Chemical Engineering

Fundamentals 2A
CEFCHA2

Lecture 6: Single-Phase Systems

V Naidoo
JOB 4134
vizellen@uj.ac.za

1
Objectives
Understand the following:
• How process variables/ physical properties influence mass balances
• What is meant by “Equation of State”
• How to transform/ manipulate the Ideal Gas Equation/ Ideal Gas Equation of State
• How to use the STP Equations (understand what STP means)
• How Partial pressure and volume relate to mole fraction & total volume
• The laws used for Ideal Gas Mixtures

NB!! Understand how these balances differ from the ones you have learnt thus far, ensure you are
familiar with using the tables and getting the acquired data needed to solve these problems

2
 Single-Phase Systems

The state of a system is the condition of the system as specified by its properties.

1. Look up Data (Tables, Graphs,

Process Variables/ Physical Properties
Databases)

𝐴+2 𝐵→ 𝐶 2. Estimate It (Based on previous data

obtained)

F P 𝝆 ,𝑻 , 𝑷 ,𝑪𝒑 3. Measure It (Experimentally)

𝝆 ,𝑻 , 𝑷 ,𝑪𝒑
𝑥 𝐴𝑥 𝐵 𝑛𝐶
𝑛 𝐴𝑛 𝐵
𝑛 𝐴 =( 𝐹 )( 𝑥 𝐴 )

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 Phases
Phase is defined as a completely homogenous state of matter.

Gas

Water Vapor = 1 Phase

Two immiscible liquids in one container:
Liquid Water = 1 Phase
Water (l) and Mercury (l)
Ice = 1 Phase
Liquid
Is this mixture homogenous?

Solid

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 Liquid & Solid Densities:
• When you heat a liquid or a solid it normally expands (i.e., its density decreases).

𝑚
=
• In most process applications, however, it can be assumed with little error that solid
and liquid densities are independent of temperature.
𝜌 𝑣
• Similarly, changes in pressure do not cause significant changes in liquid or solid
densities; these substances are therefore termed incompressible.

e :
ssum l e
• To determine the density of a mixture of liquids or a solution of a solid in a liquid is A ss i b
p r e
from experimental data.
c o m
I n l o w
F
• Perry's Chemical Engineers' Handbook provides data for mixtures and solutions of a
number of substances on pp. 2-99 through 2-118 and lists additional sources of data
on p. 2-99

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 Density of Mixtures

1 n
xi

 i 1 i

n
   xi  i
i 1

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 Ideal Gas Equation of State
Equation of state
Relates the molar quantity and volume of a gas to temperature and pressure.

Ideal gas equation of state

PV = nRT
• Simplest and most widely used

PV = nRT • Used for gas at low pressure and high temperature

(P<1 and T>0)
• Derived from the kinetic theory of gases by assuming
P = Absolute Pressure of Gas
gas molecules:
V = Volume / Volumetric flowrate of Gas
• have a negligible volume;
n = Number of moles / Molar flowrate of Gas
• Exert no forces on one another;
R = Gas Constant (Dependent on P,V, n & T) • Collide elastically with the wall of container
T = Absolute Temperature

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 Ideal Gas Equation of State

PVˆ  RT The use of this equation does not require to know

the gas species

Vˆ  V / n
Where,
1 mol of an ideal gas at 0˚C and 1 atm occupies 22.415 liters,

whether the gas is argon, nitrogen, mixture of propane and

pressure  volume air, or any other single species or mixture of gases

Unit for R 
mole  temperatur e

energy
Unit for R 
mole  temperatur e

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 Ideal Gas Equation of State
The ideal gas equation of state is an approximation.
It works well under some conditions = at temperatures above about 0oC and pressures below about 1 atm-but at other
conditions its use may lead to substantial errors.
Here is a useful rule of thumb for when it is reasonable to assume ideal gas behavior.

Rule of thumb for when it is reasonable to assume ideal gas behavior.

• Let Xideal be a quantity calculated using ideal gas equation of state (X can be P (absolute), T (absolute), n or V
• Error is estimated value is ε X ideal  X true
  100%
X true

• Let’s say quantity to be calculate is ideal specific molar volume,

  1% if Vˆideal  5 L/mol (80 ft 3 / lb  mole) diatomic gases
 20 L/mol (320 ft 3 / lb - mole) other gases

• If error calculated satisfies this criterion, the ideal gas equation of state should yield an error less than 1%
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 Ideal Gas Equation of State: Example
One hundred grams of nitrogen is stored in a container at 23.0 oC and 3.00 psig.
Assuming ideal gas behavior, calculate the container volume in liters.

