Module 4

Single-Phase Systems

641
 Module 4

Some material balance problems can be solved entirely from

information given in the problem statements.

However, problems in process analysis usually require us to determine

various physical properties of the process materials and use these
properties to derive additional relations among the system variables.

642
 Module 4
Methods to determine physical property of a process material:

1. Look it up:
• Lets us say, we need physical property of a substance— density, vapor
pressure, solubility, or heat capacity— for material balance
calculations.
• There is a good chance that someone, somewhere has measured this
property and published the result.
• Experiments are usually costly and time consuming  a reliable
source of physical property data is an invaluable asset in process
analysis.
• Excellent sources of data – Hand Books. 643
Example of look-up tables

644
 Module 4
2. Estimate it:

As chemical engineers, we deal with finite number of molecular species.

However, chemical species can be combined into mixtures in an infinite

number of ways

It is impossible to tabulate physical property data for even a small

fraction of the possible combinations.

Even when data are found they are likely to have been determined for
conditions other than the ones for which you need them. 645
 Module 4
2. Estimate it:

There are a large number of empirical correlations that express physical

properties of a mixture in terms of the pure-component properties and
the mixture composition.

These correlations can be used to estimate physical properties when no

data are available and to extrapolate available data to conditions other
than the ones at which the data were obtained.

646
 Module 4
3. Measure it:

(i) When no information on a particular physical property of a

substance can be found in the literature OR
(ii) When the property must be known with a precision greater than that
provided by general estimation formulas,

the only recourse is to determine the property experimentally.

Information on experimental techniques for measuring physical

properties can be found in any of numerous texts on experimental
physical, organic, and analytical chemistry. 647
 Module 4

Single-Phase Systems
What’s in this module?
The uses of both tabulated data and estimation formulas for
calculating densities of single phase systems - solids and liquids;
Discussion on, ideal gases, gases for which the ideal gas
equation of state (Pv=nRT ) is a good approximation and
extension to nonideal gases. 648
 LIQUID AND SOLID DENSITIES
Densities of solids and liquids – from tables and handbooks

649
 LIQUID AND SOLID DENSITIES
Densities of solids and liquids – from tables and handbooks

650
 LIQUID AND SOLID DENSITIES

Densities of solids and liquids – from tables and handbooks

When you heat a liquid or a solid it normally expands (i.e., its density
decreases). In most process applications, however, it can be assumed
with little error that solid and liquid densities are independent of
temperature. Similarly, changes in pressure do not cause significant
changes in liquid or solid densities; these substances are therefore
termed INCOMPRESSIBLE

651
 Density of Liquid Mixtures and Solutions
The most accurate way to determine the density of a mixture of liquids
or a solution of a solid in a liquid is from experimental data

Assuming volume additivity —that is, if 2 mL of liquid A and 3 mL of

liquid B are mixed, the resulting volume would be exactly 5 mL (also
known as ideal mixing assumption), the density of a mixture of n
liquids (A1, A2,…., An ) can be estimated from the component mass
fractions [xi ] and pure-component densities [ρi] as:

652
 Density of Liquid Mixtures and Solutions

The density of a mixture of n liquids (A1, A2,…., An ) can be estimated

from the component mass fractions [xi ] and pure-component densities
[ρi] can also be expressed as:

653
 Density of Liquid Mixtures and Solutions

(2)
(1)

Experimental values (Perry’s hand Book) and estimated mixture

densities for sulfuric acid–water and for methanol–water, both at 20 C.
654
 Density of Liquid Mixtures and Solutions

provides a slightly better estimate (i.e., values closer to the experimental

data) for methanol and water

provides a much better estimate for sulfuric acid and water. 655
 Density of Liquid Mixtures and Solutions
Which method should you use?

The assumption of volume additivity work best for mixtures of liquid

species with similar molecular structures (e.g., all straight-chain
hydrocarbons of nearly equal molecular weight, such as -pentane, -
hexane, and -heptane).

There are no general rules for when works better

we can rely on empirical (experimental) findings.

656
Test yourself

657
 Test yourself

Mass flow rate = Volumetic flowrate x Density

Density of water at 75 C = 0.97468 g/cc or g/ml
Volumetric flow rate at 75 C = 261.62 cc/s or ml/s 658
Test yourself

𝒏
𝒊
𝒊
𝒊 𝟏

659
 Test yourself
Determine the density in g/cm of a 50 wt% aqueous solution of H2SO4 at
20 C by assuming volume additivity of the solution components.

