Chapter 4

Single Phase System

Material and Energy Balances
Single-Phase
Systems
Liquid and
Solid
Densities
Ideal gas
relationships
Equation of
States
(EOS) for
Nonideal Gas
The
Compressibility
Factor EOS
Topic Outcomes
At the end of Chapter 4, you should:
Describe the meaning of incompressible fluids, the
term "equation of state", ideal gas behavior,
standard specific volume, partial pressure,
compressibility factors, z and the critical T and P.
Calculate PVT properties using ideal gas equation
of states.
Carry out PVT calculations for gas using truncated
virial EOS, van der Waals EOS, SRK EOS and the
compressibility factor EOS with either tabulated
compressibility factors or a generalized
compressibility chart for a single species and Kay's
rule for non-ideal mixture of gases.

Introduction
Before carried out a complete material balance, we
usually need to determine various physical
properties of materials in order to derive additional
relationship among the system variables.
3 way to obtain the values of physical properties
(such as density, vapor pressure, solubility, heat
capacity, etc)
1. Handbook or database
- Perrys Chemical Handbook, CRC Handbook of
Chemistry & Physics, TRC Database in Chemistry
& Engineering, etc
2. Estimation using empirical correlations
3. Experimental work

Density of Liquid and Solid
Liquid and solid expanded during heating and
density decreases. However, it is assumed that
the densities are independent of temp.
Change in pressure also do not caused changes
in solid and liquid densities. These substance is
termed as incompressible.
2 methods to estimate the density of mixture
consist n number of liquid.
Method 1: Volume Additivity

Method 2: Average Pure Component Densities

=
=
n
i
i
i
x
1
1

=
=
n
i
i i
x
1

Ideal Gases
Equation of state
Equation that relates the molar quantity and
volume of a gas to temperature and pressure.
Ideal gas equation of state
Simplest and most widely used for many
engineering calculations involving gases at low
pressure.
Used for gas a low pressure and high
temperature.
For high pressure and/or low temperature,
more complex equation of state for P,V and T
calculation.
Ideal Gas Equation of State
From the assumptions that gas molecules:
1)have negligible volume, 2) no force on one
another and 3) collide elastically with the wall
container. The equation:

or

The use of this equation does not require to
know the gas species:
1 mol of an ideal gas at 0C and 1 atm
occupies 22.415 liters, whether the gas is
argon, nitrogen, mixture of propane and air, or
any other single species or mixture of gases

nRT PV =
RT n V P

=
Ideal Gas Equation of State-cont.

P = absolute pressure
V = volume of the gas
n = number of moles of gas
R = gas constant which the unit depend on unit
of P, V, n, T
T = absolute temperature



nRT PV =
Ideal Gas Equation of State-cont.
Ideal gas equation of state can also be written as


Which ; specific molar volume of gas.
Unit for gas constant, R



R= 83.14 cm
3
bar mol
-1
K
-1
R= 8.314 J mol
-1
K
-1

RT V P =

n V V /

=
e temperatur mole
volume pressure
R for Unit

=
e temperatur mole
energy
R for Unit

=
Ideal Gas Equation of State-cont.
Density of ideal gas is calculated as:



Rule of thumb for when it is reasonable to
assume ideal gas behavior:
Let X
ideal
be a quantity calculated using ideal
gas equation of state (X can be pressure,
volume, temperature or mole).
Error is estimated value is

RT
M P
V
M
= =

% 100

=
true
true ideal
X
X X
c
V

To calculate is ideal specific molar volume,

If error calculated is satisfies this criterion, the
ideal gas equation of state should yield an
error less than 1%.


gases other mole) - lb / ft (320 L/mol 20
gases diatomic mole) lb / ft (80 L/mol 5

% 1
3
3
>
> <
ideal
V if c
Try Yourself
Example 5.2-1
Standard Temperature and Pressure
(STP)
A way to avoid the use of gas constant, R when
using ideal gas equation
For ideal gas at arbitrary temperature, T and
pressure, P
--------- (1)
For the same ideal gas at standard reference
temperature, Ts and standard reference pressure,
Ps (refer to STP).
-----------(2)
Divide eq. 1 to eq. 2 gives



nRT PV =
s s s
RT V P =

s
s s
T
T
n
V P
PV
=

Standard Conditions for Gases

System Ts Ps Vs ns Vs
SI 273K 1atm 0.022415 m
3
1 mol 22.4 m
3
/kmol
cgs 273K 1atm 22.415 L 1 mol 22.4 L/mol
English 492R 1atm 359.05ft
3
1 lb-mole 359.05 ft
3
/lb-mole

Value of standard conditions (Ps, Ts, Vs) are
known, above equation can be used to determine
V for a given n or vice versa
Standard cubic meters (SCM) = m
3
(STP)
Standard cubic feet (SCF) = ft
3
(STP)
^Vs= 22.4 m
3
(STP)/kmol
=22.4 L(STP)/mol=359 ft
3
(STP)/lb-mole
Try Yourself
Example 5.2-2
Try Yourself
Example 5.2-3
Try Yourself
Example 5.2-4
Ideal Gas Mixture
Suppose n
A
moles of species A, n
B
moles of
species B, n
c
moles of species C and so on, is
behave in ideal manner and contained in a
volume, V at temperature, T and pressure, P.

Partial pressure, p
A
The pressure that would be exerted by n
A

moles of species A alone in the same total
volume, V at the same temperature, T of the
mixture.


