CTDCHA2: Chemical Thermodynamics 2A

LEARNING UNIT 2

Properties of Pure
Fluids

1
Volumetric Properties of Pure
Fluids
• Volumetric or PvT properties stands for:
- Pressure-Volume/Specific volume-Temperature relations

• They are used to calculate properties of fluids such as internal

energy and enthalpy, from which Q and W requirements are
determined for industrial processes

• They are also used for metering of fluids and sizing of vessels/
pipelines (Design)
- Fluid - any material that can flow (liquid or gas)

2
3
 What is a Pure Substance?
• Pure substance - a substance
that has a fixed chemical
composition throughout e.g.
H2O, N2, He and CO2
• Pure substance/s do not have
to be of a single chemical
element/ compound as a
mixture of various chemical
elements/ compounds is also
a pure substance as long as
the mixture is homogeneous
and uniform in composition
• Air is a mixture of several
gases and is considered as
a pure substance because
it has a uniform chemical
composition throughout
• A mixture of oil and water is
not a pure substance as oil
is not soluble in water, it
‘collects’ on top of the water
forming two chemically
dissimilar regions
4
What is a mixture?
• A mixture of 2 or more phases of a pure
substance is still a pure substance as
long as the chemical composition of all
phases is the same
• A mixture of ice and liquid water is a pure
substance because both phases have
the same chemical composition
• A mixture of liquid and gaseous water is
a pure substance, but a mixture of liquid
and gaseous air is not
• A mixture of liquid air and gaseous air is
not a pure substance since the
composition of liquid air is different from
the composition of gaseous air

5
PvT Relations
•  There are 3 principle phases: solid, liquid and gas (which are
■
represented on P-v-T surface plots)

The arrangement of atoms in different phases: (a) molecules are

at relatively fixed positions in a SOLID, (b) groups of molecules
move about each other in the LIQUID phase, and (c) molecules
move about at random in the GAS phase

• Experimentally, it is known that T and v can be regarded as

independent, with P determined as a function of these two:
• A graph of such a function is a surface plot: the P-v-T
surface

6
PvT Relations
• Variations of properties during phase changes are
best studied and understood with the help of such
property diagrams (surface plots)

• Co-ordinates of a point on the P-v-T surface/s

represent values that P, v and T would assume when
the substance is at equilibrium

• Phase boundaries represent saturated conditions (T,

v and P)

7
P-T Surface Plots
• A P-T diagram does not provide any information about
volume but merely displays phase boundaries
• For each Psat there is a unique Tsat and vice versa
• Commonly known as a Phase Diagram

Critical point – highest

combination of pressure and
temperature where the fluid
exist in liq-vap equilibrium

The 2-C line, also known as

vaporization curve is where
liquid-vapor is in equilibrium

Triple point, three

The 1-2 line, also phases exist in The 2-3 line, also known as fusion
known as sublimation equilibrium curve is where solid-liquid is in
curve is where solid- equilibrium
vapor is in equilibrium

8
P-T Surface Plots
• A P-T diagram does not provide any information about
volume but merely displays phase boundaries
• For each Psat there is a unique Tsat and vice versa
• Commonly known as a Phase Diagram

A phase is a liquid if
vaporization results at
constant temperature
and pressure reduction

A phase is a gas if
condensation results at
constant pressure and
reduction in temperature

9
T-v Surface Plots
• There is little variation except
during phase change where V
changes at constant-T

• Constant P lines on the plot are

called isobars and they show
liquid, liquid/ vapour and vapour
regions

• With a change in P different

isobars are observed to shrink
until, P=Pc where they become
almost horizontal

10

• Once boiling starts, T will stop rising until liquid is
completely vaporised.
• T remains constant during entire phase-change
process if P is held constant.
• During vaporisation process, only change observed is
a large increase in volume and a steady decline in
liquid level as a result of more liquid turning to vapour.
• As heating continues, vaporization process will continue
until last drop of liquid is vaporised.
• At this point, entire cylinder is filled with vapour which is
on border line of liquid phase.
• Any heat loss from this vapour, will cause some vapour to
condense (phase change from vapour to liquid).
• A vapour, which is about to condense, is called a
saturated vapour. A substance at between 2 and 3 is
referred to as a saturated liquid-vapour mixture.

