Thermo II Lecture 2 SolutionThermo

CH2351 Chemical Engineering Thermodynamics II
Unit I, II
www.msubbu.in
Solution Thermodynamics
ww
w
.m
sub
bu
.in
Dr. M. Subramanian
Associate Professor
Department of Chemical Engineering
Sri Sivasubramaniya Nadar College of Engineering
Kalavakkam 603 110, Kanchipuram (Dist)
Tamil Nadu, India
msubbu.in[AT]gmail.com
Jan-2012
Contents
UNIT I: PROPERTIES OF SOLUTIONS
Partial molar properties, ideal and non-ideal solutions, standard
states definition and choice, Gibbs-Duhem equation, excess
ww
properties of mixtures.
w
.m
sub
bu
.in
UNIT II: PHASE EQUILIBRIA
Criteria for equilibrium between phases in multi component nonreacting systems in terms of chemical potential and fugacity
Jan-2012 M Subramanian
ww
w.m
sub
bu
.in
Typical Chemical Plant
Introduction
Most of the materials of the real world are not pure substances
with all atoms or molecules identical but rather are mixtures of
one type or another.
The pure substances from wwhich
a solution may be prepared are
ww
.m
called components, or constituents,
of the solution.
sub
bu
.in
Solutions are not limited to liquids: for example air, a mixture of
predominantly N2 and O2, forms a vapor solution. Solid solutions
such as the solid phase in the Si-Ge system are also common
Multicomponent Systems Basic Relations

Single component system:
Intensive properties: depends on Pressure, Temperature
Extensive properties: depends on Pressure, Temperature, and
amount
ww
w.m
sub
bu
.in
Multicomponent system:
Intensive properties: depends on Pressure, Temperature, and

composition
Extensive properties: depends on Pressure, Temperature,
amount of each component
Composition
Mole fraction
ww
For binary solution
w.m
sub
bu
.in
In dealing with dilute solutions it is convenient to speak of the

component present in the largest amount as the solvent, while the
diluted component is called the solute.
Other Measures of Composition

Mass fraction preferable where the definition of molecular
weight is ambiguous (eg. Polymer molecules)
Molarity moles per litre of solution
ww
w.m
sub
bu
Molality moles per kilogram of solvent.
The molality is usually
.in
preferred, since it does not depend on temperature or pressure,
whereas any concentration unit is so dependent.
Volume fraction
Mole ratio or volume ratio (for binary systems)
Properties of Solutions
The properties of solutions are, in general, not additive
properties of the pure components.
The actual contribution to any extensive property is designated
as its partial property. The term partial property is used to
designate the property of awwcomponent
when it is in admixture
w.m
with one or more other components
sub
bu
.in
Because most chemical, biological, and geological processes
occur at constant temperature and pressure, it is convenient to
provide a special name for the partial derivatives of all
thermodynamic properties with respect to mole number at
constant pressure and temperature. They are called partial
molar properties
Ethanol-Water System at 20oC

Molar volumes:
Partial molar volumes

(at 50 mole% of
Ethanol):
Water: 18 mL/mol
Ethanol: 58 mL/mol
ww
w.m
sub
Water: 16.9 mL/mol

Ethanol: 57.4 mL/mol
bu
.in
Volume before mixing = (1 mole) (18.0 mL/mole) + (1 mole) (58.0 mL/mole) = 76 mL
Volume after mixing = (1 mole) (16.9 mL/mole) + (1 mole) (57.4 mL/mole) = 74.3 mL
ww
w.m
sub
bu
.in
ww
w.m
sub
bu
.in
ww
w.m
sub
bu
.in
1 liter of ethanol and 1 liter of water are mixed at constant temperature and
pressure. What is the expected volume of the resultant mixture ?
ww
w.m
sub
bu
.in
ww
w.m
sub
bu
.in
Partial Molar Properties

The partial molar property of a given component in solution is
defined as the differential change in that property with respect to
a differential change in the amount of a given component under
conditions of constant pressure and temperature, and constant
ww
number of moles of all components
other than the one under
w.m
consideration.
sub
bu
.in
where M is any thermodynamic property.

