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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
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)
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.
PV B 1 RT V
Pitzer Acentric Factors , , a parameter that reflects the geometry and polarity of a molecule
RTc B ( Bo B1 ) P c
Bo 0.083
0.422 1.6 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
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
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.
100 gmoles of nitrogen is contained in a 5 liter vessel at -20.60C. Estimate the pressure in the cylinder.
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?