CHE 205 Chemical Process Principles

Section 3: EPCP, Chapter 5

3-1
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)
EQUATIONS OF STATE FOR GASES

Questions
- A gas enters a reactor at a rate of 255 SCMH. What does that mean?
- An orifice meter mounted in a process gas line indicates a flow rate of 24 ft
3
/min. The gas
temperature is 195
o
F and the pressure is 62 psig. The gas is a mixture containing 70 mole%
Co and the balance H
2
. What is the mass flow rate of the hydrogen in the gas?
- A reactor feed stream consists of O
2
flowing at 32 kg/s. The gas is to be compressed from
37
o
C and 2.8 atm absolute to 54
o
C and 284 atm. What are the volumetric flow rates at the
inlet and outlet (needed to rate the compressor)?
- A pitot tube indicates that the velocity of a stack gas is 5.0 m/s at 175
o
C. The stack diameter
is 4.0 m. A continuous stack analyzer indicates an SO
2
level of 2500 ppm (2500 moles
SO
2
/10
6
moles gas). At what rate in kg/s is SO
2
being discharged into the atmosphere?
- A 70.0 m
3
tank is rated at 2000 kPa. If 150 kg of helium is charged into the tank, what will
the pressure be? How much more helium can be added before the rated pressure is attained?

Answers: Need an equation of state: relationship between temperature (T), pressure (P), volume (V), and
number of moles (n) of a gas.
- In Chapter 4, streams on flow charts labeled like this:



In this chapter, stream data just as likely to look like this:



For material balances, however, we still need moles and mole fractions. The job now becomes one of
converting volumetric flow rates (or volumes) to molar flow rates (or moles), and (for gases) partial
pressures to mole fractions. (Latter is easy: y
A
=p
A
/P )
- Convert volumes to moles
Solids & liquids: use tabulated densities (volume to mass) & molecular weights (mass to moles).
Mixtureseither look up mixture density data or assume volume additivity & calculate density
from Eq. (5.1-1).
Gases, cant use tabulated densities. (Why not?) Instead, need an equation of state (EOS) a
formula relating V, n, T, and P. Simplest is the ideal gas EOS.
- Read Section 5.1. We wont lecture on it, but you need to know it.
Ideal Gas Equation of State (Sections 5.2a & 5.2b)
(batch) or (continuous)

or where / (or / ) is the of the gas
PV nRT PV nRT
PV RT V V n V n specific molar volume
= =
= =

100 mol/s
0.600 mol A/mol
0.400 mol B/mol
250 L/s @ 37
o
C, 800 mm Hg
p
A
=420 mm Hg (partial pressure of A)
CHE 205 Chemical Process Principles
Section 3: EPCP, Chapter 5



3-2
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)

- T and P must be absolute temperature (K,
o
R) and absolute pressure (not gauge). R is the gas
constantvalues given on inside back cover of text.
- Convenientapplies regardless of what the gas is, & whether the gas has a single component or is a
mixture. If you cant assume ideal gas behavior (i.e., if gas is nonideal or real),
- Approximategreatest validity at low gas densities (high T, low P), when gas molecules are far
enough apart for intermolecular forces to be negligible (behave like billiard balls). Usually ok for
temperatures at or above 0
o
C & pressures at or below 1 atm. Rule of thumb for when to use it given in
Eqs. (5.2-3) on p. 192.
- Three will get you four. Given any three of the variables , (or ), , and (or ) P V V T n n

, calculate the
fourth one.

Example
The volumetric flow rate of a stream of propane at 150
o
C and 70.0 atm being fed to a combustion furnace
is measured and found to be 29.0 m
3
/h.
(a) Determine its molar flow rate.
Solution. We are given three of the four gas law variables (_____, ______, and ______) and so can
determine the fourth one (________).

From the inside back cover, 0.08206 (L atm)/(mol K) R = .
3
3 8
70.0 atm 29.0 m mol K
kmol C H
h 0.08206 L atm h
kmol
= 58.5
h
PV
n
RT

| |
= =
|

\ .

(b) Now, suppose an analysis of the combustion chamber products shows that the molar flow rate of the
propane was 101 kmol/h. Think of four possible reasons for the discrepancy between the two stated
values of the molar flow rate.
1. _______________________________________________________________________
2. _______________________________________________________________________
3. _______________________________________________________________________
4. _______________________________________________________________________
(c) Check the assumption of ideal gas behavior.
Solution:
CHE 205 Chemical Process Principles
Section 3: EPCP, Chapter 5



3-3
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)


0.08206 L atm
L
__________ , therefore from Eq. ____________,
mol K
mol
ideal gas beh
RT
P

= =

avior is a ___________ assumption.

