Chapter 3 PROPERTIES OF PURE SUBSTANCES

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.

PURE SUBSTANCE
Pure substance: A substance that has a fixed (not necessarily single) chemical composition throughout.
Any homogeneous mixture is considered a pure substance. Non-homogeneous mixture (oil and water) is not a pure substance.
AIR

Nitrogen and gaseous air are pure substances.

A mixture of liquid water and gaseous water is a pure substance, but a mixture of liquid air and gaseous air is not.
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PHASES OF A PURE SUBSTANCE

A phase has a distinct molecular arrangement. Three principal phases Solid Liquid Gas Phase change processes are Melting: solid liquid Solidification: Liquid solid Vaporization: Liquid gas Condensation: Gas liquid Internal energy of the substance changes during phase change.

PHASES OF A PURE SUBSTANCE

In many applications, we have a mixture of the two phases (phase change). Boiler, condenser, refrigerator, etc. The properties we are interested in: P Pressure specific volume T Temperature U internal energy Cv, Cp specific heats X quality (% of mass converted to vapor) We will learn to determine these properties during thermodynamic processes.

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).

Due to increased T, v also increases slightly as P remains constant

 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).

As more heat is transferred, part of the saturated liquid vaporizes (saturated liquid vapor mixture).

At 1 atm pressure, the temperature remains constant at 100C until the last drop of liquid is vaporized (saturated vapor).

As more heat is transferred, the temperature of the vapor starts to rise (superheated vapor).

v5 > v4 > v3 > v2 > v1

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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. 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.

Exercise
What is the saturation pressure for water at 270oC? From Table A-4 (page 915) Psat = 5503.0 kPa Consider water at 270oC and 4000 kPa, is it liquid, gas, or solid Tsat = 250.35oC at P = 4000 kPa (A-5) vapor or gas state. so it is

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PROPERTY DIAGRAMS FOR PHASE

When water is kept under different pressures in a piston-cylinder system, upon heating, water follows different process paths
As the pressure is increased, the saturation line continues to shrink and it becomes a point, called critical point.

T-v diagram of constantpressure phase-change processes of a pure substance at various pressures

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T-v diagram of a pure substance.

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Critical point: The point at which the saturated liquid and saturated vapor states are identical. At supercritical pressures (P > Pcr), there is no distinct phase-change process. For water: Table A-1 for other pure substances Pcr = 22.06 MPa Tcr = 373.95oC Vcr = 0.003106 m3/kg

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T-v diagram of a pure substance.

P-v diagram of a pure substance.

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Exercise
Plot T-v diagrams for water going through the following process
Isothermal process. T = 200oC, P1 = 1 MPa, P2 = 5 MPa For T = 200oC, Psat = 1.5549 MPa (Table A-4) P1 < Psat, so initially (1) we have vapor, but P2>Psat, so at (2), we have compressed liquid

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Exercise contd
Plot P-v diagrams for water going through the following process
Isothermal process. T = 200oC, P1 = 1 MPa, P2 = 5 MPa For T = 200oC, Psat = 1.5549 MPa (Table A-4) P1 < Psat, so initially (1) we have vapor, but P2>Psat, so at (2), we have compressed liquid

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Exercise contd
What are the initial and final specific volumes, v1 and v2
At state 1, we have superheated vapor then use Table A-6, page 918 Use T1 = 200oC and P1 = 1 MPa to read v1 = 0.20602 m3/kg At state 2, we have compressed liquid, then use Table A-7, page 922 Use T2 = 200oC and P2 = 5 MPa to read v2 = 0.0011531 m3/kg

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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.

P-v diagram of a substance that contracts on freezing. P-v diagram of a substance that expands on freezing (such as water).
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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), P-T diagram of pure substances. solids evaporate without melting first (sublimation). Table 3.3 for Triple Point temperatures and pressures
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P-v-T surface of a substance that contracts on freezing.

P-v-T surface of a substance that expands on freezing (like water).