• [2] As more heat is

transferred, T keeps rising
until it reaches 100oC.
• At this point water is still a
liquid, but any heat addition,
will cause some of liquid to
vaporise.
• Phase-change process from
liquid to vapour is about to • [5] Water at State 5 is a
take place.
superheated vapour.
• A liquid which is about to
vaporise is called a saturated
liquid.
• Hence, State 2 is a saturated
liquid state.

• [4] Once phase-change process

• Heat now transferred to water.
• As T rises, liquid water will
expand slightly, and so its
specific volume will increase.
• To accommodate this
expansion, piston will move up
slightly.
• P in cylinder remains constant at
1atm during this process
because it depends on the
weight of piston, which is
constant.
completed, back to a single–
phase region (this time vapour),
and further transfer of heat will
result in an increase in both T
and specific volume.
• Vapour which is not about to
• [1] Consider piston-cylinder containing liquid water at
condense (i.e. not saturated
20oC and 1atm.
vapour) called superheated
• Under these conditions, water exits in liquid.
vapour.
• Called compressed liquid/ sub-cooled liquid, meaning
that its not about to vaporise.

11
P-v Surface Plots
• The general shape of a P-v plot of a pure substance is
similar to a T-v plot, but the constant T (isotherms) lines on
this plot have a downward trend

100 %
liquid 100 % vapor
@ boiling @
temp condensation
temp

12
P-v and T-v Surface Plots
• On P-v and T-v plots:
• Phase boundaries become areas i.e. regions where 2
phases such as, solid-liquid, solid-vapour and liquid-
vapour co-exist in equilibrium

• For a given T and P, the relative amounts of the phase(s)

determine molar (or specific) volume

• Triple point becomes a horizontal line on P-v plots

• Constant T and P lines on the diagram show liquid, liquid-

vapour and vapour regions

Click video icon for experimental

demonstration of a triple point

13
P-v and T-v Surface Plots (cont.)
• Isotherms at T<Tc and isobars at • Isotherms at T>Tc and isobars at
P<Pc cut phase boundaries of P>Pc do not cross a phase
different phases boundary

• Horizontal segments of isotherms

labelled T1 and T2 represent all
possible mixtures of liquid and
vapour in equilibrium (ranging
from 100% liquid - at the left end
to 100% vapour - at the right end)

• Isotherms in the sub-cooled-liquid

region are very steep, because
liquid volumes change little with
large changes in P

14
P-v-T Surface

• 3D P-v-T surfaces are useful

for showing general
relationships among the 3
phases of matter.

• However, it is more
convenient to work with 2D
projections of the surface

Located between single-phase regions are 2-phase regions where 2

phases exist in equilibrium: liquid-vapour, solid-liquid and solid-vapour

Click video icon for an intro PVT surface

15
Retrieving Thermodynamic
Properties
Thermodynamic property data can be retrieved in various ways,
including:

• Graphs e.g. P-v-T plots

• Equations of state (EOS) e.g. ideal gas and virial

• Tables e.g. steam tables (showing properties of water)

• Computer software

16
Tables (e.g. steam tables)
• For most substances, the relationships between the
thermodynamics properties are too complex to be expressed by
simple equations.

• Therefore, properties are frequently presented in the form of

Tables.

• Some thermodynamic properties can be measured easily, but

others can not be measured directly and are calculated by using
the relationships that relate them to measurable properties.

• The results of these measurements and calculations are

presented in such Tables in a convenient format.

17
Steam Tables
• The properties of saturated liquid, saturated vapour and saturated liquid-
vapour mixture for water are listed in the Steam Tables.

