Single-Phase Systems

Material Balances Involving Ideal Gases

Chapter 5
 Liquid and Solid Densities
• Assumption: solid and liquid densities are independent of temperature.
Similarly, changes in pressure do not cause significant changes in liquid
or solid densities; these substances are therefore termed Incompressible.
 Ideal Gases
The Ideal Gas Equation of State- The ideal gas equation of state can be
derived from the kinetic theory of gases by assuming that gas molecules have
a negligible volume, exert no forces on one another, and collide elastically
with the walls of their container.
𝑷𝑽 = 𝒏𝑹𝑻 OR P𝑽ሶ = 𝒏𝑹𝑻
ሶ

A gas whose behavior is well represented by above equation is said to behave as an ideal
gas or a perfect gas.
 1 mole of an ideal gas at 0° C and 1 atm occupies 22.415 liters,
whether the gas is argon, nitrogen, a mixture of propane and air, or
any other single species or mixture of gases.

The ideal gas equation of state is an approximation. It works

well under some conditions generally speaking, at temperatures
above about 0° C and pressures below about 1 atm but at other
conditions its use may lead to substantial errors.
 Standard Temperature and Pressure

Since the standard conditions are known, this equation may

be used to determine V for a given value of n or vice versa.

• The term standard cubic meter (or SCB ) is often used to denote
m2 (STP), and standard cubic feet (or SCF ) denotes ft3 (STP).
Conversion from Standard Conditions
Butane (C4H10 ) at 360 °C and 3.00 atm absolute flows into a reactor at a rate of 1100
kg/h. Calculate the volumetric flow rate of this stream using conversion from standard
conditions.
Soln. Always, molar quantities and absolute temperature and pressure must be used.
Standard and True Volumetric Flow Rates
The flow rate of a methane stream at 285 °F and 1.30 atm is measured with an orifice meter. The
calibration chart for the meter indicates that the flow rate is 3.95x105 SCFH.
• Calculate the molar flow rate and the true volumetric flow rate of the stream.

Soln.

Now, V1= 3.95x105 ft3/h at T1= 492 °R, P1=1.0 atm

V2= ??? ft3/h at T2= 745 °R, P2=1.3 atm,

 Ideal Gas Mixtures
• Suppose nA moles of substance A, nB moles of B, nC moles of C, and
so on, are contained in a volume V at a temperature T and total
pressure P such that each of the individual mixture components and
the mixture as a whole behave in an ideal manner. This is the
definition of an ideal gas mixture
Ideal Gas Mixtures
Material Balances on an Evaporator-Compressor
Liquid acetone (C3H6O) is fed at a rate of 400 L/min into a heated chamber, where it
evaporates into a nitrogen stream. The gas leaving the heater is diluted by another nitrogen
stream flowing at a measured rate of 419 m3 (STP)/min. The combined gases are then
compressed to a total pressure P=6.3 atm gauge at a temperature of 325 °C. The partial
pressure of acetone in this stream is pa=501 mm Hg. Atmospheric pressure is 763 mm Hg.

1. What is the molar composition of the stream leaving the compressor?

2. What is the volumetric flow rate of the nitrogen entering the evaporator if the temperature
and pressure of this stream are 27°C and 475 mm Hg gauge?

Soln. Basis: Given acetone rate (400 L/min)

Assumption: Ideal gas behaviour
Let: 𝒏𝟏ሶ , 𝒏𝟐ሶ , ……. (mol/min) be the molar flow rates of each stream
 Density of liquid acetone is 0.791 g/cm3 (791 g/L) (Table B1)

So,

Determine Mole Fractions from Partial Pressures,

So that,
Calculate n3ሶ from PVT Information,

Overall Mole Balance on Acetone,

Overall Mole Balance:

Pabs
 Equations of State
• A virial equation of state expresses the quantity 𝑷𝑽෡ൗ𝑹𝑻 as a
power series in the inverse of specific volume:

where B,C and D are functions of temperature and are known as the second,
third, and fourth virial coefficients, respectively. Note that the ideal gas equation
of state is obtained if B=C=D= ... = 0

Truncating the virial equation of state after the second term yields
෡
𝑷𝑽 𝑩
=𝟏+
𝑹𝑻 ෡
𝑽
• Pitzer acentric factor 𝝎 : A parameter that reflects the geometry and
polarity of a molecule.
Table 5.3-1 lists values of for selected compounds,
and a more complete list can be found in Reid et al.
• Reduced temperature,
Tr = 𝑻ൗ𝑻𝒄

• Estimate B using the following

equations:
The Truncated Virial Equation
Two gram-moles of nitrogen is placed in a three-liter tank at -150.8°C. Estimate the tank
pressure using the ideal gas equation of state and then using the virial equation of state
truncated after the second term. Taking the second estimate to be correct, calculate the
percentage error that results from the use of the ideal gas equation at the system conditions.

