Thermodynamics: An Engineering Approach

Seventh Edition in SI Units

Yunus A. Cengel, Michael A. Boles McGraw-Hill, 2011

Chapter 3 PROPERTIES OF PURE SUBSTANCES

Mehmet Kanoglu
University of Gaziantep
Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Objectives
Introduce the concept of a pure substance. Discuss the physics of phase-change processes.

Illustrate the P-v, T-v, and P-T property diagrams and P-v-T surfaces of pure substances.
Demonstrate the procedures for determining thermodynamic properties of pure substances from tables of property data. Describe the hypothetical substance ideal gas and the ideal-gas equation of state. Apply the ideal-gas equation of state in the solution of typical problems. Introduce the compressibility factor, which accounts for the deviation of real gases from ideal-gas behavior.

Present some of the best-known equations of state.

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PURE SUBSTANCE
Pure substance: A substance that has a fixed chemical composition throughout. Air is a mixture of several gases, but it is considered to be a pure substance.

PHASES OF A PURE SUBSTANCE

The molecules in a solid are kept at their positions by the large springlike inter-molecular forces. In a solid, the attractive and repulsive forces between the molecules tend to maintain them at relatively constant distances from each other.
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PHASE-CHANGE PROCESSES OF PURE SUBSTANCES

Compressed liquid (subcooled liquid): A substance that it is not about to vaporize. Saturated liquid: A liquid that is about to vaporize. At 1 atm and 20C, water exists in the liquid phase (compressed liquid).

At 1 atm pressure and 100C, water exists as a liquid that is ready to vaporize (saturated liquid).
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 Saturated vapor: A vapor that is about to condense. Saturated liquidvapor mixture: The state at which the liquid and vapor phases coexist in equilibrium. Superheated vapor: A vapor that is not about to condense (i.e., not a saturated vapor).

At 1 atm pressure, the As more heat is transferred, temperature remains part of the saturated liquid constant at 100C until the vaporizes (saturated liquid last drop of liquid is vaporized vapor mixture). (saturated vapor).

As more heat is transferred, the temperature of the vapor starts to rise (superheated vapor).
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If the entire process between state 1 and 5 described in the figure is reversed by cooling the water while maintaining the pressure at the same value, the water will go back to state 1, retracing the same path, and in so doing, the amount of heat released will exactly match the amount of heat added during the heating process.

T-v diagram for the heating process of water at constant pressure.

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Saturation Temperature and Saturation Pressure

The temperature at which water starts boiling depends on the pressure; therefore, if the pressure is fixed, so is the boiling temperature. Water boils at 100C at 1 atm pressure. Saturation temperature Tsat: The temperature at which a pure substance changes phase at a given pressure. Saturation pressure Psat: The pressure at which a pure substance changes phase at a given temperature.

The liquidvapor saturation curve of a pure substance (numerical values are for water).

Latent heat: The amount of energy absorbed or released during a phasechange process.
Latent heat of fusion: The amount of energy absorbed during melting. It is equivalent to the amount of energy released during freezing. Latent heat of vaporization: The amount of energy absorbed during vaporization and it is equivalent to the energy released during condensation. The magnitudes of the latent heats depend on the temperature or pressure at which the phase change occurs.

At 1 atm pressure, the latent heat of fusion of water is 333.7 kJ/kg and the latent heat of vaporization is 2256.5 kJ/kg.
The atmospheric pressure, and thus the boiling temperature of water, decreases with elevation.
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Some Consequences of Tsat and Psat Dependence

The variation of the temperature of fruits and vegetables with pressure during vacuum cooling from 25C to 0C.

In 1775, ice was made by evacuating the air space in a water tank.

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PROPERTY DIAGRAMS FOR PHASE-CHANGE PROCESSES

The variations of properties during phase-change processes are best studied and understood with the help of property diagrams such as the T-v, P-v, and P-T diagrams for pure substances.

T-v diagram of constant-pressure phase-change processes of a pure substance at various pressures (numerical values are for water).

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saturated liquid line

saturated vapor line compressed liquid region superheated vapor region saturated liquidvapor mixture region (wet region)

At supercritical pressures (P > Pcr), there is no distinct phase-change (boiling) process.

Critical point: The point at which the saturated liquid and saturated vapor states are identical.

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Extending the Diagrams to Include the Solid Phase

For water, Ttp = 0.01C Ptp = 0.6117 kPa

At triple-point pressure and temperature, a substance exists in three phases in equilibrium.

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Sublimation: Passing from the solid phase directly into the vapor phase.

Phase Diagram

At low pressures (below the triple-point value), solids evaporate without melting first (sublimation).

P-T diagram of pure substances.

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The P-v-T surfaces present a great deal of information at once, but in a thermodynamic analysis it is more convenient to work with two-dimensional diagrams, such as the P-v and T-v diagrams.

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PROPERTY TABLES
For most substances, the relationships among thermodynamic properties are too complex to be expressed by simple equations. Therefore, properties are frequently presented in the form of tables. Some thermodynamic properties can be measured easily, but others cannot and are calculated by using the relations between them and measurable properties. The results of these measurements and calculations are presented in tables in a convenient format.

EnthalpyA Combination Property

The combination u + Pv is frequently encountered in the analysis The product pressure of control volume has energy units. 17 volumes.

Saturated Liquid and Saturated Vapor States

Table A4: Saturation properties of water under temperature. Table A5: Saturation properties of water under pressure.
A partial list of Table A4.

Enthalpy of vaporization, hfg (Latent heat of vaporization): The amount of energy needed to vaporize a unit mass of saturated liquid at a given temperature or pressure.

