Tutorial on Sketching Property Diagrams for a Pure Compound

In this introductory course on chemical engineering, you will learn that chemical material is transformed by chemical process units; that is, the chemical material goes through a process of change to its temperature, pressure, flow rate, and composition. Sketching property diagrams will help to clarify your conceptual understanding of how chemical material undergoes change in its temperature and pressure. One can sketch property diagrams for a pure compound as well as for a mixture of chemical compounds. This document will focus solely on sketching property relationships for a pure compound, such as the temperature-pressure (PT) diagram, the pressure-volume-temperature (PVT) diagram, the pressureenthalpy (PH) diagram, and the pressure-internal-energy (PU) diagram. Sketching property diagrams for chemical mixtures such as temperature-composition (TXY), pressure-composition (PXY), and enthalpycomposition (HXY) diagrams will be covered under other documents. Each property relationship (like PT, PVT, PH, or PU) for pure chemical compounds has similarly-shaped property diagrams. Click the web links in the table below to see some example diagrams.
Type PT Diagram PVT Diagram PH Diagram PU Diagram Name Pressure-Temperature or Phase Diagram Pressure-Volume-Temperature Diagram Pressure-Enthalpy Diagram or Mollier Chart Pressure-Internal-Energy Diagram CO2 PT PVT PH PU H2O PT similar to PH similar to

Click here for the HYSYS plots of PT, PVT, and PH for pure water based on the SRK equation of state.

In the two examples for PT diagrams (often called phase diagrams), regions exists for solid, liquid, vapor, gas, and fluid phases, while sublimation (solid-vapor), melting (solid-liquid), and saturation (liquidvapor) lines exists where a point on each of those lines has two phases coexisting in a state of equilibrium. In the two examples for PH diagrams (often called Mollier charts), similar regions and lines exist as is the case in the PT diagrams, except a dome region exists to represent two phases (liquid-vapor) in equilibrium. The PVT, PH, and PU diagrams are normally drawn without showing the solid region, its melting line, and its sublimation line. We will follow that practice when sketching these three diagrams. When sketching PT diagrams, we will only show the nearly-vertical portion of the freezing line starting from the triple point (tp). Thus, we will ignore that portion that curves to the right in the PT diagram, because operating at very high pressures is beyond the scope of this introductory course. We sketch a property diagram to depict on it a process of change in temperature and pressure for a pure chemical compound. The sketching process is not to scale, it exaggerates the shape of the dome region, and two guideposts are needed to properly place the temperature and pressure changes occurring in the process. Those two guideposts are the critical condition and the normal boiling condition, and in addition the normal freezing point for the PT diagram only. The initial sketches of the PT, PVT, and PH diagrams for a pure compound are given in the three diagrams below.

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2011, Michael E. Hanyak, Jr., All Rights Reserved

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Tutorial on Sketching Property Diagrams for a Pure Compound

The variables TC and PC are the critical temperature and pressure of the pure compound, respectively. The variables Tm and Tb are the normal melting and boiling temperatures, respectively, at 1 atm for the pure compound. These conditions are tabulated in most textbook on the introduction to chemical engineering, see Table B.1 in the Felder and Rousseau textbook (3rd Ed., 2005) for a select list of pure compounds. For the dome region in the PVT and PH diagrams, its maximum is called the critical point, and an isotherm line labeled TC can be drawn with a point of inflection (i.e., the slope of the line changes) at the maximum on the dome region. The left portion of the dome from the critical point (cp) is called the satd liquid curve, while its right portion is called the satd vapor curve. The critical condition and the normal boiling condition at 1 atm are the two guideposts that can be easily drawn and labeled with values on these three diagrams, since tabular data readily exist for these conditions. While a point on the saturation line between the critical point (cp) to the triple point (tp) in the PT diagram corresponds to a condition of vapor-liquid equilibrium (VLE), that equilibrium condition is represented by a horizontal line that connects the saturated liquid (SL) curve to the saturated vapor (SV) curve in the PVT and PH diagrams. This vapor-liquid equilibrium condition is mathematical model by the following equations for a pure chemical compound: Knowing T Knowing P

= 1.0 = V T = H T = U T

Vf

Lf + + Lf V SL Lf H SL Lf U SL

= 1.0 = V T = H T = U T

Vf

Lf + + Lf V SL Lf H SL Lf U SL

Vf V SV Vf U SV

Vf V SV Vf U SV

Vf H SV +

Vf H SV +

,V ] = vdome [T , pure j ] [V SV SL ] = hdome [T , pure j ] [ H SV , H SL [U SV , U SL ] = udome [T , pure j ] P = psat[T , pure j ]