• Properties are listed under temperatures.

• Properties are listed under pressures.

• Subscript:
• g – denotes properties of dry saturated vapour
• f – denotes properties of saturated liquid
• fg – denotes difference between the dry saturated vapour and
saturated liquid values (of the same properties)
• vf is the specific volume of saturated liquid
• vg is the specific volume of saturated vapour
• vfg is the difference between vg and vf :
■vfg =vg - vf
18
Steam Tables

19
Steam Tables
• Steam
■   Tables are used to represent PvT data for steam (water vapour)
at different conditions
• Gives specific volume, internal energy, enthalpy and entropy.
• With Steam Tables only ONE parameter should be specified
e.g. T = 100oC gives:
Psat = 101.3 kPa; vliq=1.044cm3 g-1; vvap=1673cm3 g-1;
Uliq=419.0kJ kg-1;
Uvap=2506.5kJ kg-1; Hliq=419.1kJ kg-1; Hvap=2676.0kJ kg-1

• Using ideal gas equation for 1 g:

close to vapour specific volume

Click video icon for an introduction of

steam tables and how to use them.
20
Using Steam Tables
• A map (or GPS navigation system)
is necessary when driving in a new
area or a timetable is necessary
for learning, steam tables are
essential to steam-users in
industry
• Steam Tables are usually 2 forms:
(a) Saturated Steam tables and
(b) Superheated Steam tables
– Saturated steam tables are
used to determine saturated
steam temperature (Tsat) from
saturated steam pressure (Psat),
or Psat from Tsat
• Since Psat and Tsat are directly related to
one another, saturated Steam tables
are generally available in two different
formats:
Based on P and based on T but both
types contain the same data (simply
sorted differently)
• In addition to P and T, these Steam
tables usually include other related
values such as H, U and v
21
Using Steam Tables (cont.)
• Data found in a saturated Steam table
always refers to steam at a particular
saturation point (also known as the
boiling point)
• Boiling point - point where water (liquid)
and steam (gas/water vapour) can co-
exist at the same T and P
• Because H2O can be either liquid or gas
at its saturation point, two sets of data
are required:
• Data for saturated water (liquid), • At 150oC; H = 2761.2
which is typically marked with an "f“ • At 200oC; H = 2865.9
in subscript and
• At 190oC; H need to
• Data for saturated steam (gas), interpolate
which is typically marked using a
"g“ in subscript

Click video icon for how to

use interpolation
22
Using Steam Tables (cont.)

• Saturated Steam tables:

• Pressure can be absolute or gauge
• In this case, Pg = 0 bar and Pabs = 1 atm
• At 1 atm, Hf = 419 kJ/kg
• At 1 atm, Hg = 2676 kJ/kg
• At 1 atm, Hvap = 2257 kJ/kg

23
 Superheated Steam tables
• Values related to superheated steam cannot be obtained through a regular
saturated Steam table, but rather require use of a Superheated Steam table
• This is so because T of superheated steam, unlike saturated steam, can vary
considerably for the same pressure
• In fact, number of possible temperature-pressure combinations is so great that
it would be virtually impossible to gather them all in a single table
• As a result, a large number of superheated Steam tables use representative
pressure-temperature values to form a summary table

• Superheated Steam tables

• Pressure can be absolute or gauge
24
Example

How much more heat does superheated steam with

a temperature of 400°C and a pressure of 1.013 bar
a (0 bar g) have than saturated steam at the same
pressure?

