EOS and Non-Ideal Behaviour

Chemical Engineering
Thermodynamics – I
ChE–301
Aqeel Ahmad TAIMOOR
Class Objectives
 Understand the difference between compressible and
incompressible fluids and mathematical procedure to calculate
properties
 Understand Equation of State (EOS)
 Understand the Virial Equation (EOS)
 Understand the limitations of Virial Equation
 Understand the van der Waal EOS
 Understand how the parameters for van der Waal EOS can be
determined
Class Objectives
properties
determined
Volumetric Properties of
fluid
 Volume of fluid is required to design various chemical
equipment
 Volume is a function of temperature & pressure
 If the volume is weak function of pressure and

temperature (like for liquids at low pressures) then fluid
is termed as incompressible fluid
 Incompressible fluids volumes may be assumed constant

but a much better way to calculate the volume is by using
total differentials
P-T Diagram (Pure Substance)
P-V Diagram (Pure Substance)
Differential
Mathematics Differentials
 For a 2-D x-y graph slope =
dy/dx
 For a 3-D x-y-z graph slopes

are determined by keeping
one variable constant i.e.
partial differentials= (∂y/∂x)z
This means change in y with
x at constant z.
Total Differential
 dZ = (∂Z/∂Y)X dY + (∂Z/∂X)Y dX
 Similarly we can write for single phase diagram
 dV = (∂V/∂P)T dP + (∂V/∂T)P dT
 Let us define two quantities here
 (∂V/∂T)P = Iso-baric expansion
 β = 1/V (∂V/∂T)P
 β = Volume expansivity
Incompressible Fluids
 dV = (∂V/∂P)T dP + (∂V/∂T)P dT
 (∂V/∂P)T = Volume change at constant temperature
 κ = -1/V (∂V/∂P)T
 κ = Isothermal compressibility
 dV = -κVdP +βVdT
 ln(V2/V1) = β(T2-T1) – κ(P2-P1)
 β& κ are taken as constant but are weak function of
Temperature & Pressure.
 However the above equation is more realistic than the
assumption of incompressible fluids
Example
For liquid acetone at 20 oC and 1 bar,
β = 1.487 x 10-3 oC-1; κ = 62 x 10-6 bar-1; V= 1.287cm3/g
For acetone find the
1. Value of (∂P/∂T)V at 20 oC and 1 bar
2. Pressure generated by heating at constant V from 20 oC

and 1 bar to 30 oC
3. Change in volume for a change from 20 oC and 1 bar to 0

oC and 10 bar
Class Objectives
properties
determined
Equation of State
 Equation between P, T and V is termed as EOS
 Simplest equation PV=RT
 Non-ideal gas PV = ZRT

EOS
 Equation of state are

important to estimate
thermodynamic properties
Class Objectives
properties
determined
Virial Equation of State
 Most simple form of equation
of state is PV=RT
 Regression of isotherms
 A curve can be defined by a
polynomial of ‘n’ degree
 PV = a + bP + cP2 + …
 Such an equation is termed as
virial equation
 Above equation may be written
as
 PV = a(1+BP+CP2+…)
Non-Ideal Gas Simplest
Virial Equation
 PV = ZRT
 For pressure 0 to some

value the curve is
straight line
 So, Z = 1 + BP/RT
Virial Equations
 However straight line approximation does not valid after
certain pressure
 So other constants like ‘C’ should be taken in to account

for measuring the non-Ideal gas properties
 Viral equation in terms of Volume has proved to be more

effective than Pressure so Equation after Truncation
becomes
 Z = PV/RT = 1 + B/V + C/V2
 The above equation is cubic in Volume, So an iterative

solution is required
Example
Class Objectives
properties
determined
Virial Equations
 Virial equations does not converge rapidly to solution
 Virial coefficient beyond third are rarely known
 Truncation introduces an inherent error
 Virial coefficients are function of temperature and gas so

a large data base of every gas is required to solve above
equations
 However, research in quantum statistics has shown that

the virial equation constants are based on how two,
three, four…. Molecules interact each other
Cubic Equations of State
 An equation should be general so that it can be used for
wide range of pressure, Volume & Temperature
 The equation should not be complex to involve extensive

numerical computation.
 The cubic equations of state are the simplest equations

developed representing the behavior of fluids
 Many softwares include the routines to solve these

equations on computers
Class Objectives
properties
determined
van der Waal Correction
 Ideal gas molecules has no volume
 VR = Vig + NVmolR (Volume adjustment)
 As for one mole ‘N’ is constant and ‘Vmol’ for a certain gas
is constant thus VR = Vig + b or Vig = VR – b
 Ideal gas pressure is different than the real gas pressure
because of molecules attraction
 dU = Q + W = TdS – PdV
 For gas with no entropy change (dS = 0; assumption)
 dU/dV = –P
van der Waal Correction
 If there is no interaction between the molecules then ‘U’
does not change with the volume
 However for real gas ‘U’ is proportional to how much

gas has been squeezed?
 U = a/V
 dU/dV = –P = –a/V2 (Pressure adjustment)
 Pig Vig = RT (Ideal gas)
𝑎
𝑃+ 2 𝑉 − 𝑏 = 𝑅𝑇
𝑉
Class Objectives
properties
determined
Parameter Determination
Parameter determination
 From the figure it is clear that derivative (dP/dV)Tc and
double derivative (d2P/dV2)Tc = 0
 Or by definition the density of liquid and gas becomes

equal at critical point so the three roots will be same
 (V – Vc)3 = 0 V 3  3VcV 2  3Vc2V  Vc3  0
 Compare this with the van der Waal Equation