P y p
A A
=
Ideal Gas Mixture
The partial pressure of a component in an
ideal gas mixture is the mole fraction of that
component times the total pressure.
The summation of partial pressure of the
component of an ideal gas mixture is equal
to total pressure (Daltons Law).



P P y y y p p p
C B A C B A
= + + + = + + + ....) ( .....
Ideal Gas Mixture-cont.
Pure component volume, v
A
The volume would be occupied by n
A

moles of A alone at the same total
pressure, P and temperature, T of the
mixture.

Amagats Law


V y v
A A
=
V V y y y v v v
C B A C B A
= + + + = + + + ....) ( .....
Volume fraction = v
A
/V; percentage by volume
(%v/v)= (v
A
/V )x 100%

For an ideal gas mixture, the volume fraction is
equal to the mole fraction of the substance:
70% v/v C
2
H
6
= 70 mole% C
2
H
6

Liquid acetone (C
3
H
6
O
6
) 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
temperature of 325C. the partial pressure of acetone
ion this stream is pa=501 mmHg. Atmospheric
pressure is 763 mmHg.
a) What is the molar composition of the stream leaving
the compressor?
b) What is the volumetric flow rate of the N
2
entering the
evaporator if the temperature and pressure of this
stream are 27C and 475 mmHg gauge?
Try This
Equation of State for Nonideal
Gases
The ideal gas equation might be inaccurate for
low pressure and high temp. conditions. Hence,
more accurate equation will be introduced.

Either the ideal gas equation fits the PVT data for
a species depends on system temperature and
pressure which is critical temperature and critical
pressure.

Critical temperature (Tc)- the highest
temperature at which a species can exist in two
phases (liquid and vapor), and the corresponding
pressure is critical pressure (Pc).

Critical state- a substance at their critical
temperature and critical pressure.
Gas vs Vapor
At pressure low enough for the species to not be
a liquid:
Vapor: a gaseous species below its critical
temperature.
Gas: a gaseous species above its critical
temperature.
Species above Pc and above Tc- supercritical
fluids.

Virial Equation of State
Virial equation of state



B,C,D- second, third, fourth virial coefficients

Truncated virial equation





Tr=T/Tc
acentric factor from Table 5.3-1
Tc,Pc from Table B.1
....

1

3 2
+ + + + =
V
D
V
C
V
B
RT
V P
V
B
RT
V P

+ =
6 . 1
0
2 . 4
1 1 0
422 . 0
083 . 0 ;
172 . 0
139 . 0 ); (
r r
c
c
T
B
T
B B B
P
RT
B = = + = e
Try Yourself
Example 5.3-1
Cubic Equations of State
Refer as cubic equation because when the
equation is expanded, it become third-order
equation for the specific volume.

To evaluate volume for a given temperature and
pressure using cubic equation of state, we need
to do trial and error procedure.

Two famous cubic equation of state
a) Van der Waals equation of state
b) Soave-Redlich-Kwong (SRK) equation of state

Van der Waals Equation of State







(a/V
2
)- account for attractive force between molecules
b - correction accounting for the volume occupied by
the molecules themselves
2

V
a
b V
RT
P

=
c
c
c
c
P
RT
b
P
T R
a
8 64
27
2
2
= =
Soave-Redlich-Kwong (SRK)
Equation of state
)

(

b V V
a
b V
RT
P
+

=
o
2
2
2
1561 . 0 55171 . 1 48508 . 0
)] 1 ( 1 [ /
086 . 40
) (
42747 . 0
e e
o
+ =
+ = =
= =
m
T m T T T
P
RT
b
P
RT
a
r c r
c
c
c
c
Try This
A gas cylinder with a volume of 2.5 m
3
contains
1.00 kmol of carbon dioxide at T= 300 K. Use the
Soave-Redlich-Kwong equation of state to
estimate the gas pressure in atm.
Compressibility Factor Equation of State
or
If z=1, equation become ideal gas equation of state

The extent to which z differs from 1 is a measure
of the gas is behaving nonideally.
Alternatively; can use generalized compressibility
chart
Figure 5.4-1 generalized compressibility chart
Fig. 5.4-2 to Fig. 5.4-4 expansion on various
region in Fig. 5.4-1
zRT V P =

RT
V P
z

=

Step to Use Read Compressibility
Factor
1. Find Tc and Pc
2. If gas is either Hydrogen or Helium, determine
adjusted critical temperature and pressure form
Newtons correction equation


3. Calculate reduce pressure and reduce
temperature of the two known variables


4. Read of the compressibility factor from the chart
c
c
ideal
r
RT
V P
V
Pc
P
Tc
T
Tr

; Pr ; = = =
atm P P K T T
c
a
c c
a
c
8 8 + = + =
Class Discussion
Example 5.4-2
Nonideal Gas Mixtures
Kay Rule: estimation of pseudocritical properties
of mixture as simple average of pure a
component critical constants

Pseudocritical temperature (T
c
)
T
c
= y
A
T
cA
+ y
B
T
cB
+

Pseudocritical pressure (P
c
)
P
c
= y
A
P
cA
+ y
B
P
cB
+

Pseudocritical reduced temperature (T
r
)
T
r
= T/T
c




Pseudocritical reduce pressure (P
r
)
P
r
= P/P
c


Compressibility factor for gas mixture, zm

P
RT z
V
m
=

A mixture of 75% H2 and 25% N2 (molar basis)

is contained in a tank at 800 atm and -70C.
Estimate the specific volume of the mixture in
L/mol using Kays rule.


The End