# 2.1.- PURE SUBSTANCE:

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1 Pure substance Phase change processes Use of thermodynamic tables Diagrams -v, P-v Ideal gas equation PURE SUBSANCE: Substance that has a fixed chemical composition throughout is called a PURE SUBSANCE. Water, nitrogen, helium and carbon dioxide PHASE OF A PURE SUBSANCE: At a room temperature and pressure, cooper is a solid, mercury is a liquid, and nitrogen is a gas. here are three principal phases: Chapter 2 1

2 SOLID LIQUID GAS CHANGE-PHASE PROCESSES OF PURE SUBSANCE: here are many practical situations where two phases of a pure substance coexist in equilibrium. Water exits as a mixture of liquid and vapor in the boiler and the condenser of a steam power plant. he refrigerant turns from liquid to vapor in a freezer o refrigerator. COMPRESSED LIQUID AND SAURAED LIQUID Liquid water at 20 ºC and 1 atm pressure. Under theses conditions, water exists in the liquid phase, and it is called a COMPRESSED LIQUID or subcooled liquid, meaning that it is Not about to vaporize. SAE 1 P = 1 atm = 20 ºC COMPRESSED LIQUID Chapter 2 2

3 Heat is now added to the water until its temperature rises to, say 40ºC. As more heat is transferred, the temperature will keep rising until it reaches 100ºC. At this point, water is still a liquid, but any heat addition, will cause some of the liquid to vaporize. A liquid that is about to vaporize is called SAURAED LIQUID. SAE 2 P = 1 atm = 100 ºC SAURAED LIQUID SAURAED VAPOR AND SUPERHEAED VAPOR Once boiling starts, the temperature will stop rising until the liquid is completely vaporized (100ºC and 1 atm). Any heat loss from this vapor, will cause some of the vapor to condense (phase change from vapor to liquid). A vapor that is Chapter 2 3

4 about to condense is called a SAURAED VAPOR herefore, state 4 is a saturated vapor state. A substance at states between 2 and 4 is often referred to as a SAURAED LIQUID-VAPOR MIXURE, since the liquid and vapor phases coexist in equilibrium at these states. SAE 3 SAE 4 P = 1 atm = 100 ºC P = 1 atm = 100 ºC SAURAED LIQUID-VAPOR MIXURE SAURAED VAPOR As more heat is added will result in an increase in both the temperature and the specific volume. At 4

5 the state 5, the temperature of the vapor is, let us say, 300ºC; and if we transfer some heat from the vapor, the temperature may drop somewhat but no condensation will take place as long as the temperature remains above 100ºC (for P= 1 atm). A vapor that is not about to condense (i.e., not a saturated vapor) is called a SUPERHEAED VAPOR SAE 5 P = 1 atm = 300 ºC SUPERHEAED VAPOR 5

6 , ºC Saturated mixture Superheated vapor 20 Compressed liquid SAURAION EMPERAURE AND SAURAION PRESSURE Water boils at 100ºC is INCORREC Water boils at 100ºC at 1atm pressure is CORREC 100ºc 1 Atm ( kpa) 151.9ºC (500 kpa) 6

7 he temperature at which water starts boiling depends on the pressure, therefore if the pressure is fixed, so is the boiling temperature At a given pressure, the temperature at which a pure substance starts boiling is called the SAURAION EMPERAURE ( Sat ). Like wise, at a given temperature, the pressure at which a pure substance starts boiling is called the SAURAION PRESSURE (P Sat ). During a phase change process, pressure and temperature are obviously dependent properties, and there is a definite relation between them, that is Sat = f(p Sat ). Elevation (m) Atmospheric Pressure (kpa) Boiling emperature (ºC) : : : Chapter 2 7

8 2.4.- PROPERY DIAGRAMS FOR PHASE- CHANGE PROCESSES 1.- he - Diagram, ºC COMPRESSED LIQUID REGION Critical point SUPERHEAED VAPOR REGION SAURAED LIQUID-VAPOR REGION P 2 =Constant >P 1 P 1 =Constant Saturated liquid line Saturated vapor line Critical point may be defined as he point at which the saturated liquid and saturated vapor states are identical Chapter 2 8