The concept of partial molar quantity can be applied to any
extensive state function.
Partial Molar Volume

Benzene-Toluene: Benzene and toluene form an ideal solution.
The volume of 1 mole pure benzene is 88.9 ml; the volume of 1
mole pure toluene is 106.4 ml. 88.9 ml benzene mixed with
106.4 ml toluene results in 88.9 ml + 106.4 ml, or 195.3 ml of
solution. (ideal solution)
ww
w.m
Ethanol-Water:
sub
bu
The volume of 1 mole pure ethanol
is 58.0 ml and the volume
.in
of 1 mole pure water is 18.0 ml. However, 1 mole water
mixed with 1 mole ethanol does not result in 58.0 ml + 18.0
ml, or 76.0 ml, but rather 74.3 ml.
When the mole fraction is 0.5, the partial molal volume of
ethanol is 57.4 ml and the partial molal volume of water is
16.9 ml. (non-ideal solution)
Fundamental Equations of Solution

Thermodynamics
ww
w.m
sub
bu
.in
ww
w.m
sub
bu
.in
ww
w.m
sub
bu
.in
ww
w.m
sub
bu
.in
Gibbs-Duhem Equation
This equation is very useful in deriving certain relationships
between the partial molar quantity for a solute and that for the
solvent.
ww
w.m
sub
bu
.in
ww
w.m
sub
bu
.in
Determination of Partial Molar Properties of Binary Solutions
ww
w.m
sub
bu
.in
ww
w.m
sub
bu
.in
ww
w.m
sub
bu
.in
Partial molar properties in binary solution

For binary system
M = x1 M 1 + x 2 M 2
ww
w.m
dM = x1 d M 1 + M 1 dx1 + x 2 d M s2ub+ M 2 dx 2
bu
.in
Const. P and T, using Gibbs/Duhem equation
dM = M 1 dx1 + M 2 dx 2
x1 + x 2 = 1
dM
= M1 M 2
dx1
M 1 = M + x2
dM
dx 1
M 2 = M x1
dM
dx 1
Partial Molar Quantities Physical Interpretation

The partial molar volume of component i in a system is equal to
the infinitesimal increase or decrease in the volume, divided by
the infinitesimal number of moles of the substance which is
added, while maintaining T, P and quantities of all other
components constant.
ww
w.m
Another way to visualize this issuto think of the change in volume
bb
on adding a small amount of component
i to an infinite total
u.in
volume of the system.
Note: partial molar quantities can be positive or negative!
Example Problem
ww
w.m
sub
bu
.in
x1
H (J/mol)
H-ideal
(J/mol)
600
600
420
600
0.1
581.98
580
419.44
600.04
0.2
563.84
560
417.92
600.32
0.3
545.46
415.68
601.08
0.4
526.72
412.96
602.56
0.5
507.5
0.6
ww 540
w.m
520
sub
H1bar
(J/mol)
H2bar
(J/mol)
410
605
487.68
b
500 u.in
480
407.04
608.64
0.7
467.14
460
404.32
613.72
0.8
445.76
440
402.08
620.48
0.9
423.42
420
400.56
629.16
400
400
400
640
700
650
H (J/mol)
600
550
ww
500
H-mix
H-ideal
H1bar
H2bar
w.m
sub
bu
.in
450
400
350
0
0.2
0.4
0.6
x1 (-)
0.8
ww
w.m
sub
bu
.in
ww
w.m
sub
bu
.in
ww
w.m
sub
bu
.in
ww
w.m
sub
bu
.in
ww
w.m
sub
bu
.in
ww
w.m
sub
bu
.in
ww
w.m
sub
bu
.in
Partial Molar Properties from Experimental Data

Partial molar volume:
Density data ( vs. x1)
Partial molar enthalpy:
ww
Enthalpy data (H vs. x1); wcan
.m be directly used
sub
Heat of mixing (also called as benthalpy
change on mixing)
u.in
data (Hmix vs. x1)
Obtained using differential scanning calorimetry
Reported normally as J/mol of solute; to be converted to J/mol of
solution
Density data for Water (1) - Methanol (2) system at 298.15 K