Reveal solution

25
Equations of State
• Equation
■   of State (EoS): Functional equation to express the
relation between P, V, and T

• For the regions of the plots where a single phase exists in

equilibrium, a relationship is implied which connects P, V and T:

- solution for any one of the three quantities P, V or T as a

function of the other two can be determined

• The simplest Equation of State is for an ideal gas:

– PV = nRT,
– a relation which has approximate validity for low pressure
gas region
Click video icon for why and how to use
equations of state
28
Ideal Gas
•  As P0, Virial equations reduce to PV = RT
■

• This equation assumes that there are no

molecular interactions
• Property relations are defined by:
• Heat capacity at constant V:

• Heat capacity at constant P:

29
Property Relations for Ideal Gas
•  Ethalpy:
■

• A useful relation between Cpand Cv for an ideal gas comes

from differentiation of previous equation:
=> - =

• This means that Cpand CV are not constant for an ideal

gas, but that they vary with T in such a way that their
difference is equal to R
• and

30
Equations for Process Calculations
(for Ideal Gases)
•  For a unit mass or a mole of an ideal gas in any
■
mechanically reversible closed-system process:

• Work for a unit mass or mole for a mechanically

reversible closed-system process:
and

31
Calculating Q and W
•  For , equations become:
■
and (a)
• For , equations become:
and (b)
• For , equations become:
and (c)
• Equations are valid for ideal gases for mechanically
reversible closed systems

32
Mechanically Reversible Closed
System Process
•  Isothermal process:
■

• Isobaric process:
and

• Isochoric process:
and

33
Mechanically Reversible Closed
System Process (cont.)
•  Adiabatic Process:
■
For (a)
 (1)
Integrating (1) for constant CV gives:
For (b)
 (2)
Integrating (2) for constant CP gives:
For (c)
 (3)

34
 Mechanically Reversible Closed
System Process (cont.)
■  
Integrating (3) for constant CV and CP gives:
But

• Adiabatic equations can be summarised as (by definition: = Cp/Cv)

Equations apply to an ideal gas with

constant heat capacities undergoing a
mechanically reversible adiabatic process
• Work done:

• Integrating for constant CV:

35
Mechanically Reversible Closed
System Process (cont.)
■
•  RT1= P1V1 and RT2 = P2V2

• Then W becomes:

• V2 is eliminated (since )

• Thus:

36
Summary of Conditions
• Equations are valid for ideal gases with constant heat
capacities and mechanically reversible adiabatic
processes
• When applied to real gases, equations often yield
satisfactory approximations, provided the deviations
from ideal behaviour are relatively small
• For monatomic gases (such as He),  = 1.67
• For diatomic gases (such as N2, O2),  = 1.4
• For polyatomic gases (such as C02, SO2, NH3 and
CH4),  = 1.3

37
Polytropic Process
• Polytropic
■   (‘turning many ways’) process is a model of some
versatility and when used, the equations can be summarised as:

Click video icon for Polytropic

Process explanation

• For Isobaric process: =0

• For Isothermal process: =1
• For Adiabatic process:  = 
• For Isochoric process:  = 

38
Polytropic Process (cont.)

Isobaric
process

Isothermal
process

Adiabatic
process
Isochoric process

• =0, results in P=constant i.e. isobaric process

• =, results in V=constant i.e. isochoric process
• =1, results in PV=constant, which is an isothermal process for a perfect gas
• =, results in a reversible adiabatic process for a perfect gas

39
Polytropic Process (cont.)
• Equations relating changes in state functions are only valid for ideal
gases regardless of the process (apply equally to reversible and
irreversible processes, for closed and open systems)
• Equations for Q or W are specific to the process considered in its
derivation.
• W for an irreversible process (Wir) is obtained by a 2-step
procedure:
• W is determined for a mechanically reversible process (Wrev)
that accomplishes the same change of state as the actual
irreversible process (Wirr)
• Wrev is multiplied or divided by an efficiency to give the actual
Wirr
• If process does work, absolute value Wrev is too large and must be
multiplied by an efficiency whilst for a process requiring work, the
value for Wrev is too small and must be divided by an efficiency

40
Example
Air is compressed from an initial condition of 1 bar and 298.15K
(25oC) to a final state of 5 bar and 298.15K by three mechanically
reversible processes in a closed system:
(a) Heating at constant volume followed by cooling at constant
pressure
(b) Isothermal compression
(c) Adiabatic compression followed by cooling at constant
volume