9 2.- he P- Diagram P Critical point SUPERHEAED VAPOR REGION COMPRESSED LIQUID REGION SAURAED LIQUID-VAPOR REGION 2 =Constant > 1 1 =Constant Saturated liquid line Saturated vapor line PROPERY ABLES he properties are frequently presented in the form of tables. Chapter 2 9

10 ENHALPY- A Combination Property u 1 P, 1 1 CONROL VOLUME u 2 P, 2 2 In the analysis of certain types of process, particularly in power generation and refrigeration, we frequently encounter the combination of properties U+PV. For the sake of simplicity and convenience, this combination is defined as a new property, ENHALPY, and given the symbol H: H = U+ PV (kj) h = u+ P (kj/ kg) Chapter 2 10

11 1- Saturated Liquid and Saturated Vapor States he properties of saturated liquid and saturated vapor for water are listed in table A-4 emp. ºC Sat. Press kpa P Sat Sat. Liquid Specific volume m 3 /Kg f Sat. Vapor g Specific temperature Corresponding saturation pressure Specific volume of saturated liquid Specific volume of saturated vapor f = specific volume of saturated liquid g = specific volume of saturated vapor fg = difference between g and = fg g f ) f (that is Chapter 2 11

12 he quantity h fg is called the ENHALPY OF VAPORIZAION (or latent heat of vaporization). It represents the amount of energy needed to vaporize a unit mass of saturated liquid at a given +temperature o pressure. It decreases as the temperature or pressure increases, becomes zero at the critical point. SAURAED LIQUID-VAPOR MIXURE.- and it During a vaporization process, a substance exists as part liquid and part vapor. hat is, it is a mixture of saturated liquid and saturated vapor. o analyze this mixture properly, we need to know the proportions of liquid and vapor phases in the mixture. his done by defining a new property called QUALIY x as the ratio of the mass of vapor to the total mass of the mixture: m x = m vapor total Chapter 2 12

13 Where: m = m + m = m + m total liquid vapor f g P or Critical point Saturated liquid states Saturated vapor states Sat. vapor Sat. liquid he quality of a system that consist of SAURAED LIQUID is 0 (or 0 percent), and the quality of a system consisting of SAURAED VAPOR is 1 (or 100 percent). Consider a tank that contains a saturated liquidvapor mixture. he volume occupied by saturated Chapter 2 13

14 liquid is V f, and the volume occupied by saturated vapor is V g. he total volume V is the sum of these two: v g Saturated vapor v g Saturated liquid v fg Saturated liquidvapor mixture V = V f + V g V = mv m v = m v + t av f f m g v g m = m m m v = (m m )v + f t g t av t g f m g v g Dividing by mt yields v = ( 1 x)v + av f xv g Chapter 2 14

15 Since x = expressed as m g m t. his relation can also be v + av = vf xv fg (m 3 /kg) Where obtain v fg = vg vf.solving for quality, we x = v av v fg v f his analysis given above can be repeated for internal energy and enthalpy with the following results: u + av av = uf xu fg (kj/kg) h + = hf xh fg (kj/kg) Chapter 2 15

16 2- Superheated Vapor In the region to the right of the saturated vapor line, a substance exists as superheated vapor. Since the superheated region is a single phase region (vapor phase only). At pressures sufficiently below the critical pressure or temperatures sufficiently above the critical temperature, a superheated vapor can be approximated as an IDEAL GAS. 2- Compressed Liquid he properties of compressed liquid are relatively independent of pressure. Increasing the pressure of a compressed liquid 100 times often causes properties to change less than 1 percent. he property most affected by pressure is enthalpy. In the absence of compressed liquid data, a general approximation is O REA COMPRESSED LIQUID AS SAURAED LIQUID A HE GIVEN EMPERAURE. his is because Chapter 2 16