(kg/m3)
x1
avgMW
Videal
Vmix
m3/kmol
m3/kmol
m3/kmol
786.846
32.042
0.040722
0.040722
0.00000000
0.1162
806.655
30.41032
0.037699
0.038088
-0.00038867
0.2221
825.959
28.92327
0.035018
0.035687
-0.00066954
0.2841
837.504
28.05267
0.033496
0.034282
-0.00078631
0.3729
855.031
ww
26.80574
0.032269
-0.00091829
0.4186
864.245
0.031233
-0.00095908
0.5266
887.222
.m 0.031351
s0.030274
ub
26.16402
bu
.in
24.64748
0.027781
0.028785
-0.00100419
0.6119
905.376
23.4497
0.025901
0.026851
-0.00095055
0.722
929.537
21.90368
0.023564
0.024355
-0.00079116
0.8509
957.522
20.09366
0.020985
0.021433
-0.00044816
0.9489
981.906
18.71755
0.019062
0.019212
-0.00014922
997.047
18
0.018053
0.018053
0.00000000
Videal = x1V1 + x2V2

Vmix = V - Videal
0.045
0.04
V-ideal
0.035
0.03
Volume (m /kmol)
ww
0.025
w.m
sub
bu
.in
0.02
0.015
0.01
0
0.2
0.4
0.6
x1
0.8
0.00E+00
0
0.2
0.4
0.6
-2.00E-04
Vmix
-4.00E-04
-6.00E-04
-8.00E-04
ww
w.m
sub
bu
.in
-1.00E-03
-1.20E-03
x1
0.8
ww
w.m
sub
bu
.in
wt%
H2SO4]
H
(kJ/kg)
x1
Hmix
(kJ/mol)
Hmix Model
(kJ/mol)
278
0.0000
18.00
5.00
20
85
0.0439
21.51
1.83
-3.3516
-3.3818
40
-78
0.1091
w
26.73
-2.08
-7.5264
-7.4880
60
-175
0.2160
-6.17
-12.0446
-12.0692
80
-153
0.4235
.m 35.28
sub
bu
51.88
.in
-7.94
-14.6412
-14.6637
90
-60
0.6231
67.85
-4.07
-11.5746
-11.5736
100
92
1.0000
98.00
9.02
ww
Hideal = x1H1 + x2V2
avgMW
H
(kJ/mol)
Hmix = H - Hideal
10.00
H (kJ /mol)
6.00
2.00
ww
-2.00 0.0
0.2
w.m
sub
0.4
bu
.in
-6.00
-10.00
x1
0.6
0.8
1.0
Redlich-Kister Model
Also known as Guggenheim-Scatchard Equation
Fits well the data of Mmix vs. x1
ww
w.m
sub
bu
.in
0
0.00
-2
0.20
0.40
0.60
0.80
1.00
-4
Hmix
-6
-8
-10
-12
ww
w.m
sub
bu
.in
Data
RK Model fit
-14
-16
x1
ao
-55.9287
a1
27.0094
Redlich-Kister model fits well the data of Mmix vs. x1
ww
w.m
sub
bu
.in
Calculate the partial molar volume of Ethanol and Water as a

function of composition.
ww
w.m
sub
bu
.in
Gibbs
Josiah Willard Gibbs (1839 1904)
Gibbs greatly extended the field of thermodynamics, which
originally comprised only the relations between heat and
mechanical work. Gibbs was instrumental in broadening the field
w
to embrace transformationswwof
.m energy between all the forms in
which it may be manifested, besuthey
thermal, mechanical,
bb
electrical, chemical, or radiant. u.in
He is considered to be the founder of chemical
thermodynamics.
He is an American theoretical physicist, chemist, and
mathematician. He devised much of the theoretical foundation
for chemical thermodynamics as well as physical chemistry.
ww
w.m
sub
bu
.in
Fundamental Equation for Closed System

The basic relation connecting the Gibbs energy to the
temperature and pressure in any closed system:
ww
w.m
sub
bu
.in
applied to a single-phase fluid in a closed system wherein no
chemical reactions occur.
Fundamental Equation for Open System

Consider a single-phase, open system:
( nG )
( nG )
( nG )
d ( nG ) =
dP
dT
+
dn i
+
T P ,n
P T , n
i ni
P ,T , n j
Definition of chemical potential:

ww
w.m
s
( nG ) ub
bu
i
.in
n
i
P ,T , n
j
(The partial derivative of G with respect to the mole number ni at constant