660
 Test yourself
Determine the density in g/cm of a 50 wt% aqueous solution of H2SO4 at
20 C by assuming volume additivity of the solution components.
𝒏
𝒊
𝒊
𝒊 𝟏

g/cc

Density of pure components

in g/cc

661
 Need for PVT relations

Looking up a density or specific volume at one temperature and

pressure and using it at another temperature and pressure usually works
well for a solid or a liquid, but not at all for a gas.

For gases, we need an expression that relates specific volume to

temperature and pressure (PVT Behavior), so that we can calculate one
of the quantities given the other two.

662
 Need for PVT relations

Some examples…

Propane at 120 C and 2.3 bars passes through a flowmeter that reads
250 L/min. What is the mass flow rate of the gas?

A pure hydrocarbon gas fills a two-liter vessel at 30 C with an absolute

pressure of 25 atm. How many gram-moles of gas are contained in the
vessel? If the mass of the gas is 60 g, what might the gas be?

663
 Equation of state

An equation of state relates the molar quantity (moles) and volume of a

gas to temperature and pressure.

664
 Equation of state

An equation of state relates the molar quantity (moles) and volume of a

gas to temperature and pressure. The simplest and most widely used of
these relationships which is adequate for many engineering calculations
involving gases at low pressures is the IDEAL GAS EQUATION OF STATE.

665
 Equation of state

An equation of state relates the molar quantity (moles) and volume of a

gas to temperature and pressure. The simplest and most widely used of
these relationships which is adequate for many engineering calculations
involving gases at low pressures is the IDEAL GAS EQUATION OF STATE.

However, some gases deviate from ideal behavior at nearly all conditions
and all gases deviate substantially at certain conditions (notably at high
pressures and/or low temperatures). In such cases it is necessary to use
more complex equations of state for PVT calculations

666
The ideal gas equation of state

667
 The ideal gas equation of state
The ideal gas equation of state, derived from the kinetic theory of gases,
assumes that gas molecules have a negligible volume, exert no forces on
one another, and collide elastically with the walls of their container.

668
 The ideal gas equation of state

The gases that obey these PVT relations – ideal gases or prefect gases

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

The gas constant R can take different values depending on units

669
 The ideal gas equation of state

The ideal gas equation of state is an approximation! It works well under

some conditions— generally speaking, at temperatures above about 0
C and pressures below about 1 atm—but at other conditions its use
may lead to substantial errors.

670
 The ideal gas equation of state

When are the predictions from these equations reasonable?

Xideal be a quantity calculated using the ideal gas equation of state [X = P

(absolute), T (absolute), n or V ] and  be the error in the estimated
value,

671
 The ideal gas equation of state

When are the predictions from these equations reasonable?

An error of no more than about 1% may be expected if the quantity

RP/P (the specific volume) satisfies:

Diatomic gases

Other gases
672
 Ideal gas equation of state - calculation of density

The relationship between the density ρ (mass/volume), temperature,

and pressure of an ideal gas can be obtained by relating the
specificmolar volume, (volume/mole), to the density:

Molecular weight of the

gas

673
Test yourself

674
 Test yourself

The masses and mass densities will be different by a factor given by the
ratio of molecular weights, Mw of CO2/H2  44/2=22 675
Test yourself

=
676
 Test yourself

= = =2

=
677
 Test yourself

̇
=
̇ = =2
=
Specific molar volume 678
Test yourself

679
 Ideal Gas Law - Standard Temperature and Pressure
Writing ideal gas law for

(i) an arbitrary temperature, T and pressure P:

(ii) at a specified reference temperature TS and pressure, PS (referred to

as standard temperature and pressure or STP):

Dividing the 2 equation gives:

680
 Standard Temperature and Pressure
For a flowing stream:

If the standard conditions (TS, PS ) are known, can be calculated as

RTS/PS, then above equation can be used to calculate V for a given value
of n or n for a given value of V. The standard conditions most commonly
used are:

681
 Standard Temperature and Pressure
For a standard temperature ( TS = 0 C  273 K) and standard pressure
(PS = 1 atm), the standard specific molar volume is:

The term STANDARD CUMIC METERS (or SCM) is often used to denote
m3 (STP), and STANDARD CUBIC FEET (or SCF) denotes ft3 (STP).

