what parameters are important in PVT relations, we need to understand the concepts of degrees of freedom and the phase rule. They are also important for phase equilibrium. Definition Definition Phase Rule F=C+2-P where F = degrees of freedom, C = number of components, P = number of phases}} Example Let us first consider water at room temperature. We have one component (water) and only one phase (liquid), therefore the degrees of freedom is Fe1+2- 2 We have two degrees of freedom, therefore we can independently set two variables -- say pressure and temperature. So we can hhave water at 1 bar, 25 °C; 1 bar, 80 °C; or § bar, 25 °C. Now let us consider boiling water. We still have one component, but we now have two phases (liquid and vapor). The number of degrees of freedom is now Fe1+2-2=1 We have only one degree of freedom, therefore we can set only one independent variable — pressure or temperature. We all know that at one atmosphere, the boiling point is 100 °C, not 80° or 120° Real Gases The figure on the right shows how a real gas behaves with respect fo pressure, temperature, and volume. hips: Wikieducatororg/Thermodynamics/Equalions_of State a7