Assume air to be an Ideal Gas with CV=(5/2)R , CP=(7/2)R

Calculate work required, heat transferred and the changes in internal
energy and enthalpy of the air for each process

Click here for solution

41
Virial Equations – Non-ideal Gases
• Graphical
■   representations (PVT plots) are normally complex and attempts
have been made to use equations to describe the relationships
• PV along an isotherm for gases have been expressed by power series in
different forms:
, a dimensionless factor called, compressibility factor is
used in Virial Equations as:

or

Where: B(T), B’(T), C(T), C’(T) etc., are called virial coefficients for a
given T only
• , , etc

44
Virial Equations – Non-ideal Gases
(cont.)
• Virial coefficients can be determined from experimental PVT
data or theoretically from statistical mechanics

• As pressure approaches zero, Virial equations reduce to Z = 1 or

PV = nRT (which is the ideal gas equation)

• Virial equations are applicable to gas phase of substances only

and thus, should not be used for liquids or liquid–vapour
mixtures or solids

• Many other Equations of State have been proposed for gases,

but Virial equations are the only ones having a firm basis in
theory
45
Deviation of Gases from Ideal
Gas Behaviour
• Z
■   is a measure of deviation from ideal behaviour
• If Z1, it is close to ideal gas behaviour
• Two other parameters are introduced:
Reduced P: ; Reduced T:
• At very low pressures (Pr<<1), gases behave as an ideal gas
regardless of temperature
• At high temperatures (Tr>2), ideal-gas behaviour can be assumed
with good accuracy regardless of pressure (except when Pr>>1)
• The deviation of a gas from ideal-gas behaviour is greatest in the
vicinity of the critical point

46
(a) Deviation from ideal behaviour (b) At lower P and high T,
is large at high P and low T deviation is typically small and
ideal gas law can be used to
predict behaviour with little error.
• Plotting experimentally determined value of Z for 1 mole of
various real gases as a function of P shows deviation from ideal
behaviour

47
Application of Virial Equations
• Applicable to non-ideal gases.
• For engineering purposes, use of
power series Virial equations is
practical only where convergence is
very rapid i.e. where 2 or 3 terms
suffice for reasonably close
approximations to the values of the
series.
• This is realised for gases and vapours
at low to moderate pressures
• Values of the compressibility factor Z
(as calculated from PvT data for gases
by the equation Z = PV/RT) are plotted Compressibility Factor Graph of CH4
vs P for various constant T.
• Resulting isotherms show graphically
what Virial expansion in P is intended
to represent analytically
48
Comparison of Z Factors for
Various Gases

49
Comparison of Z Factors for
Various Gases (cont.)
•  All isotherms originate at the value Z = 1 for P = 0 and they
■
are almost straight lines at low pressures
• Thus, the tangent to an isotherm at P = 0 is a good
approximation of the isotherm from P0 to some finite
pressure.
• Differentiation of:

• Gives:

• For which (truncated to two terms)

• The equation for tangent line is:
P

50
 Comparison of Z Factors for
Various Gases (cont.)
•  Substituting into tangent equation gives:
■
(Virial equation truncated to 2 terms)
• This equation satisfactorily represents the PvT behaviour of many
vapours at subcritical T for P  5 bar
• At higher T, it is appropriate for gases over an increasing P range as T
increases
• For P above the range of applicability, but below the Pc, the volume Virial
equation truncated to 3 terms often provides excellent results

• This equation can be solved directly for P, but is cubic in volume. Solution
for V is easily done by an iterative scheme with a calculator or computer
programme after re-arrangement:

51
 Comparison of Z Factors for Various
Gases (cont.)
•  A class of equations inspired by:
■

• Known as extended Virial equations, is illustrated by the Benedict-

Webb-Rubin equation:

where: Ao, Bo, Co, a, b, c,  & are all constant for a given fluid

• This equation and its modifications, despite their complexity, are

used in the petroleum and natural-gas industries for light
hydrocarbons (and a few other commonly encountered gases)