,V ] = vdome [ P, pure j ] [V SV SL ] = hdome [ P, pure j ] [ H SV , H SL [U SV , U SL ] = udome [ P, pure j ] T = tsat[ P, pure j ]

dof = 13 vars - 11 eqns = 2 is is is is is is is is

dof = 13 vars - 11 eqns = 2

Vf
Lf

V T V

the vapor fraction; that is, the moles of saturated vapor over the total moles in the equilibrium system (satd liquid + satd vapor), unitless. the liquid fraction; that is, the moles of saturated liquid over the total moles in the equilibrium system (satd liquid + satd vapor), unitless. the total specific volume of the equilibrium system, volume per mole or mass. the specific volume of the saturated vapor, volume per mole or mass. the specific volume of the saturated liquid, volume per mole or mass. the total specific enthalpy of the equilibrium system, energy per mole or mass. the specific enthalpy of the saturated vapor, energy per mole or mass. the specific enthalpy of the saturated liquid, energy per mole or mass. the total specific internal energy of the equilibrium system, energy per mole or mass. the specific internal energy of the saturated vapor, energy per mole or mass. the specific internal energy of the saturated liquid, energy per mole or mass. the temperature of the equilibrium system, degrees. the pressure of the equilibrium system, force per area.
2011, Michael E. Hanyak, Jr., All Rights Reserved Page 2 of 3

SV

V SL H

H SV H
SL

U T U

SV

U SL T

P
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Tutorial on Sketching Property Diagrams for a Pure Compound

The degrees of freedom (dof) for both mathematical models are two for all eleven equations. Note that the first three functions (vdome, hdome, and udome) are counted as two equations each, since two unknown variables are to be determined. For the first model, knowing two quantities like T and ,H , or U , you can solve the equations for the other nine unknown variables. For the second Vf , Lf , V T T T

,H , or U , you can solve the equations for the other model, knowing two quantities like P and V f , L f , V T T T
unknown variables. For the last seven equations in each mathematical model, the degrees of freedom is only one (8 - 7 = 1), which matches what is given by the Gibbs phase rule (see Page 3-15 of the CinChE manual). You can only specify temperature or pressure, in order to determine the seven unknown variables. The first four equations in each mathematical model add another degree of freedom, thus given a total of two for all eleven equations. That additional degree of freedom can be satisfied by specifying one of these variables: ,H , or U . Vf , Lf , V T T T The five functions vdome, hdome, udome, psat, and tsat can each be represented by a table, graph, equations, or computer program. For the pure compound of water, these functions are defined by the steam tables; that is, Tables B.5 B.6, and B.7 in the Felder and Rousseau textbook (3rd Ed., 2005). For other pure compounds, function psat and tsat are usually represented by the Antoine equation or computer software like ThermoSolver, while function vdome, hdome, and udome are usually represented by equations of state implemented in computer programs like AspenTech HYSYS. Once you have drawn the initial sketch of a diagram with the two guideposts, you can then represent the process that is changing the temperature and/or pressure of the pure compound. In the CinChE manual, Pages 3-13 to 3-15 described the conditions for the vapor-liquid equilibrium of a pure compound. Page 3-16 pictorially presents the vapor-liquid equilibrium concept and lists the equations that apply. Page 317 presents a pictorial representation of the process to heat pure water from 25C to 150C at a constant pressure of 1 atm. You should study this process to see how it is depicted on the sketched PT, PVT, and PH diagrams. This sketched process is reproduced below.

The 100C and 374.15C isotherms serve as the two guideposts in the PT, PVT, and PH diagrams. The 25C isotherm is draw to the left of 100C isotherm, and the 150C isotherm is between the 100C isotherm and the 374.15C isotherm. The process of heating water at a constant pressure of 1 atm is depicted by the horizontal line from Point F to Point E in all three diagrams. Remember that the sketching process is not to scale, and the shape of the dome region is exaggerated. When you specify pressure (P) and vapor fraction (Vf), you can use the PVT and PH diagrams or the ,V ,V ,H ,H ,H ,U ,U , and U . mathematical model above to determine values for T , L f , V T SV SL T SV SL T SV SL You should examine other combinations for the two degrees of freedom and the subsequent calculations, because you will be held responsible for knowing this material in the future.
Click here to view another important example problem about the vapor-liquid equilibrium of a pure chemical compound.

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2011, Michael E. Hanyak, Jr., All Rights Reserved

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