𝑎 27 𝑅 2𝑇 2
𝑃 + 2 𝑉 − 𝑏 = 𝑅𝑇 𝑎 =
𝐶
𝑉 64 𝑃 𝐶
𝑅𝑇𝐶 2 𝑎 𝑎𝑏 1 𝑅𝑇𝐶
𝑉3 − 𝑏+ 𝑉 + 𝑉− =0 𝑏=
𝑃𝐶 𝑃𝐶 𝑃𝐶 8 𝑃𝐶
Class Objectives
properties
determined
Class Objectives
 Understand the cubic equation of state roots
 Understand how to calculate the desired root from General

equation of state form
 Understand the difference between van der waal and SRK

equation
 Understand why van der waal and RK equation gives same

value for every gas
 Understand how interaction between molecules is related to

Antoine equation and acentric factor
 Be able to solve other EOS

Class Objectives


equation

value for every gas


The three roots
Liquid
Root
Ambiguous Vapour
Root Root
Example
Given that the vapour pressure of n-butane at 350oC is

9.4573bar, find the molar volumes of at these conditions
using van der Wall equation for
a. saturated vapour
b. saturated liquid
Class Objectives


equation

value for every gas


EOS in terms of reduced
Temperature and reduced
Pressure
 It is hard to construct a diagram based on the
individual gas critical properties so a method was
devised to generalise them in terms of reduced
temperature and reduced pressure
 Tr = T/Tc
 Pr = P/Pc
General form of EOS
Vapor like root
 Combining pressure volume equation with PV = ZRT a
generalized form of the EOS can be obtained
𝑍−𝛽
𝑍 = 1 + 𝛽 − 𝑞𝛽
𝑍 + 𝜀𝛽 𝑍 + 𝜎𝛽
𝑃𝑟 𝛼 𝑇𝑟
𝛽=Ω 𝑞=Ψ
𝑇𝑟 Ω𝑇𝑟
 The initial seed value is taken from the ideal gas law in
order to converge the solution i.e. Z = 1
General form of EOS
Liquid like root
1+𝛽−𝑍
𝑍 = 𝛽 + 𝑍 + 𝜀𝛽 𝑍 + 𝜎𝛽
𝑞𝛽
𝑃𝑟 𝛼 𝑇𝑟
𝛽=Ω 𝑞=Ψ
𝑇𝑟 Ω𝑇𝑟
 The initial seed value is taken as Z = β

van der Waal Equation
Problem

using van der Wall equation for
a. saturated vapour
b. saturated liquid
Problem
Class Objectives


equation

value for every gas


Redlich-Kwong Equation
 Van der Waal take ‘a’ as an independent of temperature
 The molecular interaction in reality is a function of

temperature
 Redlich-Kwong equation took molecular interaction as a

function of temperature
Redlich-Kwong Equation
Class Objectives


equation

value for every gas


Theorem of corresponding
states
 All Fluids, when compared at the same reduced

temperature and reduced pressure, have approximately the
same compressibility factor, and all deviate from Ideal-gas
behavior to about the same degree
Z = f(Tr, Pr) Nelson & Obert Charts
EOS
 Van der Waal and RK equations are not very accurate
 Thus they have very limited use
 For engineering design purposes other modifications

are required
Class Objectives


equation

value for every gas


Antoine Equation Analysis
 A regression analysis of the
saturation curve for pure
substance yields:
 Antoine equation
 logPsat = a – b/(T + c)
 Antoine equation is a key
equation to determine the
molecules interaction
 Because Antoine equation
is a boundary between
vapor and liquid (change in
molecular interaction)
Antoine Equation Analysis
 logPsat = a – b/(T + c)
 If c = 0 then
 This approximates that
 logPsat Vs 1/T is a straight

line
 logPrsat Vs 1/Tr is a straight

line
Theorem of
Corresponding States
 logPrsat Vs 1/Tr is straight line then
 d(logPrSat)/d(1/Tr) = m
 All Fluids, when compared at the same reduced

temperature and reduced pressure, have approximately the
same compressibility factor, and all deviate from Ideal-gas
behavior to about the same degree
 If the above theorem is valid then ‘m’ should be same

for all chemical species
 It is true for some simple gasses like Ar, Kr & Xe

Theorem of
Acentric factor
Theorem of
 But this is not true for all gases
 So There is a difference between the slopes for Simple

fluids (SF) and others
 logPrSat (SF) – logPrSat
 The acentric factor is defined when logPrSat (SF) = -1
 ω = -1 – logPrSat Tr = 0.7
 All fluids having same value of ω when compared at

same Tr & Pr, have about the same value of Z and all
deviate from ideal gas behavior to about the same degree
Class Objectives


equation

value for every gas


Peng Robinson
Soave-Redlich-Kwong
Class Objectives


equation

value for every gas


Class Objective
 Understand why the iterative solution is not very handy
with computers and devise an analytical solution to
cubic equation of state
 Understand Pitzer Correlations
 Understand the range of validity for Pitzer correlations
 Be able to apply the concept of total differentials to other