52
Example
■  
Reported values for the virial coefficients of isopropanol vapour at
473.15K (200oC) are: B = -0.388 m3kmol-1 and C = -26x10-3 m6kmol-2

Calculate V and Z for isopropanol vapour at 473.15K (200oC) and 1

bar by:
(a) Ideal gas equation
(b) 2nd term truncated virial equation
(c) 3rd term truncated virial equation
Virial equation truncated to 2 terms:
Click to reveal answers
Virial equation truncated to 3 terms:

53
Cubic Equations of State
• If an equation of state is to represent the PVT behaviour of both
liquids and vapours, it must encompass a wide range of
temperatures and pressures.
• Yet it must not be so complex as to present excessive numerical or
analytical difficulties in application.
• Polynomial equations that are cubic in molar volume offer a
compromise between generality and simplicity that is suitable to
many purposes.
• Cubic equations are in fact the simplest equations capable of
representing both liquid and vapour behaviour, namely:
• van der Waals equation of state
• Redlich-Kwong (RK) equation of state
• Benedict-Webb-Rubin equation of state
• Beattie-Bridgeman equation of state
• Lee-Kesler generalized correlation

55
van der Waals Equation of State
•  Proposed by J. D. van der Waals in 1873:
■

• a and b are positive constants;

• When they are zero, the equation reduces to ideal-gas equation;
• Values of a and b can be found in reference tables or determined by fitting
experimental data
• Given values of a and b for a particular fluid, one can calculate P as a
function of V for various values of T:
• At critical point;
,
• a and b are empirical parameters that correct for the interaction between gas
atoms or molecules and for the volume the gas species occupy, respectively

56
van der Waals Equation of State (cont.)

(a) Plot showing differences between (b) Plot showing differences between
3 equations of states for He. There is 3 equations of states for He at 298 K
very little difference below ~100 atm. in a 1.0 L container.

57
Generic Equations of State
•  Various cubic equations of state have been proposed after van
■
der Waals equation of state and all are special cases of the
equation
• The generic form is:

Where: b, , 𝜅,𝜆 and  are parameters which in general

depend on T and (for mixtures) composition
• Although this equation appears to possess great flexibility, it
has inherent limitations because of its cubic form

• Equation reduces to the van der Waals equation when  = b, 

= a and 𝜅 = 𝜆=0

58
Generic Equations of State (cont.)
•  Another generic equation is:
■

Where:
and  are pure numbers, the same for all substances,
whereas parameters a(T) and b are substance dependent
• Temperature dependence of a(T) is specific to each
Equation of State
• For the van der Waals equation, a(T) = a is a substance-
dependent constant, and ==0
• Comparing the 2 generic equations:
 = b;  = a(T); 𝜅 = (ϵ+)b; 𝜆 = ϵb2

59
Determination of Equation of State
Parameters
•  Constants in an Equation of State for a particular
■
substance may be evaluated by a ‘fit’ to available PvT data

• For cubic Equations of State, suitable estimates are

usually found from values for Tc and Pc

• Since the critical isotherm exhibits a horizontal inflection at

the critical point, the following mathematical conditions is
imposed:

60
Determination of Equation of State
Parameters (cont.)
•  Solving for constants gives:
■
and
Where:
 and  are pure numbers, independent of substance and
determined for a particular equation of state from the values
assigned to ϵ and a
• The result may be extended to T other than Tc by introduction of
a dimensionless function a(Tr) that becomes unity at the critical
temperature:

• Function (Tr ) is an empirical expression, specific to a particular

Equation of State

61
Parameter Assignments for Various
Equation of State(s)

62
Theorem of Corresponding States
•  Two parameter theorem of corresponding states (same
■
behaviour): All fluids when compared at the same Tr and
Pr have approximately the same compressibility factor
(Z) and all deviate from ideal-gas behaviour to about the
same degree
• For: and
• This is 2 parameter (Pr and Tr) theorem of corresponding
states
• Theorem is very nearly exact for simple fluids like argon,
krypton and xenon but systematic deviations are observed
for more complex fluids