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PROPERTY TABLES

For most substances, the relationships among thermodynamic properties are too complex , 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.

EnthalpyA Combination Property

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

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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: A rigid tank contains 50 kg of

saturated liquid at 90oC. Determine the pressure in the tank and the volume of the tank. Solution: m= 50 kg, saturated liquid water T = 90oC Find pressure from Table A-4 At T = 90oC Psat = 70.183 kPa Find vf at 90oC: vf = 0.001036 m3/kg V = vf.m = (0.001036)(50) = 0.0518 m3

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Examples: A mass of 200 g of saturated liquid

water is completely vaporized at a constant pressure of 100 kPa. Determine (a) the volume change and (b) the amount of energy transferred to the water. Solution: Table A-5 at 100 kPa

vfg = vg vf = 1.6941 0.001043 = 1.6931 m3/kg

Change in volume = m.vfg = 0.3386 m3 The amount of energy needed to vaporize a unit mass is the enthalpy of vaporization at that pressure, which is hfg = 2257.5 kJ/kg for water at 100 kPa. Thus, total energy: H = m.hfg = (0.2 kg)(2257.5 kJ/kg) = 451.5 kJ

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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.

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

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Vf = Specific volume of saturated liquid Vg = Specific volume of saturated vapor Vavg = Specific volume of saturated liquidvapor mixture

Quality is related to the horizontal distances on P-v and T-v diagrams.

The v value of a saturated liquidvapor mixture lies between the vf and vg values at the specified T or P.
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We can use quality x to determine the enthalpy, h, and internal energy, u, of the saturated liquid-vapor mixture

v, u, or h.

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Review examples 3-4, page 128

A rigid tank contains 10 kg of water at 90oC. If 8 kg of the water is in the liquid form and the rest is in the vapor form, determine (a) the pressure in the tank and (b) the volume of the tank.

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Review examples 3-5, page 129

An 80L vessel contains 4 kg of refrigerant-134a at a pressure of 160 kPa. Determine (a) the temperature, (b) the quality, the enthalpy of the refrigerant, and (d) the volume occupied by the vapor phase

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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. Table A-7 is the only table exists in this text. y v, u, or h

Compressed Liquid
Compressed liquid is characterized by

A compressed liquid may be approximated as a saturated liquid at the given temperature. A more accurate relation for h

At a given P and T, a pure substance will exist as a compressed liquid if

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Interpolation
In most applications, we cannot read the properties of water directly off the tables.

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Interpolation Example
Determine the temperature of water at P = 0.5 MPa and h = 2890 kJ/kg. From Table A-5, we determine that we have superheated water vapor. Why? Use Table A-6, superheated vapor at P = 0.5 MPa T1 = 200oC h1 = 2855.8 kJ/kg T2 = 250oC h2 = 2961.0 kJ/kg (h-h1)/(h2-h1) = (T-T1)/(T2-T1) h2 h1 = 105.2 kJ/kg h h1 = 2890 2855.8 = 34.2 kJ/kg (h-h1)/(h2 h1) = 34.2/105.2 = 0.3250 T2-T1 = 250oC-200oC = 50oC (h-h1)/(h2-h1).(T2-T1) = 0.3250 (50) = 16.44oC

T = T1 + (h-h1)/(h2-h1).(T2-T1) = 200oC = 16.44oC = 216.44oC

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Problem
A piston-cylinder device contains 0.1m3 liquid water an 0.9m3 of water vapor in equilibrium at 800 kPa. Heat is transferred at constant pressure until T= 350oC.
(a) What is the initial temperature? (b) Determine the total mass of water. (c) Calculate the final volume. (d) Show the process on a p-v diagram with respect to saturation lines. P1 = 800 kPa T1 = ? Vapor Liquid P2 = 800 kPa T2 = 350oC

(a) Initially two phases coexist, thus we have a saturated liquid-vapor mixture. Then the temperature in the tank must be the saturation temperature T = Tsat@800kPa = 170.41oC Table A-5 Page 917