 Understand the Maxwell Properties and their

importance
 Understand the fundamental Property relations

Class Objective


importance

PR & SRK equations
 The same iterative method as described earlier can be
used for the calculations by PR and SRK method
 Although iterative procedures can be programmed on

computer but programmer does not like them as they
are expensive on machine resources
 A cubic equation can be solved analytically to provide

the three roots
EOS for Property Calculations
 ‘b’ is the correction because of the molecular size of
the gases (Black – Soave Redlich Kwong, red – Peng
Robinson)
𝑅𝑇𝐶 𝑅𝑇𝐶
𝑏 = 0.08664 𝑏 = 0.077796
𝑃𝐶 𝑃𝐶
 ‘a’ is the correction because of the molecular
interactions
2
𝑅𝑇𝐶
𝑎 = 0.42748 1 + 𝜅 1 − 𝑇𝑟0.5 2
𝑃𝐶
𝑅𝑇𝐶 2
𝑎 = 0.457235 1 + 𝜅 1 − 𝑇𝑟0.5 2
𝑃𝐶
 ‘κ’ is a function of ‘ω’
𝜅 = 0.48 + 1.5741𝜔 − 0.176𝜔2

 For Peng Robinson model if ‘ω < 0.49’
𝜅 = 0.37464 + 1.54226𝜔 − 0.26992𝜔2
 For Peng Robinson model if ‘ω > 0.49’
𝜅 = 0.379642 + 1.48503 − 0.164423 − 1.01666𝜔 𝜔 𝜔

 There is another way to define the ‘EOS’ which is easy
to solve for softwares without iteration
𝑅𝑇 𝑎 𝑅𝑇 𝑎
𝑃= − 𝑃= −
𝑉−𝑏 𝑉 𝑉+𝑏 𝑉 − 𝑏 𝑉 𝑉 + 𝑏 + 𝑏(𝑉 − 𝑏)
𝑍 3 − 𝑍 2 + 𝐴 − 𝐵 − 𝐵2 𝑍 − 𝐴𝐵 = 0
𝑍 3 − 1 − 𝐵 𝑍 2 + 𝐴 − 2𝐵 − 3𝐵2 𝑍 − 𝐴𝐵 − 𝐵2 − 𝐵3 = 0
𝑎𝑃 𝑏𝑃
𝐴= 𝐵=
𝑅𝑇 2 𝑅𝑇
Solution to cubic equation
 Either use ‘the routines’ to find the roots of this
equation or one can follow the following solution to
find ‘Z’
𝑥 3 + 𝑏𝑥 2 + 𝑐𝑥 + 𝑑 = 0
𝑍 3 − 𝑍 2 + 𝐴 − 𝐵 − 𝐵2 𝑍 − 𝐴𝐵 = 0
𝑍 3 − 1 − 𝐵 𝑍 2 + 𝐴 − 2𝐵 − 3𝐵2 𝑍 − 𝐴𝐵 − 𝐵2 − 𝐵3 = 0
𝑏 = −1 𝑏 =− 1−𝐵 2𝑏 3 − 9𝑏𝑐 + 27𝑑
𝑄=
𝑐 = 𝐴 − 𝐵 − 𝐵2 27
𝑐 = 𝐴 − 2𝐵 − 3𝐵2
3𝑐 − 𝑏 2
𝑑 = −𝐴𝐵 𝑑 = −(𝐴𝐵 − 𝐵2 − 𝐵3 𝑃=
3
𝑄2 𝑃3
𝑅= +
4 27
Solution to cubic equation
 If R < 0 (three roots exist, max = gas, min = liquid)
−𝑃 3𝑄 𝑐𝑜𝑠 −1 𝑡
𝑚=2 𝑡= 𝜃=
3 𝑃𝑚 3
𝑏
𝑥1 = 𝑚 𝑐𝑜𝑠𝜃 −
3
4 𝑏
𝑥2 = 𝑚 𝑐𝑜𝑠 𝜃 + 𝜋 −
3 3
2 𝑏
𝑥3 = 𝑚 𝑐𝑜𝑠 𝜃 + 𝜋 −
3 3
 If R > 0 (above critical point)
1 1
−𝑄 3 −𝑄 3 𝑏
𝑥= + 𝑅 + − 𝑅 −
2 2 3
Problem