A volumetric flow rate of 18.2 SCMH means 18.2 m3 /h at 0  C and 1

atm.
682
 Relating ideal gas properties at two conditions
We will frequently encounter problems that involve gases at two
different states (sets of conditions)—for example, at the inlet and outlet
of a process unit.

A convenient way to determine an unknown variable (P, V, T, or n ) of the

gas at one of the states is to write the gas law for both states and divide
one equation by the other.

Any variables that are the same at both points will cancel, leaving an
equation containing only the variable you wish to determine and known
quantities.
683
Test yourself

684
Test yourself

685
Test yourself

686
Test yourself

687
 Ideal Gas Mixtures
Consider an ideal gas mixture containing - nA moles of substance A, nB
moles of B, nC moles of C, and so on, are contained in a volume V at a
temperature T and total pressure P.

We can define the partial pressure pA and pure component volume vA

of A in the mixture as:

• pA - the pressure that would be exerted by nA moles of A alone in the

same total volume V at the same temperature T.

• vA - the volume that would be occupied by nA moles of A alone at the

total pressure P and temperature T of the mixture. 688
 Ideal Gas Mixtures
Note that each of the individual mixture components and the mixture as
a whole behave in an ideal manner (This is the definition of an ideal gas
mixture).

If there are n moles of all species in the volume V at pressure P and

temperature T, then

From the definition of partial pressure of A

689
 Ideal Gas Mixtures
Dividing by

, the mole fraction of A in the mixture

The partial pressure of a component in an

ideal as mixture is the mole fraction of that
component times the total pressure.

The partial pressures of the components of an ideal as mixture add up

to the total pressure (Dalton’s law). 690
 Ideal Gas Mixtures
Dividing the expression for pure component volume by

We get

The pure component volume of a component in an ideal as mixture is

the mole fraction of that component times the total volume.

The total volume of a gas mixture = the sum of the partial volumes each
gas if it existed alone at the T and P of the mixture (Amagat’s law).
691
 Ideal Gas Mixtures
The quantity vA/V is the of volume fraction A in the mixture.

The quantity (vA/V)x100 is the of volume percentage (% v/v) of this

component.

The volume fraction of a substance in an ideal gas mixture equals the

mole fraction of this substance.

692
Test yourself

693
 Test yourself

Pabsolute = Pgauge + Patmospheric

694
Test yourself

695
 Test yourself

50 m3

= T is raised, increases
5 bar = T is raised, remains
same

696
Test yourself

697
Test yourself

698
 Problem Solving!
A stream of air (21 mole% O2, the rest N2) flowing at a rate of 10.0 kg/h
is mixed with a stream of CO2. The CO2 enters the mixer at a rate of 20.0
m3/h at 150 C and 1.5 bar. What is the mole percent of CO2 in the
product stream?

699
A stream of air (21 mole% O2, the rest N2) flowing at a rate of 10.0 kg/h
is mixed with a stream of CO2. The CO2 enters the mixer at a rate of 20.0
m3/h at 150 C and 1.5 bar. What is the mole percent of CO2 in the
product stream?

O2
mixer N2
10.0 kg/h CO2
21 mole% O2,
79 mole% N2
CO2, 20.0 m3/h
150 C and 1.5 bar
700
A stream of air (21 mole% O2, the rest N2) flowing at a rate of 10.0 kg/h
is mixed with a stream of CO2. The CO2 enters the mixer at a rate of 20.0
m3/h at 150 C and 1.5 bar. What is the mole percent of CO2 in the
product stream?
Average molecular weight = 29 g/mol
10.0 kg/h O2
21 mole% O2, mixer N2
79 mole% N2 CO2
344.83 mol/h=