For another example, work through Problem 5.10 in the workbook.
- Standard temperature and pressure (STP): 0
o
C (273.16K, 491.67
o
R), 1 atm. At STP, 1 mol occupies
22.415 L, 1 kmol occupies 22.415 m
3
, & 1 lb-mole occupies 359.05 ft
3
. (Memorize)
- Suppose you are told that a gas flows at a rate of, say, 1280 SCFH [standard cubic feet per hour, or
ft
3
(STP)/h]
(a) It does not mean that the gas is at standard temperature and pressure. It does mean that if you
brought it from whatever its temperature and pressure really are to 0
o
C and 1 atm, its volumetric
flow rate would be 1280 ft
3
/h. (See Example 5.2-4.)
(b) You can calculate the molar flow rate of the gas as
3
3
1280 ft (STP) 1 lb-mole
lb-mole
3.56
h h 359.05 ft (STP)
n = =
(c) If you know that the actual temperature of the gas is 120
o
C (393K) and 0.800 atm, you can
calculate its actual flow rate as

3
3
1280 ft (STP) 393 K 1 atm
ft
2300
h 273 K 0.800 atm h
V = =

(See Example 5.2-3.)
CHE 205 Chemical Process Principles
Section 3: EPCP, Chapter 5



3-4
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)

Ideal Gas Mixtures, Partial Pressures, and Volume Percentages (Section 5.2c)
Suppose y
A
=mole fraction of a component A in a mixture of gases at pressure P and volume V.
(Example: A mixture of gases at P =1000 mm Hg with a volume of 200 liters contains 30 mole% CH
4
,
50 mole% C
2
H
6
, and 20 mole% C
2
H
4
.)
- Partial pressure of a component of a gas:
p
A
=y
A
P
Example:
4
CH
0.30 1000 mm Hg =300 mm Hg p =
The partial pressures of all components of a mixture add up to the total pressure (prove it).
- Pure component volume and percentage by volume: The pure component volume of A is the
volume A would occupy if it were by itself at the mixture temperature and pressure
Divide A A A A
A
Pv n RT v n
y
PV nRT V n
=
= =
=
(volume fraction =mole fraction)
The percentage by volume (% v/v) is 100 times the volume fraction. Thus,
% v/v =mole% for an ideal gas mixture
% v/v has no practical significance for a nonideal gas mixture

- Three alternative ways of telling you the value of a mole fraction

From now on, any of these specifications may be given in material balance problems. You should
immediately convert the first two to mole fractions when you label the flow chart, and if you label the
partial pressure on the flow chart also label the mole fraction and count p
A
=y
A
P as another equation in
the degree-of-freedom analysis.








MOLE
FRACTIONS
y
A

PARTIAL
PRESSURE
p
A
=y
A
P
VOLUME
FRACTION
% v/v =mole%
for an ideal gas
mixture
CHE 205 Chemical Process Principles
Section 3: EPCP, Chapter 5



3-5
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)

Exercise. Liquid acetone (C
3
H
6
O) is fed at a rate of 400 L/min into a heated chamber where it evaporates
into a nitrogen stream which enters at 27
o
C and 475 mm Hg (gauge). The gas leaving the heater is diluted
by another nitrogen stream flowing at a measured rate of 419 m
3
(STP) at 25
o
C and 2.5 atm. The
combined gases are then compressed to a total pressure P =6.3 atm (gauge) at a temperature of 325
o
C.
The partial pressure of acetone in this stream is p
a
=501 torr (501 mm Hg). Atmospheric pressure is 763
torr.
(a) Write the complete set of equations you would solve to determine the molar composition of the
stream product gas stream and the volumetric flow rate of the nitrogen entering the evaporator.
(b) How is it possible for the second nitrogen stream to be at standard temperature and pressure and
at 25
o
C and 2.5 atm?
Solution. Verify that the flow chart is completely labeled.








