Section 3: FR&B, Chapter 5 (Equations of State)

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 195oF and the pressure is 62 psig. The gas is a mixture containing 70 mole%
CO and the balance H2. What is the mass flow rate of the hydrogen in the gas?
 A reactor feed stream consists of O2 flowing at 32 kg/s. The gas is to be compressed from
37oC and 2.8 atm absolute to 54oC 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 oC. The stack diameter
is 4.0 m. A continuous stack analyzer indicates an SO2 level of 2500 ppm (2500 moles
SO2/106 moles gas). At what rate in kg/s is SO2 being discharged into the atmosphere?
 A 70.0 m3 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:
100 mol/s
0.600 mol A/mol
0.400 mol B/mol

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

250 L/s @ 37oC, 800 mm Hg

pA = 420 mm Hg (partial pressure of A)

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: yA = pA/P )
 Convert volumes to moles
– First, determine the phase (solid, liquid, gas)  boiling/melting point temperature (B.1)
– Solids & liquids: use tabulated densities (volume to mass) & molecular weights (mass to moles).
Mixtures—either look up mixture density data or assume volume additivity & calculate density
from Eq. (5.1-1) or (5.1-2).
– Gases, can’t 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 won’t lecture on it, but you need to know it.

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Notes with Gaps to accompany Felder, Rousseau, & Bullard, Elementary Principles of Chemical
Processes. Copyright ©John Wiley & Sons, Inc.
 Section 3: FR&B, Chapter 5 (Equations of State)

Ideal-Gas Equation of State (Sections 5.2a & 5.2b)

PV  nRT (batch) or PV  nRT (continuous)

or PVˆ  RT where Vˆ  V / n (or V / n) is the specific molar volume of the gas

 T and P must be absolute temperature (K, oR) and absolute pressure (not gauge). R is the gas
constant—values given on inside back cover of text.
 Convenient—applies regardless of what the gas is, & whether the gas has a single component or is a
mixture. If you can’t assume ideal-gas behavior (i.e., if gas is nonideal or real),
 Approximate—greatest 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 0oC & pressures at or below 1 atm. Rule of thumb for when to use it given in
Eqs. (5.2-3):
If RT/P > 5 L/mol (80 ft3/lb-mole) diatomic gases – IGEOS is OK
RT/P > 20 L/mol (320 ft3/lb-mole) other gases – IGEOS is OK
 Three will get you four. Given any three of the variables -- P, V (or V ), T , and n (or n) -- calculate the
fourth one.
 Brainstorm everyday applications of the IGEOS (e.g. hot air balloon, …)
Example: The volumetric flow rate of a stream of propane at 150oC and 70.0 atm being fed to a
combustion furnace is measured and found to be 29.0 m3/h.

(a) Determine its molar flow rate in kmol/h.

Solution. We are given three of the four gas law variables (_____, ______, and ______) and so can
determine the fourth one (________).

From the inside back cover, R = 0.08206 (L  atm) / (mol  K) .

 kmol C3 H8  PV 70.0 atm 29.0 m3 mol  K

n  = RT =
 h  h 0.08206 L  atm
kmol
= 58.5
h
(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. _______________________________________________________________________

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Notes with Gaps to accompany Felder, Rousseau, & Bullard, Elementary Principles of Chemical Processes.
Copyright ©John Wiley & Sons, Inc.
 Section 3: FR&B, Chapter 5 (Equations of State)

(c) Check the assumption of ideal-gas behavior.

Solution:
RT 0.08206 L  atm L
= = __________ , therefore from Eq. ____________,
P mol  K mol
ideal gas behavior is a ___________ assumption.

For another example, work through Problem 5.14 and check your answer in the back of the book.
 Standard temperature and pressure (STP): 0oC (273.16K, 491.67oR), 1 atm. At STP, 1 mol occupies
22.415 L, 1 kmol occupies 22.415 m3, & 1 lb-mole occupies 359.05 ft3.
 The volumetric flow of a gas changes with P and T, so it is convenient to reference flow to a
standard condition.
 While our text (and many other thermodynamic texts) use 0oC and 1 atm as STP, there are some
other ‘standards’. In this course, please use the values in Table 5.2-1 on p. 223.
 Suppose you are told that a gas flows at a rate of, say, 1280 SCFH [standard cubic feet per hour, or
ft3(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 oC and 1 atm, its volumetric
flow rate would be 1280 ft3/h. (See Example 5.2-4.)
(b) Think of it as a process:

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Notes with Gaps to accompany Felder, Rousseau, & Bullard, Elementary Principles of Chemical Processes.
Copyright ©John Wiley & Sons, Inc.
 Section 3: FR&B, Chapter 5 (Equations of State)

(c) You can calculate the molar flow rate of the gas as
1280 ft 3 (STP) 1 lb - mole lb - mole
n= 3
= 3.56
h 359.05 ft (STP) h

(c) If you know that the actual temperature of the gas is 120oC (393K) and 0.800 atm, you can
calculate its actual flow rate as
1280 ft 3 (STP) 393 K 1 atm ft 3
V= = 2300
h 273 K 0.800 atm h

(See Example 5.2-3.)

Ideal-Gas Mixtures, Partial Pressures, and Volume Percentages (Section 5.2c)

Suppose yA = 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%
methane, CH4, 50 mole% ethane, C2H6, and 20 mole% ethylene, C2H4.)

 Partial pressure of a component of a gas:

pA = yAP
Example: pCH4  0.30 1000 mm Hg = 300 mm Hg

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
PvA  nA RT Divide vA nA
   yA (volume fraction = mole fraction)
PV  nRT V n
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

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Notes with Gaps to accompany Felder, Rousseau, & Bullard, Elementary Principles of Chemical Processes.
Copyright ©John Wiley & Sons, Inc.
 Section 3: FR&B, Chapter 5 (Equations of State)

 Three alternative ways of telling you the value of a mole fraction for a gas:

MOLE PARTIAL VOLUME

FRACTIONS PRESSURE
yA FRACTION
pA = yAP
% v/v = mole%
for an ideal-gas
mixture

From now on, any of these specifications may be given in material balance problems. You should
immediately convert the second and third specifications 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 pA = yAP as
another equation in the degree-of-freedom analysis.

Exercise. Liquid acetone (C3H6O) is fed at a rate of 400 L/min into a heated chamber where it evaporates
into a nitrogen stream which enters at 27oC and 475 mm Hg (gauge). The gas leaving the heater is diluted
by another nitrogen stream flowing at a measured rate of 419 m3/min (STP) at 25oC and 2.5 atm. The
combined gases are then compressed to a total pressure P = 6.3 atm (gauge) at a temperature of 325oC.
The partial pressure of acetone in this stream is pa = 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
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 25oC and 2.5 atm?

Solution. Verify that the flow chart is completely labeled.

V1 (m3 / min)
n1 (mol N 2 / min)
n4 (mol / min)
27 o C, 475 torr Compressor
Evaporator y4 (mol C3H6O(v)/mol)
(1–y4) (mol N2/mol)
400 L/min C3H6O (l) 325oC, 6.3 atm (gauge)
pa = 501 torr
n2 (mol / min) 419 m3/min (STP) N2/min
n3 (mol N 2 / min)
25oC, 2.5 atm

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Notes with Gaps to accompany Felder, Rousseau, & Bullard, Elementary Principles of Chemical Processes.
Copyright ©John Wiley & Sons, Inc.
 Section 3: FR&B, Chapter 5 (Equations of State)

(a) Degree-of-freedom analysis:

System equations:

(b) _________________________________________________________________________________

Nonideal (Real) Gases (Section 5.3)

 How would you measure P, V, T relationships in a laboratory?

 Would the relationships be different for each gas species?

 When you can’t assume __________ behavior (low ___, high ____, outside criteria of Eqs. 5.2-3),
rather than create massive tables of P, V, T data for each gas species, need to find a universal
‘equation of state’ that incorporates properties of the gas species.

 It turns out that different gases behave similarly at the same ________________________ (Section
5.3a). Each gas has a unique value for Tc and Pc (Table B.1). Let’s review supercritical behavior.

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Notes with Gaps to accompany Felder, Rousseau, & Bullard, Elementary Principles of Chemical Processes.
Copyright ©John Wiley & Sons, Inc.
 Section 3: FR&B, Chapter 5 (Equations of State)

 We will discuss three approaches for non-ideal equations of state:

PVˆ BP
1. Virial equations of state (Section 5.3b). 1 where B is calculated as follows:
RT RT
0.422
B0  0.083 -
Tr1.6
0.172
B1  0.139 -
Tr 4.2
RTc
B ( B0   B1 )
Pc
and  the Pitzer Acentric Factor, is found in Table 5.3-1.
2. Cubic equations of state and the SRK equation (Section 5.3c). Commonly used for single species
(for mixtures, use compressibility factor EOS). The Soave-Redlich-Kwong (SRK) equation of
state (Eq. 5.3-8) 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,Vˆ , T ) is unknown.