CO2, 20.0 m3/h

150 C and 1.5 bar
701
A stream of air (21 mole% O2, the rest N2) flowing at a rate of 10.0 kg/h
is mixed with a stream of CO2. The CO2 enters the mixer at a rate of 20.0
m3/h at 150 C and 1.5 bar. What is the mole percent of CO2 in the
product stream?
Average molecular weight = 29 g/mol
10.0 kg/h O2
21 mole% O2, mixer N2
79 mole% N2 CO2
344.83 mol/h=
=
R=8.314×10-5
(m3.bar.K-1.mol-1) CO2, 20.0 m3/h
P=1.5 bar 150 C and 1.5 bar
= 853.04 mol/h 702
What is the mole percent of CO2 in the product stream?
Average molecular weight = 29 g/mol
10.0 kg/h
21 mole% O2, mixer
79 mole% N2
344.83 mol/h O2
=
N2
R=8.314×10-5
CO2
(m3.bar.K-1.mol-1) CO2, 20.0 m3/h
P=1.5 bar 150 C and 1.5 bar
= 853.04 mol/h

molar flow rate of CO2 in the product/(total molar flow rate)

=(853.04 moles/h)(854.03 moles/h +344.83 moles/h)=0.712 703
 Problem Solving!
A schematic of a spray drying process:

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. 704
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.

• Calculate the production rate of dried milk and the volumetric flow
rate of the inlet air.

• Estimate the upward velocity of air (m/s) at the bottom of the dryer.

• What problem would you guess would occur if the velocity is too
high?
705
0.70 kg H2O/Kg 0.12 kmol H2O/kmol wet air
0.30 kg Solids/Kg 0.88 kmol dry air/ kmol wet air

1 kg/min 2 kmol/min

6m

1 kmol dry air/min 2 kg of solids/min

6m
1 m3 dry air/min
706
0.70 kg H2O/Kg 0.12 kmol H2O/kmol wet air
0.30 kg Solids/Kg 0.88 kmol dry air/ kmol wet air

1 kg/min 2 kmol/min

Volumetric flow rate is given

6m

1 kmol dry air/min 2 kg of solids/min

6m
1 m3 dry air/min
707
0.70 kg H2O/Kg 0.12 kmol H2O/kmol wet air
0.30 kg Solids/Kg 0.88 kmol dry air/ kmol wet air

1 kg/min 2 kmol/min

Volumetric flow rate is given

6m =

1 kmol dry air/min 2 kg of solids/min

6m
1 m3 dry air/min
708
0.70 kg H2O/Kg 0.12 kmol H2O/kmol wet air
0.30 kg Solids/Kg 0.88 kmol dry air/ kmol wet air

1 kg/min 2 kmol/min

Volumetric flow rate is given

6m =
R=8.2057338×10-5
(m3.atm.K-1.mol-1)
1 kmol dry air/min 2 kg of solids/min
6m
1 m3 dry air/min =10646.2 mol/min
=10.6 kmol/min 709
0.70 kg H2O/Kg 0.12 kmol H2O/kmol wet air
0.30 kg Solids/Kg 0.88 kmol dry air/ kmol wet air

1 kg/min 2 kmol/min

All the dry inlet air leaves

6m with wet air stream

1 kmol dry air/min 2 kg of solids/min

6m
1 m3 dry air/min
710
0.70 kg H2O/Kg 0.12 kmol H2O/kmol wet air
0.30 kg Solids/Kg 0.88 kmol dry air/ kmol wet air

1 kg/min 2 kmol/min

1= 0.88 2=9.37 kmol/min

6m =

1 kmol dry air/min 6m

1 m3 dry air/min
711
0.70 kg H2O/Kg 0.12 kmol H2O/kmol wet air
0.30 kg Solids/Kg 0.88 kmol dry air/ kmol wet air

1 kg/min 2 kmol/min

1= 0.88 2=9.37 kmol/min

6m =
R=8.2057338×10-5
(m3.atm.K-1.mol-1)
1 kmol dry air/min
Pabs=Patm+Pgauge=0.961 atm
6m
1 m3 dry air/min
=352.03 m3/min 712
0.70 kg H2O/Kg 0.12 kmol H2O/kmol wet air
0.30 kg Solids/Kg 0.88 kmol dry air/ kmol wet air

1 kg/min 2 kmol/min

Water Balance
6m 1/MW)=0.12 2
1/18)=0.12
1=32.71 kg/min

1 kmol dry air/min 6m

1 m3 dry air/min
713
0.70 kg H2O/Kg 0.12 kmol H2O/kmol wet air
0.30 kg Solids/Kg 0.88 kmol dry air/ kmol wet air

