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You are on page 1of 83

McGraw-Hill, 2008

Chapter 3

PROPERTIES OF PURE

SUBSTANCES

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Objectives

Introduction of pure substance

Discuss the phase-change process.

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.

2

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.

pure substances. A mixture of liquid and gaseous

water is a pure substance, but a

mixture of liquid and gaseous air

is not.

3

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.

The arrangement of atoms in different phases: (a) molecules are at relatively fixed

positions in a solid, (b) groups of molecules move about each other in the liquid

phase, and (c) molecules move about at random in the gas phase. 4

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.

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).

5

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).

part of the saturated liquid temperature remains transferred, the

vaporizes (saturated liquid constant at 100C until the temperature of the

vapor mixture). last drop of liquid is vaporized vapor starts to rise

(saturated vapor). (superheated vapor).

6

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.

heating process of

water at constant

pressure.

7

Saturation Temperature and Saturation 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.

Tsat increase with Psat

A substance at higher pressure boils at higher temperature.

In kitchen, higher boiling temperature mean shorter cooking time and energy

saving.

Pressure cooker will cooked at shorter cooking time.

The liquid

vapor

saturation

curve of a

pure

substance

(numerical

values are for

water).

8

Latent heat: The amount of energy

absorbed or released during a phase-

change 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.

- The atmospheric pressure, and

At 1 atm pressure, the latent heat of thus the boiling temperature of

fusion of water is 333.7 kJ/kg and the water, decreases with elevation.

latent heat of vaporization is 2256.5 - Therefore at higher altitude it

kJ/kg. takes longer to cook.

9

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.

As pressure increased

further, the saturation line

continues to shrink and it

become a point.

The point is called as

critical point.

= point at which the

sat.liq and sat.vapor

states are indentical.

-Refer Table A-1

pressure phase-change

processes of a pure substance

at various pressures

(numerical values are for

water).

10

P-v diagram of a pure substance. T-v diagram of a pure substance.

saturated liquid line

Critical point: The point

at which the saturated saturated vapor line

liquid and saturated vapor compressed liquid region

states are identical.

superheated vapor region

saturated liquidvapor

mixture region (wet region)

11

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.

Specific enthalpy

Enthalpy

The

combination

u + Pv is

frequently

encountered

in the analysis

of control The product pressure

volumes. volume has energy units.

12

Saturated Liquid and Saturated Vapor States

Table A4: Saturation properties of water under temperature. (use

when temperature is given)

Table A5: Saturation properties of water under pressure. (use

when pressure is given)

A partial list of Table A4.

heat of vaporization): The amount of

energy needed to vaporize a unit mass

of saturated liquid at a given

temperature or pressure.

13

14

15

Example 3-2

A piston cylinder device contains 0.06m3 of saturated water vapor at

350 kPa pressure. Determine the temperature and the mass of the

vapor inside the cyclinder.

16

17

18

19

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.

=

Saturated liq-vapor mixture

amounts of treated as a homogeneous

liquid and mixture for convenience.

vapor phases

in a saturated

mixture are

specified by

the quality x. 20

y v, u, or h.

Quality is related

to the horizontal

distances on P-v

and T-v

diagrams.

The v value of a

saturated liquid

vapor mixture lies

between the vf and vg

values at the

specified T or P.

21

22

23

24

In the region to the right of the Superheated Vapor (Table

saturated vapor line and at A-6)

Compared to saturated vapor,

temperatures above the critical

point temperature, a substance superheated vapor is characterized by

exists as superheated vapor.

In this region, temperature and

pressure are independent

properties.

At a specified

P, superheated

vapor exists at

a higher h than

the saturated

vapor.

25

26

Compressed Liquid (Table A-7)

The compressed liquid properties depend on temperature much more strongly

than they do on pressure.

saturated liquid at the given temperature.

27

Compressed liquid is characterized by

At a given P

and T, a pure

substance will

exist as a

compressed

liquid if 28

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 referance 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.

29

30

Tutorial

31

32

33

34

35

36

To be continue in next class..

TQ

37

For water,

Extending the Ttp = 0.01C

Diagrams to Include Ptp = 0.6117 kPa

the Solid Phase At triple-point pressure

and temperature, a

substance exists in three

phases in equilibrium.

contracts on freezing.

(most substance) P-v diagram of a substance that

expands on freezing (such as water)

(WHY water expand???) 38

Sublimation: Passing from Phase Diagram

the solid phase directly into

the vapor phase.

the triple-point value), P-T diagram of pure substances.

solids evaporate without Refer Table 3.3

melting first (sublimation).

