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Lecture 2

Chapter 3

Pure Substance
a substance that has a homogeneous and invariable chemical composition may exist in more than one phase (i.e., mixture of phases) but chemical composition is similar in all phases Example: A mixture of ice and liquid water A mixture of liquid water and vapor (steam)

Phase and State Changes of a Substance


A pure substance can exist in different phases (solid, liquid, or gas) It can exist in equilibrium as a mixture of different phases When a pure substance exists as a mixture of two or more phases, it is in phase equilibrium when there is no tendency for the mass of each phase to change

Phase and State Changes of a Substance

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

Definitions: Saturation Temperature - the temperature at which vaporization takes place for a given pressure Saturation Pressure - the pressure at which vaporization takes place for a given temperature For a pure substance, there is a definite relation between the saturation temperature and saturation pressure which can be shown by the vapor-pressure curve.

A substance can exist in any of the following phases Compressed Liquid Subcooled Liquid Saturated Liquid Saturated Vapor Saturated Mixture Superheated Vapor

Compressed Liquid a liquid whose pressure is higher than the saturation pressure for the existing liquid temperature (sat. temp.) Subcooled Liquid another term for compressed liquid; a liquid whose temperature is lower than the saturation temperature for the existing liquid pressure (the saturation pressure) Saturated Liquid substance that exists as liquid only at saturation temperature AND saturation pressure Saturated Vapor substance that exists as vapor only at saturation temperature AND saturation pressure

Saturated Mixture substance that exists as a mixture of liquid and vapor for a given temperature (saturation temperature) AND pressure (saturation pressure) The liquid component in the mixture has the same properties as saturated liquid for the given temperature or pressure The vapor component in the mixture has the same properties as saturated vapor for the given temperature or pressure For a liquid-vapor mixture, a property that relates the mass of vapor to the mass of the mixture is defined:

Superheated Vapor substance in vapor phase whose temperature is higher than the saturation temperature for the existing pressure OR substance in vapor phase whose pressure is lower than the saturation pressure for the existing temperature

Quality - the ratio of the mass of vapor component to the total mass of the liquid-vapor mixture x = mg / m = mass of vapor / total mass of liquid-vapor mixture where mf = mass of liquid component mg = mass of vapor component m = mf + mg Note that x = 0 for saturated liquid x = 1 for saturated vapor

Property Relationships
V Vliq Vg

mv mliq v f mg vg
v fg vg v f

v (1 x) v f x vg v f x v fg
*note

v fg average specific volume v f =specific volume of a saturated liquid vg =specific volume of a saturated gas

Critical Point The state wherein the saturated liquid and saturated vapor states are identical It is specified by the critical temperature Tc , critical pressure Pc , or critical specific volume At pressures above the critical pressure, the liquid and vapor phases do not exist in equilibrium At supercritical pressures, the substance is simply called a fluid

T-v Diagram

P-V Diagram

Processes that involve phase change


Sublimation direct phase change from solid to vapor along the sublimation line, the solid and vapor phases (solidvapor mixture) exist in equilibrium Fusion direct phase change from solid to liquid along the fusion line, the solid and liquid phases (solid-liquid mixture) exist in equilibrium Vaporization direct phase change from liquid to vapor along the vaporization line, the liquid and vapor phases (liquid-vapor mixture) exist in equilibrium

Triple Point the state in which three phases are present in equilibrium for a pure substance, there may be many triple points but only one triple point where the solid, liquid, and vapor phases exist in equilibrium

Tables of Thermodynamic Properties


The thermodynamic tables lists other properties of a substance (e.g., v, u, h, s) as a function of two independent properties, commonly T and P 1. Saturated Liquid Saturated Vapor Region Tabulates properties of saturated liquid-vapor mixtures for a given temperature ( which is also equal to Tsat ) or a given pressure ( which is also equal to Psat ) Quality - An independent property of the liquid-vapor mixture which can be used to specify its state, defined as
x mvapor mmixture mvapor mvapor mliquid mg mg m f

Property Relationships
V Vliq Vvap

mv mliq v f mvap vg
v fg vg v f

v (1 x) v f x vg v f x v fg

2. Superheated Vapor Region Tabulates properties of superheated vapor Tests 1. For a given T and P, see if P < Psat) T or Tsat) P 2. For a given T and v , see if v > vg) T 3. For a given P and v , see if v > vg) P