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Problem
(b) To find total mass we can add the mass of each phase

mf = Vf/vf = 0.1 m3/0.001115 m3/kg = 89.69 kg mg= Vg/vg = 0.9 m3/0.2404 m3/kg = 3.74 kg mTotal = mf + mg = 93.43 kg (c) At final state, water is superheated vapor. P2 = 800 kPa and T2 = 350oC Using Table A-6, v2 = 0.3544 m3/kg, thus, V2 = mv2 = (93.43) (0.3544) = 0.33.1 m3

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Problem 3-26
Complete this table for H2O
T, C P, kPa 200 140 950 80 500 800 3162.2 1800 0.0 h, kJ / kg x 0.7 Phase description

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Problem 3-26
Complete this table for H2O
T, C
120.21 140 177.66 80 350.0

P, kPa
200 361.53 950 500 800

h, kJ / kg
2045.8 1800 752.74 335.37 3162.2

x
0.7 0.565 0.0 -----

Phase description
Saturated mixture Saturated mixture Saturated liquid Compressed liquid Superheated vapor

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THE IDEAL-GAS EQUATION OF STATE

Instead of using tables to obtain properties, using simple equations (if we have them available) would be easier. 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. T: absolute temperature in Kelvin (K) V: Specific volume

Ideal gas equation of state P: absolute pressure

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

Different substances have different 38 gas constants.

Mass = Molar mass Mole number

Various expressions of ideal gas equation

Real gases behave as an ideal gas at low densities (i.e., low pressure, high temperature). Ideal gas equation at two states for a fixed mass

The ideal-gas relation often is not applicable to real gases; thus, care should be exercised when using it.

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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.

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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.

The compressibility factor is unity for ideal gases.

At very low pressures, all gases approach ideal-gas behavior (regardless of their temperature).

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How to determine Z

Reduced pressure

Reduced temperature Pseudo-reduced specific volume

Z can also be determined from a knowledge of PR and vR.

Figure A-15 (page 932) Comparison of Z factors for various gases.

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Deviation from Ideal Behavior

At very low pressure, PR<<1, the gases behave as an ideal gas At high temperature (TR>2), ideal gas behavior can be assumed (except when PR>>1) The deviation from ideal gas behavior is greatest in the vicinity of the critical point

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Example 3-11
Determine the specific volume v, of refrigerant -134a at P = 1 MPa and at 50oC. (a) Use ideal gas equation (b) Use compressibility chart Solution (a) We need to find gas constant, R, for refrigerant. From Table A-1, R = 0.08149 kJ/kgK Ideal gas equation, Pv = RT v = RT/P = 0.08149 (273+50)/1000 = 0.02632 m3/kg (b) To use compressibility chart, we need to calculate PR and TR PR = 1 MPa/4.059 MPa = 0.246

TR = 323K/374.2K = 0.863
Using the chart (Fig. 3.49), we find Z = 0.84 Then v = Z videal = 0.0221 m3/kg Note that more accurate value of v is obtained from table A-13 as v = 0.02179 m3/kg

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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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

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Problem
A piston-cylinder contains 50 L liquid water at 25oC and 300 kPa. Heat is added at constant pressure until entire liquid is vaporized. (a) What is the mass of water? (b) What is the final temperature? (c) Determine the total enthalpy change
T1 = 25oC P1 = 300 kPa water T1 < Tsat at 300 kPa Initially we have compressed water

For this case, P1 = 300 kPa this is too low to use Table A-7 Then, v1 = vf@25C = 0.001003 m3/kg h1 = hf@25C = 104.83 kJ/kg (a) m = V1/v1 = 0.05 m3 / 0.001003 m3/kg = 49.85 kg (b) At the final state, the cylinder contains saturated vapor Final temperature must be saturation temperature. For 300 kPa, T = 133.52oC
(c) Final enthalpy is h2 = hg@300kPa = 2724.9 kJ/kg H = m(h2-h1) = 130610 kJ

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