39

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.

that contracts on freezing. expands on freezing (like water).

40

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

Gas that obey this relationship is called

an ideal gas

R: gas constant

M: molar mass (kg/kmol)

Ru: universal gas constant

gas constants.

41

Table A-1 Value of R and M for several substance

42

An ideal gas is an imaginary substance that obeys the

relation Pv = RT

relation given closely approximates the P-v-T behavior

of real gases at low densities.

a gas decreases, and the gas behaves as an ideal gas

under these conditions.

such as air, nitrogen, oxygen, hydrogen, helium, argon,

neon, krypton, and even heavier gases such as carbon

dioxide can be treated as ideal gases with negligible

error (often less than 1 percent).

plants and refrigerant vapor in refrigerators, however,

should not be treated as ideal gases. Instead, the

property tables should be used for these

substances.

43

44

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.

steam to be an ideal gas, and the region where steam can be

treated as an ideal gas with less than 1 percent error. 45

The ideal-gas equation is very simple and thus

very convenient to use.

However, as illustrated in previous Fig., gases deviate from

ideal-gas behavior significantly at states near the saturation

region and the critical point.

This deviation from ideal-gas behavior at a given temperature

and pressure can accurately be accounted for by the

introduction of a correction factor called the compressibility

factor Z defined as

Z = Pv/RT or Pv = ZRT

It can also be expressed as

Z = v actual / v ideal

v ideal = RT/P

46

COMPRESSIBILITY FACTORA MEASURE

OF DEVIATION FROM IDEAL-GAS BEHAVIOR

Compressibility factor Z The farther away Z is from unity, the more the

A factor that accounts for gas deviates from ideal-gas behavior.

the deviation of real gases Gases behave as an ideal gas at low densities

from ideal-gas behavior at (i.e., low pressure, high temperature).

a given temperature and Question: What is the criteria for low pressure

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 ideal-gas behavior (regardless of their

unity for ideal gases. temperature).

47

Gases behave differently at a given temperature and

pressure, but they behave very much the same at

temperatures and pressures normalized with respect to their

critical temperatures and pressures. The normalization is

done as

same reduced pressure and temperature. This is called the

principle of corresponding states.

plotted against PR and TR for several gases.

states reasonably well.

48

Fig 3.51 Comparison of Z factors for various gases. 49

The gases seem to obey the principle of corresponding states

reasonably well.

compressibility chart that can be used for all gases (Fig. A15).

(Page 934)

50

51

When P and T given directly use compressibility chart.

When P and v, or T and v, are given instead of P and T, u

need to find pseudo-reduced specific volume, vR

52

53

54

55

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.

Equation of State

56

2. Beattie-Bridgeman Equation of State

known to be reasonably accurate for densities up to about 0.8cr.

57

3. Benedict-Webb-Rubin Equation of State

Benedict, Webb, and Rubin extended the Beattie-Bridgeman

equation in 1940 by raising the number of constants to eight.

It is expressed as

handle substances at densities up to about 2.5 cr.

58

TRY Example 3-13 by yourself.:p

59

TIME FOR TUTORIAL

LETS DO IT

60

A spring is stretched a distance of 0.8 m and attached to a paddle wheel . The paddle

wheel then rotates until the spring is unstretched. Calculate the heat transfer necessary

to return the system to its initial state

61

A spring is stretched a distance of 0.8 m and attached to a paddle wheel . The paddle

wheel then rotates until the spring is unstretched. Calculate the heat transfer necessary

to return the system to its initial state

62

A 5-hp fan is used in a large room to provide for air circulation. Assuming a well-

insulated, sealed room determine the internal energy increase after 1 h of operation

A rigid volume contains 6 ft3 of steam originally at a pressure of 400 psia and a

temperature of 900F. Estimate the final temperature if 800 Btu of heat is added

63

A 5-hp fan is used in a large room to provide for air circulation. Assuming a well-

insulated, sealed room determine the internal energy increase after 1 h of operation

A rigid volume contains 6 ft3 of steam originally at a pressure of 400 psia and a

temperature of 900F. Estimate the final temperature if 800 Btu of heat is added

64

Determine the enthalpy change for 1 kg of nitrogen which is heated from

300 to 1200 K by

( a ) using the gas tables,

( b )integrating c,(T), and

( c ) assuming constant specific heat.

Use M = 28 kg/kmol.

65

Determine the enthalpy change for 1 kg of nitrogen which is heated from

300 to 1200 K by

( a ) using the gas tables,

( b )integrating c,(T), and

( c ) assuming constant specific heat.

Use M = 28 kg/kmol.

66

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