using PR EOS
a. saturated vapour
b. saturated liquid
Class Objective


importance

Pitzer Correlation for the
compressibility factor
 Pitzer and his co-workers give a generalized correlation
for Z by
 Z = Zo +ωZl
 The values of Zo and Zl are provided in the form of

tables as a function of Tr & Pr
Pitzer Correlation for second
Virial coefficient ‘B’
 General virial equation truncated to second virial
coefficient
 Z = 1 + BP/RT = 1 + B`Pr/Tr
 B` = Bo + ωBl
 So generalized equation with second virial coefficient

become
 Z = 1 + BoPr/Tr+ ωBlPr/Tr
0.422 0.172
𝐵𝑜 = 0.083 − 1.6 𝐵𝑙 = 0.139 − 4.2
𝑇𝑟 𝑇𝑟
Pitzer Correlation for third
Virial coefficient ‘C’
 General virial equation truncated to third virial
coefficient
 Z = 1 + B`Pr/(Tr Z) + C`(Pr/(Tr Z) )2
 B` = Bo + ωBl
 C` = Co + ωCl
0.02432 0.00313
𝐶𝑜 = 0.01407 + −
𝑇𝑟 𝑇𝑟10.5
0.05539 0.00242
𝐶𝑙 = −0.02676 + 2.7 −
𝑇𝑟 𝑇𝑟10.5
Example
Class Objective


importance

Validity of the solution
Problem
Problem
Class Objective


importance

Total Differential of Internal
Energy
 Temperature and pressure can be measured
 Get an expression for internal energy as a function of

temperature and volume
 U = f(T,V)
 Write total differential
𝜕𝑈 𝜕𝑈
𝜕𝑈 = 𝜕𝑇 + 𝜕𝑉
𝜕𝑇 𝑉
𝜕𝑉 𝑇
Thermodynamic Properties
𝜕𝑈
 Constant volume heat capacity = 𝐶𝑉
𝜕𝑈 𝜕𝑇 𝑉
∗
 For ideal gas = 𝐶𝑉
𝜕𝑇 𝜕𝐻
 Constant pressure heat capacity = 𝐶𝑃
𝜕𝑇 𝑃
𝜕𝐻
 For ideal gas = 𝐶𝑃∗
𝜕𝑇
 Coefficient of thermal expansion (works for 1 𝜕𝑉
liquids and solids over limited range) =𝛼
𝑉 𝜕𝑇 𝑃
 Isothermal compressibility (works for liquids
and solids over limited range) 1 𝜕𝑉
− =𝜅
𝑉 𝜕𝑃 𝑇
Class Objective


importance

Thermodynamic relation
 Define mathematically U,  Alternatively U, H, A and
H, A and G G
𝜕𝑈 = 𝑄 + 𝑊 𝜕𝑈 = 𝑇𝜕𝑆 − 𝑃𝜕𝑉
𝜕𝑄 = 𝑇𝜕𝑆
𝜕𝐻 = 𝜕U + 𝜕 𝑃𝑉 𝜕𝐻 = 𝑇𝜕𝑆 + 𝑉𝜕𝑃
𝜕𝐴 = 𝜕U − 𝜕 𝑇𝑆 𝜕𝐴 = −𝑃𝜕𝑉 − 𝑆𝜕𝑇
𝜕𝐺 = 𝜕H − 𝜕 𝑇𝑆 𝜕𝐺 = 𝑉𝜕𝑃 − 𝑆𝜕𝑇
Thermodynamic Identities
𝜕𝑈 = 𝑇𝜕𝑆 − 𝑃𝜕𝑉 𝜕𝐻 = 𝑇𝜕𝑆 + 𝑉𝜕𝑃 𝜕𝐴 = −𝑃𝜕𝑉 − 𝑆𝜕𝑇 𝜕𝐺 = 𝑉𝜕𝑃 − 𝑆𝜕𝑇
𝜕𝑈 𝜕𝐻 𝜕𝐴 𝜕𝐺
=𝑇 =𝑇 = −𝑃 =𝑉
𝜕𝑆 𝜕𝑆 𝑃
𝜕𝑉 𝑇
𝜕𝑃 𝑇
𝑉
𝜕𝑈 𝜕𝐻 𝜕𝐴 𝜕𝐺
= −𝑃 =𝑉 = −𝑆 = −𝑆
𝜕𝑉 𝑆 𝜕𝑃 𝜕𝑇 𝑉
𝜕𝑇 𝑃
𝑆
𝜕𝑈 𝜕𝑇 𝜕𝐻 𝜕𝑇
= 𝐶𝑉 =𝑇 = 𝐶𝑃 =𝑇
𝜕𝑆 𝑉
𝜕𝑆 𝑉
𝜕𝑆 𝜕𝑆
𝑃 𝑃
Maxwell relations
𝜕𝑈 = 𝑇𝜕𝑆 − 𝑃𝜕𝑉 𝜕𝐻 = 𝑇𝜕𝑆 + 𝑉𝜕𝑃
𝜕𝑈 𝜕𝑈 𝜕𝐻 𝜕𝐻
=𝑇 = −𝑃 =𝑇 =𝑉
𝜕𝑆 𝜕𝑉 𝜕𝑆 𝑃 𝜕𝑃
𝑉 𝑆 𝑆
𝜕2𝑈 𝜕𝑇 𝜕2𝑈 𝜕𝑃 𝜕2𝐻 𝜕𝑇 𝜕2𝐻 𝜕𝑉