𝑛=
100.00 𝑔
=3.57 𝑚𝑜𝑙
PV = nRT ( 𝒏)(𝑹)(𝑻 )
28.0 𝑔/ 𝑚𝑜𝑙 𝑽=
(𝑷 )

𝑇 =23 +273=296 𝐾

𝑃 𝑎𝑏𝑠 =14.7 𝑝𝑠𝑖+ 3.00 𝑝𝑠𝑖𝑔=17.7 𝑝𝑠𝑖𝑎

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 Standard Temperature & 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

PV  nRT (1)
For the same ideal gas at standard reference temperature, Ts and standard reference pressure, Ps (refer to STP).

PsVˆs  RTs (2)

Divide eq. 1 to eq. 2

PV T
n
PsVˆs Ts (3)

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) : m3 (STP)
• Standard cubic feet (SCF) : ft3 (STP)
• Let say 18 SCMH mean 18 m3 (STP)/h
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 Standard Temperature & Pressure (STP)

System Ts Ps Vs ns Vs (in STP)

SI 273K 1atm 0.022415 m3 1 mol 22.4 m3/kmol
CGS 273K 1atm 22.415 L 1 mol 22.4 L/mol
American 492˚R 1atm 359.05ft3 1 lb-mole 359.05 ft3 /lb-mole
Engineering

Temperature = 0
NB!! Learn this data,
Pressure = 1 atm will not be given
Volume = 22.415 L

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 STP: Example
Butane (C4HIO ) 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.

Solution:
As always, molar quantities and absolute temperature and pressure must be used.

1100
𝑛= =19.0 𝑘𝑚𝑜𝑙 / h
PV T 58.1
n
PsVˆs Ts T = 633 K
P = 3.00 atm

3
19.0 𝑘𝑚𝑜𝑙 22.4 𝑚 (𝑆𝑇𝑃 ) 633 𝐾 1.00 𝑎𝑡𝑚 𝑚3
𝑉= × × × =329
h 𝑘𝑚𝑜𝑙 273 𝐾 3.00 𝑎𝑡𝑚 h

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 Effect of T & P on Volumetric Flowrates

Ten cubic feet of air at 70°F and 1.00 atm is heated to 610°F and compressed to
2.50 atm. What volume does the gas occupy in its final state?

𝑛1 (𝑙𝑏 − 𝑚𝑜𝑙𝑒 𝑎𝑖𝑟 ) 𝑛2 ( 𝑙𝑏− 𝑚𝑜𝑙𝑒 𝑎𝑖𝑟 )

3 3
𝑉 1=10 𝑓𝑡 𝑉 2=? 𝑓𝑡
𝑇 1=70 ℉ (530 ° 𝑅) 𝑇 2=610 ℉ ( 1070 ° 𝑅)
P1V1=nRT1 atm atm

P2V2=nRT2

𝑃2𝑉 2 𝑇2
=
𝑃1𝑉 1 𝑇1 Answer= 8.08
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 Ideal Gas Mixtures

Suppose nA moles of species A, nB moles of species B, nc moles of species C and so on, contained in a volume, V at
temperature, T and pressure, P
• Partial pressure, pA
• The pressure that would be exerted by nA moles of species A alone in the same total volume, V at the
same temperature, T of the mixture.
pA  yAP
• Pure component volume, vA
• The volume would be occupied by nA moles of A alone at the same total pressure, P and temperature,
T of the mixture.

v A  y AV
• Ideal gas mixture
• Each of the individual species component and the mixture as whole behave in an ideal manner

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 Ideal Gas Mixtures
Dalton’s Law
• The summation of partial pressure of the component of an ideal gas mixture is equal to total
pressure
p A  p B  pC  .....  ( y A  y B  y C  ....) P  P

Amagat’s Law

v A  v B  vC  .....  ( y A  y B  y C  ....)V  V

• Volume fraction = vA/V; percentage by volume (%v/v)= (vA/V )x 100%

• For an ideal gas mixture, the volume fraction is equal to the mole fraction of the substance:
70% v/v C2H6 = 70 mole% C2H6

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Liquid acetone (C3H60) 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?

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 Equations of State: Non-Ideal Gases
• 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)

• Other definition: highest temperature at which isothermal compression of the species vapor results in the
formation of a separate liquid phase.

• Critical state- a substance at their critical temperature and critical pressure.

• Species below Pc:

• Species above Tc- gas • Virial Equation of State
• Species below Tc- vapor • Cubic Equations of State
- Van De Waal Equation of
• Species above Pc and above Tc- supercritical fluids State
- SRK Equation of State
• Z Compressibility Factor

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