63
Theorem of Corresponding States
(cont.)
•  A third corresponding-state parameter, characteristic of
■
molecular structure; the acentric factor ω is introduced to
improve results making it 3 parameter (Pr; Tr and ω) theorem
of corresponding states
• Acentric factor defined as difference at Tr= 0.7
OR
Where:
 can be determined for any fluid from Tc, Pc and a single
vapour-pressure measurement made at Tr= 0.7
• Values of  and critical constants Tc, Pc and Vc for a number
of fluids are listed in literature

64
Theorem of Corresponding States
(cont.)
• Definition of  makes its value 0 for argon, krypton
and xenon
• Experimental data yield(s) compressibility factors for
all three fluids that are correlated by the same curves
when Z is represented as a function of Tr and Pr
• This leads to the three-parameter theorem of
corresponding states:
All fluids having the same value of , when
compared at the same Tr and Pr have about
the same value of Z, and all deviate from ideal-
gas behaviour to about the same degree

65
Generalised Correlations for Gases
•  Pitzer correlations for the compressibility factor
■

Where:
Z0 and Z1are functions of both Tr and Pr
Z – compressibility factor of interested fluid
Z0 – compressibility factor of simple fluids, f(T r, Pr)
Z1 – correction parameter, f(Tr, Pr)
w – acentric factor, f(species)

• When  = 0, as is case for simple fluids (Ar, Kr and Xe),

the second term disappears, and Z0 becomes identical
with Z
66
Generalised Correlations for Gases
(cont.)
• Based on theorem of corresponding states
• Pitzer-type correlations developed by Lee and Kesler widely
preferred
• Generalized correlations developed by Lee and Kesler are
presented as Tables in Appendix E (Tables E.1 to E.4) of textbook
• It was developed based on a modified form of the
Benedict/Webb/Rubin Equation of State and it takes the form of
Tables which present values of Z0 and Z1 as functions of Tr and Pr
• Accuracy good for non-polar or slightly polar gases
• Big error for highly polar gases
• Can be used for both gases and liquids

67
 • To use Pitzer-type correlations:
• Determine Pr from P/Pc and Tr from T/Tc
• From the Tables, determine Zo and Z1
• Use equation: to get Z

68
Pitzer Correlations for the Second
Virial Coefficient
•  Problem with Pitzer’s 1st correlation is that Z0 and Z1 data not
■
readily available for most liquids and gases

• Generalised compressibility-factor correlation presented in

Tables made the process complex but the complexity of the
functions Z0 and Z1 means equations cannot be represented
by simple equations

• Approximate analytical expression to these functions for a

limited range of pressures can be given from the Virial
equation:
(1)

69
Pitzer Correlations for the Second
Virial Coefficient (cont.)
•  Pitzer and co-workers proposed a second correlation used in
■
conjunction with Virial equations, which yield values for
BPc/RTc

• Substituting into Virial equation (1) gives:

• Comparison with 1st Pitzer correlation gives:

and

70
Pitzer Correlations for the Second
Virial Coefficient (cont.)
•  Second virial coefficients are functions of T only
■

• Similarly B0and B1 are functions of Tr only (making

calculations easier)
• They are well represented as follows:
and

• These equations are most accurate for non-polar

species and least accurate for highly polar molecules

71
Example
■
Determine
  the molar volume of n-butane at 510 K and 2.5 bar by each
of the following:
(a) The Ideal-Gas equation
(b) The generalized compressibility-factor correlation
(c) The generalized Virial-coefficient correlation
Use: Tc= 425.1K; Pc = 37.96 bar and  = 0.2
Solution:
(a)
(b) and