= =− = =
𝜕𝑉𝜕𝑆 𝜕𝑉 𝜕𝑆𝜕𝑉 𝜕𝑆 𝜕𝑃𝜕𝑆 𝜕𝑃 𝜕𝑆𝜕𝑃 𝑆𝑃
𝜕𝑆 𝑃
𝑉𝑆 𝑆 𝑆𝑉 𝑉 𝑃𝑆 𝑆
𝜕𝑇 𝜕𝑃 𝜕𝑇 𝜕𝑉
=− =
𝜕𝑉 𝜕𝑆 𝜕𝑃 𝑆
𝜕𝑆 𝑃
𝑆 𝑉
Maxwell relations
𝜕𝐴 = −𝑃𝜕𝑉 − 𝑆𝜕𝑇 𝜕𝐺 = 𝑉𝜕𝑃 − 𝑆𝜕𝑇
𝜕𝐴 𝜕𝐴 𝜕𝐺 𝜕𝐺
= −𝑃 = −𝑆 = −𝑆 =𝑉
𝜕𝑉 𝜕𝑇 𝜕𝑇 𝑃
𝜕𝑃 𝑇
𝑇 𝑉
𝜕2𝐴 𝜕𝑃 𝜕2𝐴 𝜕𝑆 𝜕2𝐺 𝜕𝑆 𝜕2𝐺 𝜕𝑉

=− =− =− =
𝜕𝑇𝜕𝑉 𝑇𝑉
𝜕𝑇 𝑉
𝜕𝑉𝜕𝑇 𝑉𝑇
𝜕𝑉 𝑇
𝜕𝑃𝜕𝑇 𝑃𝑇
𝜕𝑃 𝑇
𝜕𝑇𝜕𝑃 𝑇𝑃
𝜕𝑇 𝑃
𝜕𝑃 𝜕𝑆 𝜕𝑆 𝜕𝑉
= − =
𝜕𝑇 𝑉
𝜕𝑉 𝑇
𝜕𝑃 𝜕𝑇
𝑇 𝑃
Class Objective


