CHNG 2002

Chemical Process Principles

II

VOLUMETRIC PROPERTIES OF
FLUIDS (PVT DATA)
THE IDEAL GAS
• A gas with the following properties is an ideal gas:

• Attractive and repulsive forces between molecules are negligible.

• Volume of molecules negligible compared to volume of gas.

• Molecules are like perfectly elastic spheres.

• Duration of a collision is negligible compared to the time between collisions.

THE IDEAL GAS
• PVT relationship is given by the ideal gas equation of state

• 𝑃𝑉 = 𝑛𝑅𝑇
• Where P = Pressure
V = Volume
n = Number of Moles
R = Universal Gas Constant
T = Absolute Temperature
THE IDEAL GAS
• NB: 1) The ideal gas law is universal, i.e. it applies to any gas and is
independent of the nature of the gas.

2) The P-V plot is a rectangular hyperbola at a given temperature.

3) Real gases do not obey this law, however, at high temperature

and low pressure, real gases tend to follow the law more
closely.

4) At room temperature and pressure, a suitable approximation

can be used for real gases.
THE IDEAL GAS
• Alternate expressions of the ideal gas law (done in class)

• Units for universal gas constant, R

• R = 8.314 J mol-1 K-1 (Pa m3 mol-1 K-1)
• R = 8.314 kJ mol-1 K-1 (kPa L mol-1 K-1)
• R = 0.08206 atm L mol-1 K-1
• R = 62.36 mmHg L mol-1 K-1
• R = 1.987 cal mol-1 K-1
THE REAL GAS
• Real gases have finite molecular volumes and inter-molecular/repulsive
forces do exist.

• Consider the following graphs (drawn in class)

• Critical Temperature, Tc – temperature at or below which the gas of a substance
can be liquefied. Above this temperature, the liquid cannot exist.

• Critical Pressure, Pc – maximum pressure required to liquefy a gas at its critical

temperature.

• Critical Molar Volume, vc – volume occupied buy one mole of gaseous substance
at the critical temperature and pressure.
THE REAL GAS – Equations of State (EOS)
• Classical EOS is the van der Waals EOS
• Corrects real gas volume by allowing for molecular volume
• Corrects pressure term by accounting for attractive forces

Where a and b are constants

unique to each gas

• Since V = nv, then we get

• The van der Waals EOS can also be expressed as

 THE REAL GAS – Equations of State (EOS)
• Example 1: Calculate the pressure in a 1 m3 vessel containing 25 kg of
steam at 100 ℃. [a = 5.48 x 106 atm (cm3)2 mol-2 & b = 30.6 cm3 mol-1]
THE REAL GAS – Equations of State (EOS)
• NB: We can solve for a and b in the van der Waals EOS by using Pc and
Tc
THE REAL GAS – Equations of State (EOS)
• Redlich-Kwong EOS – improvement of van der Waals EOS
THE REAL GAS – Compressibility Factor

• Where z = compressibility factor

• For an ideal gas, z = 1

• Any deviation in z from a value of 1 is a measure of the deviation from

ideal gas behaviour.

• If we can determine z, we can use

• This correlation is known as the generalized gas law.

THE REAL GAS – Compressibility Factor
• Law of Corresponding States – all gases, when compared at the same
reduced temperature and pressure, have approximately the same
compressibility factor and all deviate from ideal gas behaviour to
about the same degree.

• We define reduced parameters as follows:

Where Ir is the reduced property and Ic is the critical

property
THE REAL GAS – Compressibility Factor
• From the general reduced property form, we can define the following.

• For all gases, z = z(Pr , Tr)

• Where no EOS or experimental data is available, we can use the
generalized compressibility chart.
• To use the chart, we require Pc and Tc for the substance.
• Then, calculate Pr and Tr which we then use to read off z from the chart.
THE REAL GAS – Compressibility Factor
• There are exceptions to the rule!
• In the case of H2, He and Ne, we need to use a modified critical
temperature, Tc’ and modified critical pressure, Pc’ in order to use the
chart.

• Thus, we have
THE REAL GAS – Compressibility Factor
• Example 2: Calculate the volume occupied by 5 kg of ethane at 150 ℃ and
15 atm. For ethane, Pc = 48.2 atm and Tc = 306 K.

• Example 3: Calculate the pressure in a 1 m3 reactor, containing 242 kg of

methane at 107 ℃. For methane, Pc = 45.4 atm and Tc = 190.6 K. Note that
since z = z(Pr , Tr), a trial and error procedure is needed.

• Example 4: Calculate the temperature in a 5 m3 storage vessel, containing

241.5 kg of hydrogen at 62.4 atm. For hydrogen, Pc = 12.84 atm and Tc =
33.3 K. Note that since z = z(Pr , Tr), a trial and error procedure is needed.
THE REAL GAS – Compressibility Factor
• Modification of the law of corresponding states
• The original law claims that the critical compressibility factor, zc is the same
for all gases.