17 the compressed liquid properties depend on temperature more strongly that they do on pressure. hus y = y HE IDEAL-GAS EQUAION OF SAE Any equation that relates the pressure, temperature, and specific volume of a substance is called an EQUAION OF SAE. here are several equation of state. he simplest and the best known equation of state for substances in the gas phase is HE IDEAL-GAS EQUAION OF SAE. In 1802, J. Charles and J. Gay-Lussac, experimentally determined that a low pressures the volume of a gas is proportional to its temperature. hat is, P = R Chapter 2 17

18 P = R or..(2.4) Where the constant of proportionality R is called the GAS CONSAN. Equation 2.4 is called the IDEAL-GAS EQUAION OF SAE, or simply the IDEAS-GAS RELAION, and a gas that obeys this relation is called an IDEAL GAS. In this equation, P is the absolute pressure, is the absolute temperature, and is the specific volume. he gas constant R is different for each gas (table 2-3) and is determined from R M [ kj /( kg.k ) or kpa.m /( kg.k )] u 3 R = Where Ru is the UNIVERSAL GAS CONSAN and M is the molar mass (also called molecular Chapter 2 18

19 weight) of the gas. he constant for all substances, and its value is R u is the same kj/(kmol.k) kpa.m 3 /(kmol.k) bar.m 3 /(kmol.k) R u 1.986Btu/(lbmol.R) psia.ft 3 /(lbmol.r) 1545 ft.lbf/(lbmol.r) he MOLAR MASS (M) can simply be defined as the mass of one mole (also called a gram-mole, abbreviated gmol ) of a substance in grams, or the mass of one kmol (also called a kilogrammole, abbreviated kgmol) in kilograms. In English units, it is the mass of 1 lbmol (1 pound-mole = kmol) in lbm (1 pound-mass = kg). Chapter 2 19

20 Notice that the molar mass of a substance has the way it is defined. When we say the molar mass of nitrogen is 28, it simply means the mass of 1 kmol of nitrogen is 28 kg, or the mass of 1 lbmol of nitrogen is 28 lbm. hat is, M = 28 kg/kmol = 28 lbm/lbmol he mass of a system is equal to the product of its molar mass M and the mole number N: m = MN he values of R and M for several substances are given in able A-1. he ideal-gas equation of state can be written in several different forms: V = m PV = mr mr= ( MNR ) = NR PV NR u = u V = N P = R u Chapter 2 20

21 Where is the molar specific volume, i.e., the volume per unit mole (in m 3 /kmol or ft 3 /lbmol) P V = P V An ideal gas is an IMAGINARY substance that obeys the relation: P = R IS A WAER VAPOR AN IDEAL GAS? he error involved in treating water vapor as an ideal gas is calculated and plotted in Fig It is clear from this figure that 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). But at higher pressures, the ideal-gas assumption yields unacceptable errors, particularly in the vicinity of the critical point and saturated vapor line. Chapter 2 21

22 Fig Chapter 2 22

23 2.7.- COMPRESSIBILIY FACOR- A MEASURE OF DEVIAION FROM IDEAL-GAS BEHAVIOR he deviation from ideal-gas behavior at a given temperature and pressure can accurately be accounted by introduction of a correction factor called COMPRESSIBILIY FACOR Z. It is defined as: P Z = or P = R ZR It can also be expressed as Z = actual ideal Where: ideal = R P Chapter 2 23

24 Obviously, z = 1 for ideal gases, and for real gases > 1 Z = < 1 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. he normalization is done as: P P R = and R = P cr cr GENERALIZED COMPRESSIBILIY CHAR is given in the Appendix in Fig. A-13 Chapter 2 24

25 Chapter OHER EQUAIONS OF SAE. Van der Waals Equation of State ( ) R b a P = + 2 Beattie-Bridgeman Equation of State ( ) = A B c R P u Benedict-Webb-Rutin Equation of State γ γ + + α = e c a a br C A R B R P u u u Virial Equation of State... d() c() b() a() R P =

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