importance

Example
 Total differential
𝜕𝑈 𝜕𝑈 𝜕𝑈
𝜕𝑈 = 𝜕𝑇 + 𝜕𝑉 𝜕𝑈 = 𝐶𝑉 𝜕𝑇 + 𝜕𝑉
𝜕𝑇 𝜕𝑉 𝜕𝑉 𝑇
𝑉 𝑇
𝑇𝜕𝑆 − 𝑃𝜕𝑉
𝜕𝑈 = 𝐶𝑉 𝜕𝑇 + 𝜕𝑉
𝜕𝑉 𝑇
𝜕𝑆 𝜕𝑉
𝜕𝑈 = 𝐶𝑉 𝜕𝑇 + 𝑇 −𝑃 𝜕𝑉
𝜕𝑉 𝑇
𝜕𝑉 𝑇
 Maxwell relation
𝜕𝑃 𝜕𝑆 𝜕𝑃
= 𝜕𝑈 = 𝐶𝑉 𝜕𝑇 + 𝑇 − 𝑃 𝜕𝑉
𝜕𝑇 𝑉
𝜕𝑉 𝑇
𝜕𝑇 𝑉
Example
 Derive a relation for enthalpy using H = f(T,P)
Solution
𝜕𝐻 𝜕𝐻
𝜕𝐻 = 𝜕𝑇 + 𝜕𝑃
𝜕𝑇 𝑃
𝜕𝑃 𝑇 𝜕𝑆 𝜕𝑉
− =
𝜕𝑃 𝑇
𝜕𝑇 𝑃
𝜕𝐻
𝜕𝐻 = 𝐶𝑃 𝜕𝑇 + 𝜕𝑃
𝜕𝑃 𝑇
𝜕𝐻 = 𝑇𝜕𝑆 + 𝑉𝜕𝑃 𝜕𝑉
𝜕𝐻 = 𝐶𝑃 𝜕𝑇 + 𝑉 − 𝑇 𝜕𝑃
𝑇𝜕𝑆 + 𝑉𝜕𝑃 𝜕𝑇 𝑃
𝜕𝐻 = 𝐶𝑃 𝜕𝑇 + 𝜕𝑃
𝜕𝑃 𝑇
𝜕𝑆 𝜕𝑃
𝜕𝐻 = 𝐶𝑃 𝜕𝑇 + 𝑇 +𝑉 𝜕𝑃
𝜕𝑃 𝑇
𝜕𝑃 𝑇
Solution
 The term dV/dT is avoided as the EOS is hard to
differentiate in this form. It is preferable to replace
dV/dT by dP/dT
𝜕𝐻 = 𝜕U + 𝜕 𝑃𝑉
𝜕𝑃
𝜕𝑈 = 𝐶𝑉 𝜕𝑇 + 𝑇 − 𝑃 𝜕𝑉
𝜕𝑇 𝑉
𝜕𝑃
𝜕𝐻 = 𝐶𝑉 𝜕𝑇 + 𝑇 − 𝑃 𝜕𝑉 + 𝜕 𝑃𝑉
𝜕𝑇 𝑉
Example
 Entropy fundamental relation
Entropy relation solution
 S=f(T,V)
𝜕𝑆 𝜕𝑆 𝜕𝑃 𝜕𝑆
𝜕𝑆 = 𝜕𝑇 + 𝜕𝑉 =
𝜕𝑇 𝜕𝑉 𝜕𝑇 𝑉
𝜕𝑉 𝑇
𝑉 𝑇
𝜕𝑇 𝐶𝑉 𝜕𝑃
𝐶𝑉 =𝑇 𝜕𝑆 = 𝜕𝑇 + 𝜕𝑉
𝜕𝑆 𝑉 𝑇 𝜕𝑇 𝑉
𝜕𝑆 𝐶𝑉
=
𝜕𝑇 𝑉
𝑇
Fundamental Relation
𝜕𝑃
𝜕𝑈 = 𝐶𝑉 𝜕𝑇 + 𝑇 − 𝑃 𝜕𝑉
𝜕𝑇 𝑉
𝜕𝑃
𝜕𝐻 = 𝐶𝑉 𝜕𝑇 + 𝑇 − 𝑃 𝜕𝑉 + 𝜕 𝑃𝑉
𝜕𝑇 𝑉
𝐶𝑉 𝜕𝑃
𝜕𝑆 = 𝜕𝑇 + 𝜕𝑉
𝑇 𝜕𝑇 𝑉
Problem
Determine the relation between Joule-Thomson coefficient
and temperature and pressure
Joule – Thomson Coefficient
 Joule Thomson effect is define as the change in
temperature with change in pressure at constant enthalpy
𝜕𝑇
 Mathematically 𝜇=
𝜕𝑃 𝐻
𝜕𝑉
𝜕𝐻 = 𝐶𝑃 𝜕𝑇 + 𝑉 − 𝑇 𝜕𝑃
𝜕𝑇 𝑃
𝜕𝑉
𝜕𝑉 − 𝑉−𝑇
0 = 𝐶𝑃 𝜕𝑇 + 𝑉 − 𝑇 𝜕𝑃 𝜕𝑇 𝜕𝑇 𝑃
𝜕𝑇 = 𝜕𝑃
𝑃 𝜕𝑃 𝐻
𝐶𝑃
Class Objective


importance

Class Objective
 Understand departure function and why ideal properties
are essential
 Understand the procedure to calculate thermodynamic

properties for pure component
 Understand the procedure to calculate the

thermodynamic properties using incompressibility
factors
 Know the procedure to calculate the thermodynamic