From Table E.1 and E.2: Z0 = 0.865 and Z1 = 0.038 (see next 3 slides)

72
Solution (cont.)

73
 Solution (cont.)
Z0
Pr 0.60 0.659 0.80
Tr = 1.2 0.8779 ? 0.8330

74
Solution (cont.)
Z1
Pr 0.60 0.659 0.80
Tr = 1.2 0.0326 ? 0.0499

75
Solution (cont.)
■  

(c)

Experimental value is 1.4807 m3 kmol-1 (closer to answer determined

by the generalized compressibility-factor correlation)

76
Example
■  
Calculate Z and V for ethane at 50oC and 15 bar by the following (the critical
parameters of ethane are Tc = 305.3K, Pc = 48.72 bar and acentric factor, =
0.100) :
a. Ideal gas equation
b. Truncated Virial equation, using experimental value of virial
coefficients:
B = -156.7 cm3/mol and C = 9650 cm6/mol2
c. Truncated Virial equation, using a value of B from the generalised
Pitzer correlation
d. Generalised Pitzer correlation with parameters from Lee/Kesler
correlation
e. Redlich/Kwong (RK) equation, with estimated parameter a and b
f. Soave-Redlich-Kwong (SRK) equation
g. Peng-Robinson (PR) equation

77
 Formulae
■
(a)  PV = RT Z=1
(b) 
(c) and
for and
(d)
(e) and whereby,

78
Formulae (cont.)

(f)

(g)

(Click here to reveal solutions)

79
Generalised Correlations for Liquids

• Molar volumes of liquids can be calculated by means

of generalised cubic Equations of State but the results
are often not of high accuracy.

• However, Lee/Kesler correlation includes data for sub-

cooled liquids (provided in Tables valid for non-polar
and slightly polar fluids).

• In addition, generalised equations are available for

estimation of molar volumes of saturated liquids.

81
Equations of State (cont.)
•  For example, if V is considered a function of T and P,
■
then V = V(T, P):

• The partial derivatives have definite physical meaning

and are related to two properties (commonly tabulated
for liquids) and defined as follows:
• Volume expansivity:

• Isothermal compressibility:

82
Equations of State (cont.)
•  Combining the 3 equations gives:
■

• For conditions not close to critical point (Tc, Pc and

Vc), β and κ are weak functions of T and P

• For small changes in T and P, 𝛽 and 𝜅 can be

considered constant
• Integrating gives:

83
Example
•  For liquid acetone at 20oC and 1 bar:
■
o 𝛽 = 1.487x10-3 K-1;
o 𝜅 = 62x10-6 bar-1;
o V = 1.287x10-3 m3 kg-1

• Find:
(a) The value of at constant V
(b) The pressure generated by heating at constant V from
20oC and 1 bar to 30oC
(c) The change in volume for a change from 20oC and 1
bar to 0oC and 10 bar

Click here for solution

84
Generalised Correlations for Liquids
(cont.)
•■  Rackett correlation:
(Valid only for saturated liquids)
Only data required: Critical constants and results are usually accurate to 1
or 2%
• Lydersen, Greenkorn and Hougen correlation:
where: ris density at critical point
Giving:

Where:
V2 = required volume; V1 = known volume; r1, r2 = reduced densities
(read from (Figures - next slide)
Method gives good results and uses experimental data only

87
Generalised Correlations for Liquids
(cont.)

Generalised density correlation for liquids

88
Example

For ammonia at 310K (36.85oC), estimate the density of:

a) The saturated liquid;
b) The liquid at 100 bar
Use: Tc= 405.7; Pc = 112.8 bar; Vc= 0.07247 m3kmol-1;
Zc= 0.242

(Click here to reveal solutions)

89
• Make use of other lecturer(s)
and support divisions within
UJ

• Make effective use of the

tutors

• Make use of working in

groups

Source: http://www.glasbergen.com/wp-content/gallery/teamwork/toon359.gif

92
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