Definitions

Critical Temperature (Tc): Highest temperature at which a species can coexist in two phase (liquid and vapor) Critical Pressure (Pc): Pressure that corresponds to critical temperature Critical Point (Critical State) of a fluid: The critical point refers to the state when the fluid is at Tc and the corresponding critical pressure,Pc. Such a fluid can still coexist, at Tc and Pc, as a liquid and vapor mixture.

Reduce Pressure (Pr): This is the actual pressure of a fluid divided by its critical pressure, Pr=P/Pc
Reduce Temperature (Tr): This is the actual temperature of a fluid divided by its critical pressure, Tr=T/Tc

Pitzer Acentric Factor: This factor (symbol ) is a parameter used in non ideal equations of state that takes into account the geometry and polarity of a molecule

Calculate the reduced temperature and pressure:

Standard conditions
Standard conditions can be conveniently used calculate the PVT relations at the other condition.
PV nT PsVs nsTs
System SI CGS Ts 273 K 273 K Ps 1 atm 1 atm Vs 0.022415 m3 22.415 liters Ns 1 mol 1 mol

English

492 oR

14.7 psi

359.05 ft3

1 lb=-mol

Non-ideal gases
In reality molecules of a gas do interact, all real gases are nonideal. At, higher pressures and/or lower temperatures the impact of intermolecular interactions on gas behavior increases Non ideal gas method must be used to account for the effect of these interaction on the relationship between P,V and T ( and related properties such as density) of a gas Below, the following five methods will be introduced:
Virial Equation of State Van der Waals Equation of State Soave-Redlich-Kwong (SRK) equation of state Compressibility Factor Equation of State Kays Rule (for non ideal gas mixtures)

Virial Equations of State

The virial expansion, also called the virial equation of state, is the most interesting and versatile of the equations of state for gases.. The virial expansion is a power series in powers of the variable, n/V, and has the form,

The coefficient, B(T), is a function of temperature and is called the "second virial coefficient. C(T) is called the third virial coefficient, and so on. The expansion is, in principle, an infinite series, and as such should be valid for all isotropic substances. In practice, however, terms above the third virial coefficient are rarely used in chemical thermodynamics.

Truncated virial equation (truncated at 2nd term)

PV B 1 RT V

Pitzer Acentric Factors , , a parameter that reflects the geometry and polarity of a molecule

Estimate B using the following equations:

RTc B ( Bo B1 ) P c

Bo 0.083

0.422 1.6 Tr

0.172 B1 0.139 4.2 Tr

Example:

Two gram-moles of nitrogen is placed in a three liter Estimate the tank pressure using; i) ideal gas equation of state ii) the virial equation of state truncated after the sec Taking the second estimate to be correct, calculate t error that results form the use of the ideal gas equati systems conditions

Van Der Waals Equation of State

Based on a modification of the ideal gas law Van Der Waals Constant

a v
2

The parameters a and b change from one gas to another but are independent of temperature Accounts for attractive forces between molecules

Correction accounting for the volume occupied by the molecules themselves

Soave-Redlich-Kwong (SRK) Equation of State

A more accurate cubic EOS is the empirical SRK equation: SOAVE-REDLICH-KWONG (SRK) EQUATION

The parameters of the SRK EOS are calculated the following

COMPRESSIBILITY FACTOR
The compressibility factor,Z is a useful thermodynamic property for modifiying the ideal gas law to account for the real gas behaviour

For ideal gas Z=1 The value Z generally increase with pressure and decreases with temperature At high pressures molecules are colliding more often, and at low temperatures they are moving less rapidly.

The procedure for using the generalized compressibility chart is as follows:

1. Find the critical pressure and the critical temperature for the fluid of interest( note: if the fluid is hydrogen or helium these critical values must be corrected) 2. Calculate the reduced pressure and temperature (note: all temperatures used must be absolute) 3. Use the compressibility chart to determine Z

The generalized Compressibility Chart

100 gmoles of nitrogen is contained in a 5 liter vessel at -20.60C. Estimate the pressure in the cylinder.

EXAMPLE : What is the compressibility factor of nitrogen at 800 ps

Example : A mountaineer on Mount Everest has a cylinder of suppl The volume of oxygen is 3.0 L and there are 1071 g oxyg The temperature outside is -30C. Estimate the pressure the tank using compressibility factors.

NON IDEAL GAS MIXTURE -Gas contains more than one species

EXAMPLE : A mixture containing 30 mole% isobutane and 70 mole% a container at 500 atm and -120C. What is the specific v mixture?