RT a
P - where (5.3 - 8)
V - b V (Vˆ  b)
ˆ ˆ

( RTc ) 2
a  0.42747 (5.3 - 9)
Pc
RTc
b  0.08664 (5.3 -10)
Pc
m  0.48508  1.55171 - 0.1561 2 (5.3 -11)
Tr  T / Tc (5.3 -12)
2
  1  m(1- Tr )  (5.3 -13)

Procedure:
 For given species, look up Tc, Pc, and the Pitzer acentric factor  (Table 5.3-1 for selected
species). Calculate a, b, and m from Eqs. 5.3-9, 5.3-10, & 5.3-11.
 If T and Vˆ are known, evaluate Tr from Eq. 5.3-11 and  from Eq. 5.3-12, solve Eq. 5.3-8 for P.
 If T and P are known, enter Eq. 5.3-7 in Solver or APEx, enter all known values, and solve for Vˆ
as in Example 5.3-3.
 If P and Vˆ are known, enter Eqs. 5.3-8, 5.3-12 for Tr, and 5.3-13 for  into Excel’s Solver or
APEx, enter all known values, and solve for T.
3. 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 Kay’s Rule (Section 5.4a) to estimate z.
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Notes with Gaps to accompany Felder, Rousseau, & Bullard, Elementary Principles of Chemical Processes.
Copyright ©John Wiley & Sons, Inc.
 Section 3: FR&B, Chapter 5 (Equations of State)

Procedure: Given two of the variables T, P, and Vˆ (or V and n or V and n )

1. Look up Tc and Pc (e.g. in Table B.1). Apply Newton’s corrections for H2, He (p. 238).
2. Calculate two of the quantities reduced temperature. Tr = T/Tc , reduced pressure Pr = P/Pc , and
Vˆ
ideal reduced volume, Vˆrideal  , depending on which two of the variables T, P, and Vˆ are
RTc / Pc
known.
3. Look up z on one of the generalized compressibility charts, Figs. 5.4-1 – 5.4-4. (Which one
should you use? Whichever one you can clearly find the conditions and read the values. If Pr is
provided, this makes it easier since the horizontal axis is Pr).
4. Substitute known variables and z into the compressibility factor equation of state (PV = znRT) to
determine the unknown variable.

 Example: Example 5.4-2

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 at the end of Section 5.4.
 Kay’s rule: PVT calculations for nonideal-gas mixtures using compressibility charts (Section 5.4a):
Calculate pseudocritical temperature Tc' and pseudocritical pressure Pc' by weighting Tci and Pci by
mole fractions of i th component (Eqs. 5.4-9 and 5.4-10), then proceed as for single component. See
Example 5.4-2. This is the only method we will present in this book for doing PVT calculations on
nonideal-gas mixtures. You will see more later in your Thermodynamics classes.

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Notes with Gaps to accompany Felder, Rousseau, & Bullard, Elementary Principles of Chemical Processes.
Copyright ©John Wiley & Sons, Inc.
 Section 3: FR&B, Chapter 5 (Equations of State)

Exercise. A natural gas (85 mole% CH4, 15% C2H6) at 20oC and 80 atm is burned completely with 30%
excess air. Vnatural gas = 285 L / s. The stack gas emerges at 280oC and 1 atm. What is Vstack gas ?

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

Furnace

CH4 + 2O2  CO2 + 2H2O

7
C2H6 + 2
O2  2CO2 + 3H2O

(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).

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Notes with Gaps to accompany Felder, Rousseau, & Bullard, Elementary Principles of Chemical Processes.
Copyright ©John Wiley & Sons, Inc.
 Section 3: FR&B, Chapter 5 (Equations of State)

(d) Write out the seven equations required to solve for the unknowns, letting (Tcm , Pcm) and (Tce , Pce)
equal the critical temperatures of methane and ethane, respectively. (You could find their values in Table
B.1 but don’t bother.)

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Notes with Gaps to accompany Felder, Rousseau, & Bullard, Elementary Principles of Chemical Processes.
Copyright ©John Wiley & Sons, Inc.
 Section 3: FR&B, Chapter 5 (Equations of State)

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Notes with Gaps to accompany Felder, Rousseau, & Bullard, Elementary Principles of Chemical Processes.
Copyright ©John Wiley & Sons, Inc.