Chapter 5

Single-Phase Systems
Dr. Nahid Sanzida
nahidsanzida@che.buet.ac.bd
 Density of Liquids and Solids
The density of a liquid or solid solution can be determined
by the following two equations:
5.1.1

5.1.2
where, xi is the mass fraction of component i.
ρ is the density of the solution,
ρi is the density of pure component i.
Equation 5.1.1 assumes that the total volume is the sum of the
individual volumes; Volume additivity is relatively accurate for solutions
of liquids with similar molecular structures.
The accuracy of equation 5.1.2 over equation 5.1.1 depends on
the system considered.
 Example 5.1-1 Determination of a Solution Density
Determine the density in g/cm3 of a 50 wt% aqueous
solution of H2S04 at 20°C, both by
(1) looking up a tabulated value and
(2) assuming volume additivity of the solution components.

Answer: Strategy: To calculate the density of H2S04 and water

mixture, we will need the values of the densities of the pure
components of the liquid mixture.
Example 5.1-1 Determination of a Solution Density

We then estimate from Equation 5.1-1:

l/p = (0.500/0.998 + 0.500/1.834) cm3/g= 0.7736 cm3/g

p= 1.29 g/cm3
This leads to an estimation error of [(1.29 - 1.3951)/l.3951] X 100%
= -7.3%.
Alternatively, we could estimate the density from Equation 5.1-2:

P = (0.500 X 0.998 + 0.500 X 1.834) = 1.42 g/cm3

This leads to an estimation error of [(1.42-1.3951)/1.3951] X 100%
= 1.5%.
Clearly, the accuracy
of Equation 5.1-2 is better in this instance than that of Equation 5.1-1.
Properties of Pure Ideal Components
Incompressible: This term is used to specify the assumption
of constant density of a material. Incompressibility is
closely followed by liquids and solids under many
situations of interest.
Correlation: This is a mathematical fit of experimental data
(usually using statistical methods). These are used either
in place of or in conjunction with physics based models.
Equations of State (EOS): These are correlation or
physically based equations that relate Pressure, Volume,
and Temperature that exist inside a material (typically
gas). These three thermodynamic variables are easily
measured and make up what is known as a PVT
relationship.
 The Ideal Gas Equation of State
An equation of state relates the molar quantity and volume of a
gas to temperature and pressure. The simplest and most widely
used of these relationships is the ideal gas equation of state
which usually appears in the form
PV = nRT or PV  n RT 5.2.1
The Ideal Gas Equation of State
A gas whose PVT behavior is well represented by
Equation 5.2-1 is said to behave as an ideal gas or a
perfect gas.
The ideal gas EOS is based on the primary
assumptions that
• There are no intermolecular forces between
the gas particles.
• The volumes of molecules are negligible (i.e.
the gas particles can be treated as “point”
particles).
 Ideal Gas Mixtures
Imagine we have a gas mixture inside a container. We can
then define:
Partial Pressure (PA): This is the pressure, PA, that the
moles of gas A in the gas mixture would exert if the moles of
gas A was all that was present in the container (at the same
temperature T).
Pure Component Volume (vA): This is the volume, vA, that
the moles of pure gas A would occupy at the total pressure P
and temperature T of the mixture.
In an ideal gas mixture, the various gas molecules do not interact. This
means that the pressure exerted by each component A is independent of
the others; thus its partial pressure is given by
PAV= nART
 Ideal Gas Mixtures
Dividing the second equation by PV = nRT yields
p A nA
  y A (the mole fraction of A in the
P n gas mixture)

or pA = yAP 5.2-7

That is, the partial pressure of a component in an ideal gas

mixture is the mole fraction of that component times the total
pressure. Since, yA + yB +… = 1.

pA + pB +… = (yA + yB +…)P = P 5.2-8

Or, the partial pressures of the components of an ideal gas

mixture add up to the total pressure (Dalton’s law).
 Ideal Gas Mixtures
A similar series of calculations can be performed for
pure components volumes:
PvA = nA RT.