Soln.
T= (-150+273)=122.4 K
෡=3.00L/2.00 mol=1.5 L/mol
V
 Virial
coefficients,

Error in the pressure calculated using the ideal gas equation of state is,
 Cubic Equations of State
• A number of analytical PVT relationships are referred to as cubic equations
of state because, when expanded they yield third order equations for the
specific volume. The Van der Waals equation of state is the earliest of
these expressions, and it remains useful for discussing deviations
fromideal behavior. 𝑹𝑻 𝒂
𝑷= − 𝟐
෡−𝒃 𝑽
𝑽 ෡

𝟐𝟕𝑹𝟐 𝑻𝟐𝒄 𝑹𝑻𝒄

Where 𝒂= 𝒃=
𝟔𝟒𝑷𝒄 𝟖𝑷𝒄

• Other important cubic equations of state are the Redlich-Kwong, Soave

Redlich-kwong(SRK), and Peng-Robinson equations.
 𝑹𝑻 𝒂
The SRK equation of state is 𝑷 = − 𝟐
෡−𝒃 𝑽
𝑽 ෡
where the parameters a, b, and 𝜶 are empirical functions of the critical
temperature and pressure (Tc and Pc are from Table B.1)

• Following correlations are used to estimate these three parameters:

The SRK Equation of State
A gas cylinder with a volume of 2.50 m3 contains 1.00 kmol of carbon dioxide at T= 300
K. Use the SRK equation of state to estimate the gas pressure in atm.

Soln.

Specific molar volume,

Tc=304.2K and Pc=72. 9 atm (Table B1)

ω=0.225 (Table 5.3-1)
So, the parameters in the SRK equation of state are evaluated as,
The SRK equation (5.3-7) can now be solved for the tank,

 Use of the ideal gas equation of state leads to an estimated pressure of

9.85 atm (verify ), a deviation of 5% from the more accurate SRK-
determined value.
 Critical Temperature and Pressure
• At a very low pressure, and the density of the liquid is more than four orders
of magnitude greater than that of the vapour. At higher temperatures, the
condensation pressure increases and the densities of the vapour and liquid at
condensation approach each other.

• Densities of water vapour (ρv) and liquid water (ρl)

Table B.1
• Highest temperature at which a species can coexist in two phases (liquid
and vapour) is the critical temperature of that species, Tc, and the
corresponding pressure is the critical pressure, Pc

• A substance at Tc and Pc is said to be at its critical state

• The terms “gas” and “vapour” are often used interchangeably, but there is a
technical difference between them.

A vapour is a gaseous species below its critical temperature, and a gas is a

species above its critical temperature at a pressure low enough for the
species to be more like a vapour than a liquid (i.e., a density closer to 1 g/L
than 1000 g/L)
Phase diagrams are basically plots between temperature and pressure
which are used to summarize the conditions under which different phases
of the substances can exist.
Examples of equations of state
• All of them are based on modifying the
ideal gas law

• They are semi-empirical:

modifications are based on
thermodynamic theories constants based
on curve fitting experimental data

• Conditions/range of applicability vary

from theory to theory

• Most wide used equations of state

include:
Van der Waals equation of state
Redlich Kwong equation of state
 The Compressibility Factor Equation of State
The compressibility factor of a gaseous species is defined as the ratio
෡
𝑷𝑽
𝒛=
𝑹𝑻
If the gas behaves ideally, z=1. The extent to which z differs from 1 is a
measure of the extent to which the gas is behaving nonideally.

The above equation may be rearranged to form the compressibility factor

equation of state
෡ = 𝒛𝑹𝑻
𝑷𝑽

෡ = 𝑽Τ𝒏 for a fixed quantity of gas and 𝑽ሶ ൗ𝒏ሶ for following stream
since 𝑽
𝑷𝑽 = 𝒛𝒏𝑹𝑻
𝑷𝑽ሶ = 𝒛𝒏𝑹𝑻
ሶ
Compressibility Chart
Newton’s correlation
(Kay’s rule): A mixture of 75% H2 and 25% N2 (molar basis) is contained in a tank
at 800 atm and 70 °C. Estimate the specific volume of the mixture in L/mol using
Kay’s rule.

Soln.
Critical constants (Table B1)

(Newton’s correlation)

(Newton’s correlation)

Pseudo-critical constants:
Mixture Compressibility:
Values of R Units
8.314 J⋅K−1⋅mol−1
8.314×10−2 L⋅bar⋅K−1⋅mol−1
8.314 m3⋅Pa⋅K−1⋅mol−1
62.364 L⋅Torr⋅K−1⋅mol−1
1.987×10−3 kcal⋅K−1⋅mol−1
8.206×10−5 m3⋅atm⋅K−1⋅mol−1
0.082 L⋅atm⋅K−1⋅mol−1
Spray drying is a process in which a liquid containing dissolved or suspended solids is
injected into a chamber through a spray nozzle or centrifugal disk atomizer. The resulting mist
is contacted with hot air, which evaporates most or all of the liquid, leaving the dried solids to
fall to a conveyor belt at the bottom of the chamber.
Powdered milk is produced in a spray dryer 6 m in diameter by 6 m high. Air enters at 167°C
and -40 cm H2O. The milk fed to the atomizer contains 70% water by mass, all of which
evaporates. The outlet gas contains 12 mole% water and leaves the chamber at 83°C and 1
atm (absolute) at a rate of 311 m3/min.

Calculate the production rate of dried milk and the volumetric flow rate of the inlet
air. Estimate the upward velocity of air (m/s) at the bottom of the dryer.