T>

3. Compressed or Subcooled Liquid Region Tabulates properties of compressed or subcooled liquid Tests 1. For a given T and P, see if P > Psat) T or T< Tsat) P 2. For a given T and v , see if v < vf) T 3. For a given P and v , see if v < vf) P

Approximations In the absence of tables for the compressed liquid, its properties in most cases can be approximated by Using the property values of the saturated liquid state at the given temperature. Thus,
v (T , P)comp liq v f (T )
u (T , P)comp liq u f (T )

h (T , P)comp liq u f (T ) P v f (T ) h f (T ) v f (T ) P Psat (T )

Example
A rigid tank contains 50 kg of saturated liquid water at 90C.Determine the Pressure and Volume in the tank and draw its T-v Diagram

Example
A piston cylinder device contains 2m of saturated water vapor at 57.83 kPa pressure. Determine the temperature and the mass of vapor inside the cylinder, then draw its P-V Diagram.

Examples
Determine the Phase of each of the following water states and indicate the relative position in the T-v and P-v Diagram A) 120C,500 kPa B) 120C,0.5m/kg

Example

Examples
Determine the phase for each of the following states and indicate the relative position in the T-v and P-v Diagram a) Ammonia @ 30C,1000 kPa

B) R-22 @ 200 kPA,0.15 m/kg

Examples
A closed vessel contaions 0.1m of saturated liquid and 0.9m of saturated vapor R-134a in equilibrium at 30C.Determine the percent vapor on a mass basis

Seatwork
A closed vessel contaions 0.3m of saturated liquid and 0.7 m of saturated vapor R-134a in equilibrium at 81.24C.Determine the percent liquid on a mass basis

Extending the Diagrams to Include the Solid Phase


*P-v Diagram of a substance that contracts on freezing

Extending the Diagrams to Include the Solid Phase


**P-v Diagram of a substance that expands on freezing

Thermodynamic Surfaces We can represent the P-v-T behavior of a substance as a surface in space.

P-v-T Diagram of a substance that contracts on freezing

P-v-T Diagram of a substance that expands on freezing

Equations of State for the Gas Phase of a Simple Compressible Substance


Experimental observations established that the P v T behavior of gases at low density closely follows the following equation of state, also known as the Ideal Gas Equation of State , on a per mol basis
where Pv P = absolute pressure v = specific volume per mol R = universal gas constant = 8.3145 ( kJ / kmol-K ) = 1545 ( ft-lbf / lb mol-R ) T = absolute temperature

RT

P v RT
The equation of state expressed on a unit mass basis is where v = v / M = specific volume per unit mass (kg or lbm) R = R / M = gas constant (depends on gas species) M = gas molecular weight (depends on gas species) In terms of total volume, the above two equations become
PV n RT

PV m RT where V = gas total volume ( m3 or ft3 ) n = total number of mols of gas m = total mass of gas

For the same gas undergoing a change of state, the equation of state can be used to relate the initial and final states as P V1 mT P V1 n1 T1 1 1 1 1 or
P2 V2 m2 T2

P2 V2

n2 T2

Restrictions: The ideal gas equation of state may be applied to real gases or vapors only at very low densities May be applied to real gases or vapors at a given T, P only when the compressibility factor Z is close to 1.0

Compressibility Factor of a Gas


Is defined as

Pv Z RT

Z = 1 for an ideal gas The closer the value of Z to unity for a given T, P , the closer is the substance to ideal gas behavior

For a given T, P , if Z < 1 actual density is greater than predicted from ideal gas equation due to greater intermolecular attractive force Z > 1 actual density is less than predicted from ideal gas equation due to greater intermolecular repulsive force caused by much reduced intermolecular distances

GENERALIZED COMPRESSIBILITY CHART

This plot of the generalized compressibility factor Z in terms of the reduced pressure Pr and reduced temperature Tr is applicable to various simple substances.

Pr = P / Pc = reduced pressure Tr = T / Tc = reduced temperature Pc = critical pressure Tc = critical temperature See Table A.2 for Pc and Tc of various substances

The generalized compressibility chart indicates that ideal gas behavior can be assumed when P << Pc T > 2Tc up to P 4 to 5 times Pc For other conditions, especially in the superheated vapor region, it is more accurate to use the thermodynamic tables May be used to estimate P-v-T data of substances if no tables are available