Dividing the PV= nRT

vA nA
  yA
V n
or
vA = yAV 5.2-9

vA + vB +… = V (Amagat’s Law)
 Non-ideal Gases
 An ideal gas is a theoretical idea – in which there are no
attractive forces between the molecules, and in which the
molecules take up no space. Both of these assumptions are
incorrect.
 if there were no attractive forces between molecules, no
substances would ever condense from the gas state to
become liquids and solids. In fact, every substance does
condense when it is cooled and compressed enough.
Therefore there must be attractive forces between molecules.
 if molecules took up no space, then we could compress
substances until they had no volume at all. In fact, solids and
liquids are almost incompressible, since their molecules are
basically touching each other. Since solids and liquids take up
space, the molecules of which they are made must take up
space also.
 Non-ideal Gases
Critical Temperature (Tc) and Critical Pressure (Pc):
The highest temperature at which a species can
coexist in two phases (liquid and vapor) is the critical
temperature of that species, Tc, and the corresponding
pressure is the critical pressure, Pc.
Critical Point (Critical State) of a Fluid: A substance at
Tc and Pc is said to be at its critical state.
Table B.l confirms that, for water,
Tc = 374.15°C and Pc = 218.3 atm.
Supercritical Fluids: Substances at temperatures
above Tc and pressures above Pc are referred to as
supercritical fluids.
 Non-ideal Gases
Reduced Pressure (Pr): This is the actual pressure of a
fluid divided by its critical pressure, Pr = P/Pc
Reduced Temperature (Tr): This is the actual
temperature of a fluid divided by its critical temperature,
Tr = T/Tc
Law of Corresponding States: This is an empirically
based principle that states that all fluids deviate from
ideality in a similar fashion, when compared at the
same reduced temperature Tr and reduced pressure Pr
 Non-ideal Gases

Pitzer Accentric Factor (ω):

This factor is a parameter
used in non-ideal equations
of state that takes into
account the geometry and
polarity of a molecule.
 EQUATIONS OF STATE FOR
NONIDEAL GASES
 Because in reality molecules of a gas do interact, all real
gases are nonideal.
 The ideal gas EOS may be a very good approximation at
low pressures and high temperatures.
 At higher pressures and/or lower temperatures the impact
of intermolecular interactions on gas behavior increases.
 Methods for nonideal gases must be used to account
for the effect of these interactions on the relationship
between P,V, and T (and related properties such as
density) of a gas.
 Below, the following three methods will be introduced:
1. Virial Equation of State
2. Van der Waals Equation of State
3. Soave-Redlich-Kwong (SRK) Equation of State
 EQUATIONS OF STATE FOR NONIDEAL GASES
Virial Equation of State
The Virial Equation of State is an infinite power series in the inverse
of the specific molar volume:

where B, C, and D are functions of temperature and are known as the

second, third, and fourth virial coefficients, respectively. Most often,
the virial EOS is truncated after the second term to simplify to:

B, can be estimated from the

following corresponding
states correlations:

Our text lists values for the Pitzer accentric factor in table 5.3-1 and for
the critical pressure and temperature in Appendix B (table B.1).
Example 5.3-1: 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.

Solution:

From the ideal gas equation of state,

Example 5.3-1:
Example 5.3-1:
 Cubic Equations of State
Van der Waals Equation of State
It is the earliest of these expressions, and it remains
useful for discussing deviations from ideal behavior.

In the van der Waals derivation, the second term on the right
accounts for attractive forces between molecules and b is a
correction accounting for the volume occupied by the
molecules themselves.
 Cubic Equations of State
Soave-Redlich-Kwong (SRK) Equation of State

The parameters of the SRK EOS are calculated from the following:
Exercise 5.58: A 5.0m3 tank is charged with 75.0 kg
of propane gas at 25°C. Use the SRK equation of
state to estimate the pressure in the tank; then
calculate the percentage error that would result
from the use of the ideal gas equation of state for
the calculation.
Solution:
 TEST YOURSELF
1. Why is the SRK equation of state called a cubic
equation of state?
Ans: The equation to determine V for given values
of T and P is a cubic equation.
2. What physical properties of a species do you
have to look up in order to use the SRK
equation of state? Where can you find values of
these properties in this text?
Ans: Critical temperature and pressure (Table B.l),
Pitzer acentric factor (Table 5.3-1)
Exercise 5.25:
An ideal gas mixture contains 35% helium, 20% methane, and 45%
nitrogen by volume at 2.00 atm absolute and 90° C. Calculate
(a) the partial pressure of each component,
(b) the mass fraction of methane,
(c) the average molecular weight of the gas, and
(d) the density of the gas in kg/m3 .

Solution
Exercise 5.17: 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.
a) Calculate the production rate of dried milk and the
volumetric flow rate of the inlet air.
b) Estimate the upward velocity of air (m/s) at the bottom of the
dryer.
c) What problem would you guess would occur if the velocity is
too high?
5.30: fuel gas containing 86% methane, 8% ethane, and 6%
propane by volume flows to a furnace at a rate of 1450 m3/h
at 15° C and 150 kPa (gauge), where it is burned with 8%
excess air. Calculate the required flow rate of air in SCMH
(standard cubic meters per hour).
5.30: fuel gas containing 86% methane, 8% ethane, and 6%
propane by volume flows to a furnace at a rate of 1450 m3/h
at 15° C and 150 kPa (gauge), where it is burned with 8%
excess air. Calculate the required flow rate of air in SCMH
(standard cubic meters per hour).