• However, zc varies from 0.2 to 0.3.

• Two approaches have been used to improve the law.

 THE REAL GAS – Compressibility Factor
• 1) Use of zc
• zc is defined as

• Hence, zc is now a third parameter in addition to Pr and Tr and the law of

corresponding states is now written as

• 2) Use of Pitzer’s acentric factor, ω (not to be used for water or other

strongly polar substances)
• The compressibility factor is written as

• The correlation is given by and

• Where z0 is the compressibility factor for simple fluids, ω is the acentric factor, z1 corrects z
for the effects of non-spherical intermolecular forces (primarily dispersion and overlap) and Prs
is the reduced saturated vapour pressure of the pure substance at a reduced temperature of 0.7.
GAS MIXTURES – DALTON’S LAW
• Dalton’s Law – total pressure of a gas is made up of the sum of
pressures exerted by the individual molecules of each component gas,
and that each gas in a gaseous mixture can hypothetically be
considered to exert a partial pressure.
• The partial pressure is the pressure obtained if the same mass of the
component gas were to occupy by itself the same total volume, at the
same temperature.

Where PT = Total Pressure

Pi = partial pressure of species I
n = number of component gases
GAS MIXTURES – DALTON’S LAW
• Dalton postulated ………(1)
Where Pi = pressure of species i; V = total volume; ni = number of
moles of species I; R = universal gas constant; T = absolute temperature

• Finding the sum of all species in the mixture, we get

… ..….(2)
Where nT = total number of moles
• Dividing (1) and (2), we get
GAS MIXTURES – DALTON’S LAW
𝑛𝑖
• This implies since 𝑦𝑖 =
𝑛𝑇
• And

• If the mole fraction, yi, of an individual gaseous component in a gas

mixture is known, and the total pressure is known, then we can
calculate the partial pressure of that component.
GAS MIXTURES – AMAGAT’S LAW
• This law is based on additive volumes as opposed to additive
pressures in Dalton’s law.

• Where VT = total volume; Vi = partial volume

of species i.

• Amagat postulated ……(3)

• Finding the sum of all species in the mixture, we get

……(4)
GAS MIXTURES – AMAGAT’S LAW
• Dividing (3) and (4), we get

𝑛𝑖
• This implies since 𝑦𝑖 =
𝑛𝑇
• And

• We can find the volume occupied by a species in the mixture if we

know the mole fraction of the species and the total volume of the
mixture.
MEAN COMPRESSIBILITY FACTOR – DALTON’S
LAW
• Recall from Dalton’s Law
• Assume for a real gas that where zi is the compressibility

factor of species I measure at Pi, T, i.e the partial pressure of species I

and the system temperature.
• Combining both equations, we get

• Defining the mean compressibility factor, zm, we get

• This implies and therefore,

• Reasonable to use up to 50 atm.

MEAN COMPRESSIBILITY FACTOR – AMAGAT’S
LAW
• Recall from Amagat’s Law
• Assume for a real gas that where zi is the compressibility factor of
species I measured at PT, T, i.e. the system pressure and system
temperature.
• Combining both equations gives
• zm is defined for the mixture as

• This implies and hence,

• Reasonable to use up to 300 atm.

PSEUDO CRITICAL METHOD – KAY’S RULE
• Use of compressibility factor chart for mixtures using pseudo critical
constants.

• The reduced properties of the gas mixture can then be determined

using the above pseudo critical properties.

• A compressibility factor, z can then be determined using the

compressibility chart.
QUESTION
• Calculate the molal volume of a mixture containing 40.1 moles of N2
and 59.9 moles of C2H4 at 600 atm and 50 ℃, by the following
methods.
1) Ideal Gas Law
2) Amagat’s Law and Chart
3) Dalton’s Law and Chart
4) Pseudo Critical Method

The critical temperature and pressure are respectively, for N2 (126 K

and 33.5 atm) and for C2H4 (292 K and 50 atm).
APPLICATIONS OF EOS TO MIXTURES
• Recall the van der Waals EOS where a and b are constants for a gas.
• For mixtures of gases, we define mixing rules that allow for mean
constants to be determined for the mixture, am and bm.
• Recall van der Waals EOS equations

• For the constants, we have

APPLICATIONS OF EOS TO MIXTURES
• For a binary mixture of gases,

• Several methods are used to determine a12.

• In cases where k12 is not known, an initial value is k12 = 0.

 QUESTION
• Dry air contains 78.09 % N2, 20.95 % O2, 0.03 % CO2 and 0.93 % Ar by
volume. The density of the air is 5.739 x 103 mol m-3 at 200 K and 8.0 x 106
Pa. Compare the true pressure with that obtained using the van der Waals
EOS.