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Examples:
Saturated liquid and saturated vapor states of water on T-v and P-v diagrams.

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Saturated LiquidVapor Mixture

Quality, x : The ratio of the mass of vapor to the total mass of the mixture. Quality is between 0 and 1 0: sat. liquid, 1: sat. vapor. The properties of the saturated liquid are the same whether it exists alone or in a mixture with saturated vapor. Temperature and pressure are dependent properties for a mixture.

The relative amounts of liquid and vapor phases in a saturated mixture are specified by the quality x.

A two-phase system can be treated as a homogeneous mixture for convenience.

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v, u, or h.

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Examples: Saturated liquid-vapor

mixture states on T-v and P-v diagrams.

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In the region to the right of the saturated vapor line and at temperatures above the critical point temperature, a substance exists as superheated vapor. In this region, temperature and pressure are independent properties.

Superheated Vapor
Compared to saturated vapor, superheated vapor is characterized by

At a specified P, superheated vapor exists at a higher h than the saturated vapor.

A partial listing of Table A6.

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The compressed liquid properties depend on temperature much more strongly than they do on pressure. y v, u, or h

Compressed Liquid
Compressed liquid is characterized by

A more accurate relation for h

A compressed liquid may be approximated as a saturated liquid at the given temperature.

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Reference State and Reference Values

The values of u, h, and s cannot be measured directly, and they are calculated from measurable properties using the relations between properties. However, those relations give the changes in properties, not the values of properties at specified states. Therefore, we need to choose a convenient reference state and assign a value of zero for a convenient property or properties at that state. The reference state for water is 0.01C and for R-134a is -40C in tables. Some properties may have negative values as a result of the reference state chosen. Sometimes different tables list different values for some properties at the same state as a result of using a different reference state. However, In thermodynamics we are concerned with the changes in properties, and the reference state chosen is of no consequence in calculations.

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THE IDEAL-GAS EQUATION OF STATE

Equation of state: Any equation that relates the pressure, temperature, and specific volume of a substance. The simplest and best-known equation of state for substances in the gas phase is the ideal-gas equation of state. This equation predicts the P-v-T behavior of a gas quite accurately within some properly selected region.

Ideal gas equation of state

R: gas constant M: molar mass (kg/kmol) Ru: universal gas constant

Different substances have different gas constants.

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Mass = Molar mass Mole number

Ideal gas equation at two states for a fixed mass

Various expressions of ideal gas equation

Real gases behave as an ideal gas at low densities (i.e., low pressure, high temperature).

Properties per unit mole are denoted with a bar on the top.

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Is Water Vapor an Ideal Gas?

At pressures below 10 kPa, water vapor can be treated as an ideal gas, regardless of its temperature, with negligible error (less than 0.1 percent). At higher pressures, however, the ideal gas assumption yields unacceptable errors, particularly in the vicinity of the critical point and the saturated vapor line.

In air-conditioning applications, the water vapor in the air can be treated as an ideal gas. Why?
In steam power plant applications, however, the pressures involved are usually very high; therefore, ideal-gas relations should not be used.

Percentage of error ([|vtable - videal|/vtable] 100) involved in assuming steam to be an ideal gas, and the region where steam can be treated as an ideal gas with less than 1 percent error.

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COMPRESSIBILITY FACTORA MEASURE OF DEVIATION FROM IDEAL-GAS BEHAVIOR

Compressibility factor Z A factor that accounts for the deviation of real gases from ideal-gas behavior at a given temperature and pressure. The farther away Z is from unity, the more the gas deviates from ideal-gas behavior. Gases behave as an ideal gas at low densities (i.e., low pressure, high temperature). Question: What is the criteria for low pressure and high temperature? Answer: The pressure or temperature of a gas is high or low relative to its critical temperature or pressure.

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Reduced pressure

Reduced temperature Pseudo-reduced specific volume Z can also be determined from a knowledge of PR and vR.

Comparison of Z factors for various gases.

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OTHER EQUATIONS OF STATE

Several equations have been proposed to represent the P-v-T behavior of substances accurately over a larger region with no limitations.

Van der Waals Equation of State

Critical isotherm of a pure substance has an inflection point at the critical state.

This model includes two effects not considered in the ideal-gas model: the intermolecular attraction forces and the volume occupied by the molecules themselves. The accuracy of the van der Waals equation of state is often inadequate.

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Beattie-Bridgeman Equation of State

The constants are given in Table 34 for various substances. It is known to be reasonably accurate for densities up to about 0.8cr.

Benedict-Webb-Rubin Equation of State

The constants are given in Table 34. This equation can handle substances at densities up to about 2.5 cr.

Virial Equation of State

The coefficients a(T), b(T), c(T), and so on, that are functions of temperature alone are called virial coefficients.
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Percentage of error involved in various equations of state for nitrogen (% error = [(|vtable - vequation|)/vtable] 100).

Complex equations of state represent the P-vT behavior of gases more accurately over a wider range.

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Summary
Pure substance Phases of a pure substance Phase-change processes of pure substances
Compressed liquid, Saturated liquid, Saturated vapor, Superheated vapor Saturation temperature and Saturation pressure

Property diagrams for phase change processes

The T-v diagram, The P-v diagram, The P-T diagram, The P-v-T surface

Property tables
Enthalpy Saturated liquid, saturated vapor, Saturated liquid vapor mixture, Superheated vapor, compressed liquid Reference state and reference values

The ideal gas equation of state

Is water vapor an ideal gas?

Compressibility factor Other equations of state

van der Waals Equation of State, Beattie-Bridgeman Equation of State Benedict-Webb-Rubin Equation of State, Virial Equation of State
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