T and P and mole numbers nj nj )
The fundamental property relation for single-phase fluid systems

of constant or variable composition:
d ( nG ) = ( nV ) dP ( nS ) dT + i dn i
i
When n = 1,
dG = VdP SdT + i dx i
G = G ( P , T , x1 , x 2 ,..., x i ,...)
ww
G
V =
P T , x
w.m
sub
bu Gibbs energy is expressed as a
The
.in
function of its canonical variables.
Solution properties, M
Partial properties, M i
Pure-species properties, Mi
i Gi
G
S =
T P , x
ww
w.m
sub
bu
.in
Chemical potential and phase equilibria

Consider a closed system consisting of two phases in
equilibrium:
w
d ( nG ) = ( nV ) dP ( nS ) dT + iwdn
w.mi d ( nG ) = ( nV ) dP ( nS ) dT + i dn i
sub
i
i
bu
.in
nM = ( nM ) + ( nM )
d ( nG ) = ( nV ) dP ( nS ) dT + i dn i + i dn i
i
Since the two-phase system is

closed,
Mass balance:
dn i = dn i
i = i
Multiple phases at the same T and P are in equilibrium
when
chemical
potential of each species is the same in all phases.
Jan-2012
M Subramanian
ww
w.m
sub
bu
.in
Partial Molar Energy Properties and Chemical

Potentials
The partial molar Gibbs free energy
is
chemical potential; however, the other partial
molar energy properties such as that of
internal energy, enthalpy, and Helmholtz free
energy are not chemical potentials: wbecause
ww
chemical potentials are derivatives .mwith
sub
respect to the mole numbers with the naturalbu
.in
independent variables held constant.
ww
w.m
sub
bu
.in
Variation of with T and P

Variation of with P: partial molar volume
Variation of with T: partial
molar entropy, can be
ww
w.m
expressed in terms of partial
molar enthalpy
sub
bu
.in
ww
w.m
sub
bu
.in
ww
w.m
sub
bu
.in
ww
w.m
sub
bu
.in
Entropy Change
The second law of thermodynamics
For an isolated system
ww undergoing a reversible change and the

in which the equality refers to a system
.m
inequality refers to a system undergoing san
ub irreversible change.
bu
.in
For systems that are not isolated it will be convenient to use the criteria of
reversibility and irreversibility such as in the following equation:
Mixing at Constant T and P
ww
w.m
sub
bu
.in
To carry out the mixing process in a reversible manner, the external pressure P on
the right piston is kept infinitesimally less than the pressure of B in the mixture; and
the external pressure P on the left piston is kept infinitesimally less than the
pressure of A in the mixture.
ww
w.m
sub
bu
.in
As the mixing process is isothermal, and the mixture is an ideal gas,
ww
w.m
sub
bu
.in
Entropy Change of Mixing

Consider the process, where nA moles of ideal gas A are confined
in a bulb of volume VA at a pressure P and temperature T. This
bulb is separated by a valve or stopcock from bulb B of volume
VB that contains nB moles of ideal gas B at the same pressure P
and temperature T. When the stopcock is opened, the gas
molecules mix spontaneously and irreversibly, and an increase in
entropy Smix occurs.
ww
w.m
sub
The entropy change can be calculated
by recognizing that the
bu
.in the gases are ideal. Smix is
gas molecules do not interact, since
then simply the sum of SA, the entropy change for the
expansion of gas A from VA to (VA + VB) and SB, the entropy
change for the expansion of gas B from VB to (VA + VB). That is,
Smix = SA + SB
For the isothermal process involving ideal gases, H is zero.

Therefore,
ww
w.m
sub
bu
.in
Partial Molar Entropy of Component i in an ideal gas mixture
ww
w.m
sub
bu
.in
Gibbs free energy change of mixing
ww
w.m
sub
bu
.in
Chemical potential of component i in an ideal gas mixture
ww
w.m
sub
bu
.in
iig G i ig = G iig + RT ln y i
G iig = i (T ) + RT ln P
ww
w.m
sub
iig = i (T ) + RT ln y i P bu
.in
Residual Property
ww
w.m
sub
bu
.in
Fugacity of a component i
ww
w.m
sub
bu
.in
Chemical potential of component i in a solution

in terms of fugacity
ww
w.m
sub
bu
.in
Fugacity and fugacity coefficient: species

in solution
For species i in a mixture of real gases or in a solution
of liquids:
i wi (T ) + RT ln fi
ww
.m
s
ub
bu
.in
Fugacity of species i in solution