1 kg/min 2 kmol/min

6m Solid Balance

1 kmol dry air/min 2 kg of solids/min

6m
1 m3 dry air/min
714
0.70 kg H2O/Kg 0.12 kmol H2O/kmol wet air
0.30 kg Solids/Kg 0.88 kmol dry air/ kmol wet air

1 kg/min 2 kmol/min

Solid Balance
6m 1= 2
1=32.71 kg/min
2= 9.81 kg/min

1 kmol dry air/min 2 kg of solids/min

6m
1 m3 dry air/min Production rate of dried milk
is 9.81 kg/min 715
0.70 kg H2O/Kg 0.12 kmol H2O/kmol wet air
0.30 kg Solids/Kg 0.88 kmol dry air/ kmol wet air

1 kg/min 2 kmol/min

Upward velocity
of air

1 kmol dry air/min 2 kg of solids/min

6m
1 m3 dry air/min
716
0.70 kg H2O/Kg 0.12 kmol H2O/kmol wet air
0.30 kg Solids/Kg 0.88 kmol dry air/ kmol wet air

1 kg/min 2 kmol/min

Upward velocity Uair= 1/Cross sectional area

of air =(352.03 m3/min)/(pi*3*3 m2)
=12.46 m/min
=0.208 m/s

1 kmol dry air/min 2 kg of solids/min

6m
1 m3 dry air/min
717
• What problem would you guess would occur if the velocity is too
high?

Uair
Uparticle=gDp2(ρp- ρair)/(18µ air)

Uparticle

718
Problem Solving!

719
Problem Solving!

720
Flow Chart and Solution Procedure

721
 EQUATIONS OF STATE FOR NONIDEAL GASES
The ideal gas is the basis of the simplest and most convenient equation
of state. The calculations are independent of the species of the gas and
is the same for single species and mixtures.

Its shortcoming is that it can be seriously inaccurate. At a sufficiently low

temperature and/or a sufficiently high pressure, a value of predicted
with the ideal gas equation could be off by a factor of two or three or
more in either direction.

Therefore, there is need for complex but more accurate equations of

state for single species: Virial equation, van der Waals equation, Soave–
Redlich–Kwong equation 722
 Cubic Equations of State
van der Waals Equation of State:

723
 Cubic Equations of State
van der Waals Equation of State:

b accounts for the volume

occupied by the molecules
themselves.

724
 Cubic Equations of State
van der Waals Equation of State:

This term accounts for

b accounts for the volume
attractive forces between
occupied by the molecules
molecules
themselves.

725
 Cubic Equations of State
van der Waals Equation of State:

This term accounts for

b accounts for the volume
attractive forces between
occupied by the molecules
molecules
themselves.

726
Physical significance of Tc and Pc

727
 Physical significance of Tc and Pc

• Critical pressure: the pressure above which liquid and gas cannot
coexist at any temperature.

• Critical temperature: the temperature above which the gas cannot

become liquid, irrespective of the applied pressure.

728
Physical significance of Tc and Pc
• Consider a closed piston-fitted cylinder with water.

729
Physical significance of Tc and Pc
• Consider a closed piston-fitted cylinder with water.

• The cylinder temperature is first set to a specific value

with the cylinder pressure low enough for all the
water to be vapor  the water is compressed at
constant temperature by lowering the piston until a
drop of liquid water appears.

730
 Physical significance of Tc and Pc
• Consider a closed piston-fitted cylinder with water.

• The cylinder temperature is first set to a specific value

with the cylinder pressure low enough for all the
water to be vapor  the water is compressed at
constant temperature by lowering the piston until a
drop of liquid water appears.

• The pressure at which condensation begins (Pcond) and the densities

of the vapor (ρV) and of the liquid (ρl ) at that point are recorded 
repeat experiments at progressively higher temperatures.
731
Physical significance of Tc and Pc

732
• At 25 C, water condenses at a very low pressure, and the density
of the liquid is about five orders of magnitude greater than that of
the vapor.
733
• At higher temperatures, the condensation pressure increases and
the densities of the vapor and liquid at condensation approach each
other. 734
• At 374.15 C, the densities of the two phases are virtually equal, and
above that temperature no phase separation is observed, no matter
how high the pressure is raised. 735
• The highest temperature at which a species can coexist in two
phases (liquid and vapor) is the critical temperature (TC) of that
species, , and the corresponding pressure is the critical pressure (PC).
736
 Things to know!
• A VAPOUR is a gaseous species below its critical temperature, and a
GAS is a species above its critical temperature at a pressure low
enough for the species to be more like a vapor than a liquid (i.e., a
density closer to 1 g/L than 1000 g/L).