(a) Degree-of-freedom analysis:






System equations:








(b) _________________________________________________________________________________

3
1
1 2
o
(m/ min)
(mol N / min)
27 C, 475 torr
V
n

400 L/min C
3
H
6
O (l)
2
(mol/min) n

Evaporator
419 m
3
(STP) N
2
/min
3 2
(mol N / min) n
25
o
C, 2.5 atm
Compressor
4
(mol/ min) n
y
4
(mol C
3
H
6
O(v)/mol)
(1y
4
) (mol N
2
/mol)
325
o
C, 6.3 atm (gauge)
p
a
=501 torr
CHE 205 Chemical Process Principles
Section 3: EPCP, Chapter 5



3-6
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)

Nonideal (Real) Gases (Section 5.3)
When you cant assume ideal gas behavior (low T, high P, outside criteria of Eqs. 5.2-3), need to use a
more complex equation of state, all of which incorporate properties of the species in the gas. (Ideal gas
EOS is independent of species.) Read p. 5-4 of the workbook.
- Note definitions of critical temperature and pressure in Section 5.3a. You can look up T
c
and P
c
in
Table B.1.
- Virial equations of state (Section 5.3b). Mostly of theoretical interestrarely used in practice.
- Cubic equations of state and the SRK equation (Section 5.3c). Commonly used for single species (for
mixtures, use compressibility factor EOS). The SRK equation of state (Eq. 5.3-7) may be the most
commonly used EOS other than the ideal gas equation. Easy or hard to use, depending on which of
the three variables

( , , ) P V T is unknown.
Procedure:
For given species, look up T
c
, P
c
, and the Pitzer acentric factor e (Table 5.3-1 for selected
species). Calculate a, b, and m from Eqs. 5.3-8, 5.3-9, & 5.3-10.
If T and

V are known, evaluate T

r
from Eq. 5.3-11 and o from Eq. 5.3-12, solve Eq. 5.3-7 for P.
If T and P are known, enter Eq. 5.3-7 in E-Z Solve, enter all known values, and solve for

V .
(Alternatively, use Goal Seek in Excel, as in Example 5.3-3.)
If P and

V are known, enter Eqs. 5.3-7, 5.3-11 for T

r
, and 5.3-12 for o into E-Z Solve, enter all
known values, and solve for T.
- Compressibility factor equation of state (Section 5.4): PV = znRT , where z is the compressibility
factor (a fudge factor the farther it is from 1, the farther the gas is from ideal).
- Either you have tables where you can look up z for a given T and P (Section 5.4a, single species
only), or you use the law of corresponding states (Section 5.4b) to estimate z.
Procedure: Given two of the variables T, P, and

V (or V and n or and V n

)
1. Look up T
c
and P
c
(e.g. in Table B.1). Apply Newtons corrections for H
2
, He (p. 208).
2. Calculate two of the quantities reduced temperature. T
r
= T/T
c
, reduced pressure P
r
= P/P
c
, and
ideal reduced volume,
ideal

/
r
c c
V
V
RT P
= , depending on which two of the variables T, P, and

V are
known.
3. Look up z on one of the generalized compressibility charts, Figs. 5.4-1 5.4-4.
4. Substitute known variables and z into the compressibility factor equation of state to determine the
unknown variable.






CHE 205 Chemical Process Principles
Section 3: EPCP, Chapter 5



3-7
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)

- Example: Example 5.4-2, p. 209.
Note: If the gas were anything other than nitrogen, then Z will change because the critical
constants are different. For example, Z =1.4 for hydrogen.
- Go through Test Yourself on p. 210.
- Kays rule: PVT calculations for nonideal gas mixtures using compressibility charts (Section 5.4c):
Calculate pseudocritical temperature and pseudocritical pressure by weighting T
ci
and P
ci
by mole
fractions of i
th
component (Eqs. 5.4-9 and 5.4-10), then proceed as for single component. This is the
only method we will present in this book for doing PVT calculations on nonideal gas mixtures.
CHE 205 Chemical Process Principles
Section 3: EPCP, Chapter 5



3-8
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)

Exercise. A natural gas (85 mole% CH
4
, 15% C
2
H
6
) at 20
o
C and 80 atm is burned completely with 30%
excess air.
natural gas
285 L/s. V =

The stack gas emerges at 280

o
C and 1 atm. What is
stack gas
? V

Solution.
(a) Draw and label the flow chart.










(b) What equations of state should you use to relate the volumetric flow rates of the fuel and stack gases
to their molar flow rates?
Fuel gas: __________________________________________________
Stack gas: _________________________________________________
(c) Do the degree-of-freedom analysis (use atomic balances).












Furnace
CH
4
+2O
2
CO
2
+2H
2
O
C
2
H
6
+
7
2
O
2
2CO
2
+3H
2
O
CHE 205 Chemical Process Principles
Section 3: EPCP, Chapter 5



3-9
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)

(d) Write out the seven equations required to solve for the unknowns, letting (T
cm
, P
cm
) and (T
ce
, P
ce
) =
critical temperatures of methane and ethane, respectively. (You could find their values in Table B1 but
dont bother.)