properties using Pitzer correlations
Class Objective
are essential


factors

Enthalpy Calculations
𝜕𝑃
𝜕𝐻 = 𝐶𝑉 𝜕𝑇 + 𝑇 − 𝑃 𝜕𝑉 + 𝜕 𝑃𝑉
𝜕𝑇 𝑉
𝜕𝑃
𝜕𝑃 𝜕𝐻 = 𝑇 − 𝑃 𝜕𝑉 + 𝜕 𝑃𝑉
𝜕𝐻 = 𝑇 − 𝑃 𝜕𝑉 + 𝜕 𝑃𝑉 𝜕𝑇 𝑉
𝜕𝑇 𝑉
Ideal properties
are used to
calculate the real
properties
𝜕𝐻
= 𝐶𝑃∗
𝜕𝑇
Departure Function
Departure Function
P≈0
𝜕𝑃
Reference T 𝜕𝐻 = 𝑇 − 𝑃 𝜕𝑉 + 𝜕 𝑃𝑉
𝜕𝑇
Point 𝑉
Departure function
𝜕𝑃
𝜕𝐻 = 𝑇 − 𝑃 𝜕𝑉 + 𝜕 𝑃𝑉
𝜕𝑇 𝑉
𝑉
𝜕𝑃
𝐻 − 𝐻 𝑖𝑔 =න 𝑇 − 𝑃 𝜕𝑉 + 𝑃𝑉 − 𝑃𝑉 𝑖𝑔
𝑉≈∞ 𝜕𝑇 𝑉
𝑉
𝜕𝑃
𝐻− 𝐻 𝑖𝑔 = 𝑅𝑇 𝑍 − 1 න 𝑇 − 𝑃 𝜕𝑉
𝑉≈∞ 𝜕𝑇 𝑉
Enthalpy From PR
𝑉
𝜕𝑃
𝐻− 𝐻 𝑖𝑔 = 𝑅𝑇 𝑍 − 1 න 𝑇 − 𝑃 𝜕𝑉
𝑉≈∞ 𝜕𝑇 𝑉
𝑅𝑇 𝑎 Peng Robinson
𝑃= −
𝑉 − 𝑏 𝑉 𝑉 + 𝑏 + 𝑏(𝑉 − 𝑏) Equation of State
𝜕𝑃 𝑅 𝑑𝑎ൗ
= − 𝑑𝑇
𝜕𝑇 𝑉
𝑉 − 𝑏 𝑉 𝑉 + 𝑏 + 𝑏(𝑉 − 𝑏)
𝑉
𝑅 𝑑𝑎ൗ 𝑅𝑇 𝑎
𝐻 𝑑𝑒𝑝 = 𝑅𝑇 𝑍 − 1 + න 𝑇 − 𝑑𝑇 − + 𝜕𝑉
𝑉≈∞ 𝑉 − 𝑏 𝑉 2 + 2𝑏𝑉 − 𝑏 2 𝑉 − 𝑏 𝑉 2 + 2𝑏𝑉 − 𝑏 2
Enthalpy From PR
𝑉
𝑅 𝑑𝑎ൗ 𝑅𝑇 𝑎
𝐻 𝑑𝑒𝑝 = 𝑅𝑇 𝑍 − 1 + න 𝑇 − 2 𝑑𝑇 − + 𝜕𝑉
𝑉≈∞ 𝑉 − 𝑏 𝑉 + 2𝑏𝑉 − 𝑏 2 𝑉 − 𝑏 𝑉 2 + 2𝑏𝑉 − 𝑏 2
𝑑𝑥 1 2𝑎𝑥 + 𝑏 − 𝑏 2 − 4𝑎𝑐
න 2 = 𝑙𝑛
𝑎𝑥 + 𝑏𝑥 + 𝑐 2
𝑏 − 4𝑎𝑐 2𝑎𝑥 + 𝑏 + 𝑏 2 − 𝑎𝑎𝑐
𝑇 𝑑𝑎ൗ𝑑𝑇 − 𝑎 𝑍+ 1+ 2 𝐵
𝐻 − 𝐻 𝑖𝑔 = 𝑅𝑇 𝑍 − 1 + 𝑙𝑛
2 2𝑏 𝑍+ 1− 2 𝐵
PR to calculate properties
𝑇 𝑑𝑎ൗ𝑑𝑇 − 𝑎 𝑍+ 1+ 2 𝐵
𝐻 − 𝐻 𝑖𝑔 = 𝑅𝑇 𝑍 − 1 + 𝑙𝑛
2 2𝑏 𝑍+ 1− 2 𝐵
𝑑𝑎ൗ
𝑑𝑇 𝑍+ 1+ 2 𝐵
𝑆 − 𝑆 𝑖𝑔 = 𝑅𝑙𝑛 𝑍 − 𝐵 + 𝑙𝑛
2 2𝑏 𝑍+ 1− 2 𝐵
𝑃𝑉
𝑍=
𝑅𝑇
𝑃𝑏
𝐵=
𝑅𝑇
SRK to calculate properties
𝑎 𝑇 − 𝑇 𝑑𝑎ൗ𝑑𝑇 𝑍+𝐵
𝐻 − 𝐻 𝑖𝑔 = 𝑅𝑇 𝑍 − 1 − 𝑙𝑛
𝑏 𝑍
𝑑𝑎 1 𝑍+𝐵
𝑆 − 𝑆 𝑖𝑔 = 𝑅𝑙𝑛 𝑍 − 𝐵 + 𝑙𝑛
𝑑𝑇 𝑏 𝑍
𝑃𝑉
𝑍=
𝑅𝑇
𝑃𝑏
𝐵=
𝑅𝑇
Class Objective
are essential


factors

Procedure to use EOS for
Property Calculations
 Calculate ‘b’ and ‘a’
 Calculate da/dT 1 + 𝜅 1 − 𝑇ൗ𝑇

𝑑𝑎 𝑅2 𝑇𝑐2 𝑐
= −Ψ 𝜅
𝑑𝑇 𝑃𝑐 𝑇𝑇𝑐
 Where ‘κ’ is the acentric term in ‘α’
 Calculate Z
Procedure to use EOS for
Property Calculations
 Ideal gas enthalpy is either calculated by using heat
capacity or by using polynomial functions
𝐻 𝑖𝑔 = 𝑎 + 𝑏𝑇 + 𝑐𝑇 2 + 𝑑𝑇 3 + ⋯
 Calculate enthalpy and entropy with respect to

reference temperature
 Use U = H-PV and G = H-TS to calculate internal

and Gibbs energy
Problem
Find the values for the enthalpy and residual entropy
(departure functions) for n-butane gas at 500 K and 50 bar as
given by SRK and PR EOS.
Problem
Estimate V, U, H and S for 1-butane vapour at 200οC and 70
bar, if H and S are set to zero for saturated liquid at 0οC.
Assume that the only data available are
Tc =420 K
Pc = 40.43 bar
ω = 0.191
Cp/R = 1.967 + 31.63 x 10-3T – 9.837 x 10-6T2