• We can condense a vapor by compressing it isothermally  liquid-

vapor phase separation
• We can make a gas denser and denser by compressing it isothermally,
however, we will never achieve a separation into two phases.

• Substances at temperatures above TC and pressures above PC are

referred to as SUPERCRITICAL FLUIDS 737
Cubic Equations of State
Soave–Redlich–Kwong (SRK)
Equation of State
Cubic Equations of State
Soave–Redlich–Kwong (SRK)
Equation of State

Pitzer acentric factor, ω , is parameter that reflects the geometry and

polarity of a molecule.
Cubic Equations of State

740
Virial Equation of State (VES)
VES is a power series in
inverse specific volume

Truncated form

• B,C, and D are functions of temperature and are known as the second, third,
and fourth virial coefficients, respectively.

• The ideal gas equation of state is obtained if B=C=D=…=0.

Virial Equation of State (VES)

ω is the Pitzer acentric factor, Tr=T/TC is the reduced pressure

THE COMPRESSIBILITY FACTOR EQUATION OF STATE

743
 THE COMPRESSIBILITY FACTOR EQUATION OF STATE

The compressibility ( ) of a gaseous species is defined as:

• z=1  the gas behaves ideally.

• The extent to which z differs from 1 is a measure of the extent to

which the gas is behaving nonideally.

744
 THE COMPRESSIBILITY FACTOR EQUATION OF STATE
The compressibility factor equation of state is:

• As ,

• Since / for a following gas stream

These equations serve as alternative to using a nonideal gas equation of

state. We need to determine z prior to using these equations.
745
 Compressibility Factor Tables

Use appropriate compressibility factor table

 Obtain z

 substitute in the compressibility factor equation of state

 solve for the unknown variable

746
747
 The Law of Corresponding States and Compressibility
Charts
It would be convenient if the compressibility factor at a single
temperature and pressure were the same for all gases, so that a single
chart or table of z(T,P) could be used for all PVT calculations. 
unfortunately this is not the case.
Example:
for nitrogen at 0 C and 100 atm is 0.9848 while
for carbon dioxide at the same temperature and pressure is 0.2020.
Consequently, to use tabulated values for all calculations we would have
to measure compressibilities as functions of temperature and pressure
separately for every chemical species.
748
 Alternate approach:

z can be estimated for a species at a given temperature, T , and pressure,

P, with the following procedure:

• Look up Tables  get critical temperature (TC) and critical pressure

(PC) of the species.

749
How to get critical temperature and pressure data?

750
 Alternate approach:

z can be estimated for a species at a given temperature, T , and pressure,

P, with the following procedure:

• Look up Tables  get critical temperature (TC) and critical pressure

(PC) of the species.

• Calculate the reduced temperature (Tr) and reduced pressure (Pr)

• Look up the value of z on the generalized compressibility chart 

plots z versus Pr for specified values of Tr
751
 Alternate approach:

The basis for estimating z in this way is the empirical law of

corresponding states, which states that:

the values of certain physical properties of a gas as—such as the

compressibility factor— depend to great extent on the proximity to its
critical state

752
 Alternate approach:

The reduced temperature and pressure provide a measure of this

proximity; the closer Tr and Pr are to 1, the closer the gas is to its critical
state.

This observation suggests that a plot of z versus Tr and Pr should be

approximately the same for all substances, which proves to be the case.

Such a plot is called the generalized compressibility chart

753
754
Generalized compressibility chart, low pressures

755
Generalized compressibility chart, medium pressures

756
Generalized compressibility chart, high pressures

757
Z(0), accounts for simple molecules, while the second
term, Z(1), is a correction factor for the “nonsphericity”
of a species. Z(0) and Z(1) depend only on Tr and Pr 758
 Nonideal Gas Mixtures
Key’s rule estimates pseudocritical properties of mixtures as simple
averages of purecomponent critical constants:

759
 Solve!
Dry ice (solid CO2) has been used as a mine explosive in the following
manner. A hole is drilled into the mine wall, filled with dry ice plus a
small charge of gunpowder, and then plugged. The gunpowder is lit with
a fuse, vaporizing the CO2 and building up an explosively high pressure
within the hole. Use each of the following correlations to estimate the
pressure that will develop if 5.00 g of dry ice is placed in a 50.0-mL hole
and heated to 1000 K:

(a) the ideal gas equation of state,

(b) the compressibility-factor equation of state, and
(c) the SRK equation of state.
760
 Solve!
Dry ice (solid CO2) has been used as a mine explosive in the following
manner. A hole is drilled into the mine wall, filled with dry ice plus a
small charge of gunpowder, and then plugged. The gunpowder is lit with
a fuse, vaporizing the CO2 and building up an explosively high pressure
within the hole. Use each of the following correlations to estimate the
pressure that will develop if 5.00 g of dry ice is placed in a 50.0-mL hole
and heated to 1000 K:

(a) the ideal gas equation of state 

P=(n/V)RT=((5 g/44.01 g/mol)/(50 mL))*(1000)*(82.06 mL.atm)

=186.46 atm 761
 Solve!
(b) the compressibility-factor equation of state:

762
Generalized compressibility chart, high pressures

763
764
 Solve!
(b) the compressibility-factor equation of state:

Tc= 304.5 K
Tr=T/ Tc = 1000 K/304.5 K =
Pc= 72.9 atm = 3.29

=
= 1.28
765
Generalized compressibility chart, high pressures

Z=1.05

766
 Solve!

(b) the compressibility equation of equation of state 

P=zRT/ =1.05*82.06*(1000)/(440.1)=195.07 atm

767
 Solve!
Dry ice (solid CO2) has been used as a mine explosive in the following
manner. A hole is drilled into the mine wall, filled with dry ice plus a
small charge of gunpowder, and then plugged. The gunpowder is lit with
a fuse, vaporizing the CO2 and building up an explosively high pressure
within the hole. Use each of the following correlations to estimate the
pressure that will develop if 5.00 g of dry ice is placed in a 50.0-mL hole
and heated to 1000 K:

(a) the ideal gas equation of state,

(b) the compressibility-factor equation of state, and
(c) the SRK equation of state.
768
Cubic Equations of State
Soave–Redlich–Kwong (SRK)
Equation of State

Pitzer acentric factor, ω , is parameter that reflects the geometry and

polarity of a molecule.
Tc= 304.5 K, Pc= 72.9 atm, ω=0.225

3.66×106 (mL)2/atm

29.70 (mL)/atm

0.826 P=197.9 atm

3.29

0.108
0.48508+1.55171*0.225-0.1561*0.225*0.225
771
772
The compressibility-factor equation of state:

T=27+273 = 300 K Trinitial=300/133=2.26

Prinitial=2514.7/507.15
Tc= 133 K
Pinitial=2500 psi + 14.7 psi = 2514.7 psi = 4.96
Pc= 34.5 atm
P60 hr=2245 psi + 14.7 psi = 2259.7 psi Tr60 hr =300/133=
= 507.15 psi
Pr60 hr=2259.7/507.15
=4.46

773
Generalized compressibility chart, medium pressures

774
The compressibility-factor equation of state:

Trinitial=300/133=2.26 zinitial=1.01 to 1.02 ninitial=1022 mol

Prinitial=2514.7/507.15
= 4.96

Tr60 hr =300/133=
Pr60 hr=2259.7/507.15
=4.46 z60 hr =1.01 to 1.02 n60 hr =918 mol

Leakage rate  1022 mol – 918 mol/ 60 hr= 1.73 mol/hr

775
Calculate the moles of CO in the room corresponding to TLV-C

776
Assume that room is filled with air initially. Since the concentration of
CO is in ppm, we can assume ideal gas mixture (1 atm and 300 K)

Moles of CO corresponding to TLV-C = mole fraction of CO

=(200x10-6 mol CO/mol air)*
(1 atm*30.7 m3)/(8.2x10-5 m3.atm.K-1.mol-1 300 K)
=0.25 mol

The minimum time required to reach TLV-C = 0.25 mol/(leakage rate)

=0.25 mol/1.73 mol/hr  0.14 hr

777
778
 Nonideal Gas Mixtures
Key’s rule estimates pseudocritical properties of mixtures as simple
averages of purecomponent critical constants:

779
780