LESSON 1

PROPERTIES OF PURE SUBSTANCES

 The State Principle

 The state of an equilibrium system can be defined by its thermodynamic properties

 In systems undergoing equilibrium processes or that can be approximated by equilibrium

processes, the number of independent properties necessary to define the system is one
more than the number of relevant work interactions.

 For simple compressible systems (mechanical work) in the absence of potential and
kinetic energies that are included in the total energy term, two independent properties
can define the state.

 For simple compressible systems, the first law can be written as Q = ∆E + ∫ pdV we
can define all the other properties of the system, using two independent intensive
properties.

o Ex. if we know the temperature, T, and pressure, p, other properties can be

determined: h = h(T, p); u = u(T, p); v = v(T, p).

 Pure substance

 substance that is of constant chemical composition, regardless of phase.

 it is homogeneous by nature, does not undergo chemical reactions, and is not a

mechanical mixture of different species.

 Note: There is usually a sharp distinction between phases, inasmuch as the properties of
one phase are decidedly different from those of another phase.

 Liquid-Vapor Equilibrium
 Saturated Properties

o a - subcooled or compressed liquid

o b - saturated liquid
o c - mixture of liquid and vapor (saturated vapor)
o d - saturated vapor
o e - superheated vapor
o Saturation Temperature (Tsat ) – temperature of water when it is saturated liquid and
vapor, for a given pressure

 Critical Properties

o Critical point - a point that has a unique T and P known as critical temperature and
critical pressure
 1. (Fig 4.3) At pressures higher than the critical pressure, the liquid could be heated from a
low temperature to a high temperature without a phase transition occurring.

2. (Fig 4.4) At temperatures that are greater than the critical temperature, the pressure may
be increased to very high values, and no liquefaction will occur.
 Solid-Liquid-Vapor Equilibrium

o Triple point - the only point at which all three phases may coexist.
o Latent heat of fusion - the change of enthalpy between a solid and liquid phase
o Latent heat of vaporization -the change of enthalpy between a liquid and vapor phase
o Latent heat of sublimation - the change of enthalpy in going from a solid to a vapor
phase

 Quality, x

 mass of vapor in the system divided by the total mass of thesystem(mass of vapor plus
mass of liquid)
 Three-Dimensional Surface

LESSON 2
IDEAL AND REAL GASES

Ideal-Gas Equation of State

 relates the dependence of pressure, volume, temperature, and mass at a state

 The ideal-gas equation of state represents all the states on the AB surface, relating the
various properties to each other.

 Ideal-Gas Equation
pV=mRT

where:

 p - absolute pressure
 V - total volume
 m - mass
 R - individual gas constant
 T - temperature

dividing by the mass yields

pV=RT
 where

 v is the specific volume in m3/kg

Nonideal-Equation of States

 For actual gases

o molecular collisions are inelastic there are intermolecular forces (at high
densities)
o There are many gas equations of state that attempt to correct for the nonideal
behavior of gases.
 The disadvantage of all methods is that the equations are more complex and require the
use of experimental coefficients.

van der Waals Equation of State

 developed in 1873 as an improvement on the ideal-gas law

where

 a and b are coefficients to compensate for the nonideal characteristics of the gas
 constant b accounts for the finite volume occupied by gas molecules accounts
for intermolecular forces
Compressibility Factor

 The ideal-gas law works well for gases at low densities.

 As the pressure of the gas is increased for a given temperature, the molecules are
packed closer and closer together.
 This brings about nonideal behavior due to additional forces acting on the molecules
 For ideal gas,

Specific Heat at Constant Volume

Specific Heats at Constant Pressure

For an ideal gas, the changes in internal energy and enthalpy depend only on the temperature;
if the initial and final temperatures are known, the enthalpy and internal energy changes may be
calculated.

Further Considerations

Kinetic Theory - Pressure and Specific Heat of an Ideal Gas

 The pressure that a gas creates is caused by the impact of the gas molecules against a
surface.
 The force created by the impact is due to the change of momentum of a gas particle as it
hits and bounces from the surface
 Assumptions:
o volume of the molecule is negligible,
o the forces between the molecules are negligible,
o the molecules can be treated as rigid spheres that have elastic collisions with
themselves and with any surface.