Class Objective
are essential


factors

 For some range, for liquids iso-baric expansion and
isothermal compressibility factors can be used
𝜕𝑉
𝜕𝐻 = 𝐶𝑃 𝜕𝑇 + 𝑉 − 𝑇 𝜕𝑃
𝜕𝑇 𝑃
1 𝜕𝑉
𝛽=
𝑉 𝜕𝑇 𝑃
𝜕𝐻 = 𝐶𝑃 𝜕𝑇 + 1 − 𝛽𝑇 𝑉𝜕𝑃
 If S = f(T,P) then a relation can be obtained
𝐶𝑃 𝜕𝑉
𝜕𝑆 = 𝜕𝑇 − 𝜕𝑃
𝑇 𝜕𝑇 𝑃
1 𝜕𝑉
𝛽=
𝑉 𝜕𝑇 𝑃
𝐶𝑃
𝜕𝑆 = 𝜕𝑇 − 𝛽𝑉𝜕𝑃
𝑇
𝛽 1 𝜕𝑉
𝜕𝑈 = 𝐶𝑉 𝜕𝑇 + 𝑇−𝑃 𝜕𝑉 𝜅=−
𝜅 𝑃
𝑉 𝜕𝑃 𝑇
Class Objective
are essential


factors

Pitzer/Lee Kesler Correlations
 Z = Zo + ωZl
 Values of Zo and Zl are provided in ‘Appendix E’ of

Smith & van Ness
𝑑𝑒𝑝 𝑜 𝑑𝑒𝑝 𝑙
𝐻 𝑑𝑒𝑝 𝐻 𝐻
= +𝜔
𝑅𝑇𝑐 𝑅𝑇𝑐 𝑅𝑇𝑐
𝑑𝑒𝑝 𝑜 𝑑𝑒𝑝 𝑙
𝑆 𝑑𝑒𝑝 𝑆 𝑆
= +𝜔
𝑅𝑇𝑐 𝑅𝑇𝑐 𝑅𝑇𝑐
Class Objective
are essential


factors


EOS and Non-Ideal Behaviour

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Chemical Engineering

 Understand Equation of State (EOS)

 Understand the Virial Equation (EOS)

 Understand the limitations of Virial Equation

 Understand the van der Waal EOS

 Understand Equation of State (EOS)

 Understand the Virial Equation (EOS)

 Understand the limitations of Virial Equation

 Understand the van der Waal EOS

 Volume is a function of temperature & pressure

 If the volume is weak function of pressure and

 Incompressible fluids volumes may be assumed constant

 For a 3-D x-y-z graph slopes

β = 1.487 x 10-3 oC-1; κ = 62 x 10-6 bar-1; V= 1.287cm3/g

For acetone find the

1. Value of (∂P/∂T)V at 20 oC and 1 bar

2. Pressure generated by heating at constant V from 20 oC

3. Change in volume for a change from 20 oC and 1 bar to 0

 Understand Equation of State (EOS)

 Understand the Virial Equation (EOS)

 Understand the limitations of Virial Equation

 Understand the van der Waal EOS

 Equation between P, T and V is termed as EOS

 Simplest equation PV=RT

 Non-ideal gas PV = ZRT

 Equation of state are

 Understand Equation of State (EOS)

 Understand the Virial Equation (EOS)

 Understand the limitations of Virial Equation

 Understand the van der Waal EOS

 For pressure 0 to some

 So other constants like ‘C’ should be taken in to account

 Viral equation in terms of Volume has proved to be more

 Z = PV/RT = 1 + B/V + C/V2

 The above equation is cubic in Volume, So an iterative

 Understand Equation of State (EOS)

 Understand the Virial Equation (EOS)

 Understand the limitations of Virial Equation

 Understand the van der Waal EOS

 Virial coefficient beyond third are rarely known

 Truncation introduces an inherent error

 Virial coefficients are function of temperature and gas so

 However, research in quantum statistics has shown that

 The equation should not be complex to involve extensive

 The cubic equations of state are the simplest equations

 Many softwares include the routines to solve these

 Understand Equation of State (EOS)

 Understand the Virial Equation (EOS)

 Understand the limitations of Virial Equation

 Understand the van der Waal EOS

 However for real gas ‘U’ is proportional to how much

 dU/dV = –P = –a/V2 (Pressure adjustment)

 Pig Vig = RT (Ideal gas)

 Understand Equation of State (EOS)

 Understand the Virial Equation (EOS)

 Understand the limitations of Virial Equation

 Understand the van der Waal EOS

 Or by definition the density of liquid and gas becomes

 (V – Vc)3 = 0 V 3  3VcV 2  3Vc2V  Vc3  0