(replacing the particle pressure)
Multiple phases at the same T and P are in equilibrium

when the fugacity of each constituent species is the
same in all phases:
fi = fi = ... = fi
The residual property:
The partial residual property:
= M M ig
M iR = M i M iig
G i R = G i G i ig
i i (T ) + RT ln fi
ww ig = (T ) + RT ln y P
w.m i
i
i
sub
bu
fi
ig
.
i
n
i i = RT ln
yi P
( nG )
i
= Gi
n i P ,T , n
j
Gi = 0
R
f
i = i = 1
yi P
For ideal gas,
fi = y i P
fi
G i R = RT ln i
i
yi P
The fugacity coefficient of species i
in solution
The excess Gibbs energy and the activity

coefficient
The excess Gibbs energy is of particular interest:
G E G G id
G i = i (T ) + RT ln fi
ww
w.mRT ln x i f i
G i = i (T ) +
id
Gi E
fi
= RT ln
xi f i
fi
i
xi f i
G i E = RT ln i
G i R = RT ln i
c.f.
sub
bu
.in
The activity coefficient of species i in solution.

A factor introduced into Raoults law to account for
liquid-phase non-idealities.
For ideal solution,
E
G i = 0,
i =1
fi
i =
=1
yi P
Gi = 0
R
fi = yi P
ww
w.m
sub
fi
i
xi f i
Gi E = RT ln i
bu
.in
For ideal solution,

Gi E = 0, i = 1
Fugacity of a pure liquid

The fugacity of pure species i as a compressed liquid:
fi
G i G isat = RT ln
ln
fi
f i sat
1
=
RT
f i sat
Pi
sat
Vi dP
Gi G
sat
i
ww
Pi sat
Vi dP
(isothermal process )
w.m
sub
bu
.in
Since Vi is a weak function of P
ln
fi
fi
sat
Vi l ( P Pi sat )
=
RT
f i sat = isat Pi sat
f i = isat Pi sat
Vi l ( P Pi sat )
exp
RT
ww
w.m
sub
bu
.in
Infinite dilution of girls in boys

Thermo II Lecture 2 SolutionThermo

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Thermo II Lecture 2 SolutionThermo

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CH2351 Chemical Engineering Thermodynamics II

UNIT II: PHASE EQUILIBRIA

Typical Chemical Plant

Multicomponent Systems Basic Relations

Intensive properties: depends on Pressure, Temperature, and

For binary solution

In dealing with dilute solutions it is convenient to speak of the

Other Measures of Composition

Ethanol-Water System at 20oC

Partial molar volumes

Water: 16.9 mL/mol

Partial Molar Properties

where M is any thermodynamic property.

Partial Molar Volume

Fundamental Equations of Solution

Determination of Partial Molar Properties of Binary Solutions

Partial molar properties in binary solution

Partial Molar Quantities Physical Interpretation

Partial Molar Properties from Experimental Data

Density data for Water (1) - Methanol (2) system at 298.15 K

Videal = x1V1 + x2V2

Hideal = x1H1 + x2V2

Redlich-Kister model fits well the data of Mmix vs. x1

Calculate the partial molar volume of Ethanol and Water as a

Fundamental Equation for Closed System

Fundamental Equation for Open System

Definition of chemical potential:

(The partial derivative of G with respect to the mole number ni at constant

The fundamental property relation for single-phase fluid systems

Chemical potential and phase equilibria

Since the two-phase system is

Partial Molar Energy Properties and Chemical

Variation of with T and P

ww undergoing a reversible change and the

Mixing at Constant T and P

As the mixing process is isothermal, and the mixture is an ideal gas,

Entropy Change of Mixing

For the isothermal process involving ideal gases, H is zero.

Partial Molar Entropy of Component i in an ideal gas mixture

Gibbs free energy change of mixing

Chemical potential of component i in an ideal gas mixture

Chemical potential of component i in a solution

Fugacity and fugacity coefficient: species

Fugacity of species i in solution

Multiple phases at the same T and P are in equilibrium

The residual property:

The partial residual property:

For ideal gas,

The excess Gibbs energy and the activity

The activity coefficient of species i in solution.

For ideal solution,

Fugacity of a pure liquid

Since Vi is a weak function of P

f i sat = isat Pi sat

Infinite dilution of girls in boys

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