Thermodynamics Lecture Notes

Chemical Engineering 623
Applications of Thermodynamics to Chemical Engineering
Lecture Notes
James C. Holste
Fall Semester
ACKNOWLEDGMENT
Professors Kenneth R. Hall, Philip T. Eubank and David M. Ford made substantial contributions
to the philosophy and content of this course. I am most grateful to them for their contributions.
TABLE OF CONTENTS
INTRODUCTION .........................................................................................................................1
Basic Definitions for Thermodynamics ...........................................................................................1
THERMODYNAMIC LAWS .......................................................................................................7
ZEROTH LAW OF THERMODYNAMICS ..................................................................................8
FIRST LAW OF THERMODYNAMICS .....................................................................................13
Single Particle ...........................................................................................................................13
One Dimension .....................................................................................................................13
Three Dimensions ................................................................................................................16
Collections of Particles .............................................................................................................19
Kinetic Energy Calculation ..................................................................................................21
Potential Energy Calculations ..............................................................................................24
Consequence of the First Law of Thermodynamics .................................................................30
General Energy Balance............................................................................................................31
SECOND LAW OF THERMODYNAMICS ................................................................................35
Physical Observations ...............................................................................................................35
Formal Statements of the Second Law .....................................................................................36
Kelvin ...................................................................................................................................36
Clausius ................................................................................................................................36
Planck ...................................................................................................................................36
Heat Engine: .........................................................................................................................37
Notation: ...............................................................................................................................38
Proof of Equivalence of Kelvin and Clausius Statements: ..................................................39
Carnot Cycle .........................................................................................................................45
Consequences Of Second Law ..................................................................................................46
Consequence No. 1:..............................................................................................................46
Consequence No. 2:..............................................................................................................52
Consequence No. 3:..............................................................................................................58
Consequence No. 4:..............................................................................................................62
Summary Statement of Second Law .........................................................................................66
Irreversible Processes:...............................................................................................................67
Practical Applications - Efficiencies .........................................................................................69
CHEN 623 Lecture Notes (Date of last revision: 11/07/2014)
ii
Summary Statement of Combined First and Second Laws.......................................................74

THIRD LAW OF THERMODYNAMICS ....................................................................................75
Nernst-Simon Statements of Third Law ...................................................................................75
Lewis-Randall Statement of Third Law ....................................................................................75
Consequences of Third Law .....................................................................................................76
Heat Capacity .......................................................................................................................76
Thermal Expansion ..............................................................................................................77
Phase Transitions (Vapor/Liquid, Vapor/Solid, Solid/Liquid) ............................................77
Practical Thermometry ..............................................................................................................78
Primary Thermometer: .........................................................................................................78
Secondary Thermometer: .....................................................................................................79
Philosophy of Practical Temperature Scales ........................................................................80
History of Temperature Scales .............................................................................................81
Evolution of International Temperature Scales ....................................................................85
Proposed Redefinition of Temperature in SI Unit System ...................................................90
MICROSCOPIC INTERPRETATIONS: TEMPERATURE, ENTROPY, WORK, HEAT........91
Microscopic (Statistical) Viewpoint of Entropy .......................................................................93
Model system .......................................................................................................................93
Some necessary definitions ..................................................................................................94
Microstates and the connection with entropy .......................................................................95
Macrostates...........................................................................................................................97
Connection with macroscopic property measurements ........................................................99
Microscopic (Statistical) Viewpoint of Energy and Temperature ..........................................108
Model system .....................................................................................................................108
Temperature .......................................................................................................................109
Energy Temperature Relationship for Model System .....................................................110
MATHEMATICAL IMPLICATIONS OF THERMODYNAMIC LAWS ................................117
Functions .................................................................................................................................117
Multivariable calculus .............................................................................................................122
Summary of Math Results ..................................................................................................130
Legendre Transformations .................................................................................................131
Applications of Mathematics to Physics Summary ................................................................132
Legendre Transformations of Internal Energy: ..................................................................134
Alternative Forms of Physics Summary Statement .......................................................136
Extension to Mixtures and Open Systems: ....................................................................137
Physics Summary Statements for Open Systems: .........................................................138
Thermodynamic Definitions ..............................................................................................139
Maxwell Relations..............................................................................................................141
Partial Molar Properties .....................................................................................................142
iii
Property Change Calculations .................................................................................................143

General Approach ..............................................................................................................143
Manipulation of Thermodynamic Variables ......................................................................145
Common Physical Observables: ....................................................................................146
Heat Capacity at Constant Volume: .........................................................................147
Heat Capacity at Constant Pressure: .........................................................................149
Relations Between Heat Capacities - (CP - CV) ........................................................151
Relations Between Heat Capacities - (CP /CV): .........................................................153
Systematic Approach to Manipulations Involving Derivatives: ...................................155
Residual functions ..............................................................................................................168
Density Form (Definition) .............................................................................................169
Pressure Form (Definition) ............................................................................................169
Methods for Calculation ................................................................................................173
Residual Expressions (Density Forms) .....................................................................175
Pressure ................................................................................................................175
Internal Energy.....................................................................................................176
Helmholtz Energy ................................................................................................180
Enthalpy ...............................................................................................................183
Entropy.................................................................................................................183
Gibbs ....................................................................................................................183
Summary of Density Forms .................................................................................184
Residual Functions (Pressure Form) .........................................................................185
Volume.................................................................................................................186
Internal Energy.....................................................................................................186
Helmholtz Energy ................................................................................................188
Enthalpy ...............................................................................................................190
Entropy.................................................................................................................190
Gibbs Energy .......................................................................................................190
Summary of Pressure Forms ................................................................................191
Ideal Gas Changes ..............................................................................................................192
Internal Energy ..............................................................................................................193
Enthalpy .........................................................................................................................195
Entropy ..........................................................................................................................196
Helmholtz Energy ..........................................................................................................199
Gibbs Energy .................................................................................................................200
General Formulae for Property Changes ............................................................................201
Internal Energy ..............................................................................................................201
Enthalpy .........................................................................................................................202
Entropy ..........................................................................................................................203
Helmholtz Energy ..........................................................................................................204
Gibbs Energy .................................................................................................................205
Properties relative to a reference state................................................................................207
Ideal Gas Reference State ..............................................................................................209
iv
Change of reference state ..............................................................................................210

Alternate Form for Change of Reference State .............................................................220
Equilibrium Criteria ................................................................................................................222
Entropy and Energy Functions ...........................................................................................222
First Derivatives (T, P, i) ..................................................................................................231
Second Derivatives (CX, T) ...............................................................................................235
Gibbs Phase Rule ...............................................................................................................241
Comments On Energy Functions ............................................................................................245
Internal Energy ...................................................................................................................245
Enthalpy .............................................................................................................................246
Helmholtz Energy ..............................................................................................................247
Gibbs Energy ......................................................................................................................249
Summary .................................................................................................................................251
PROPERTIES OF PURE FLUIDS ..........................................................................................252
IDEAL GAS HEAT CAPACITIES .............................................................................................253
EQUATIONS OF STATE ...........................................................................................................255
General P, V, T Behavior ........................................................................................................255
Brief History of Equations of State .........................................................................................258
Important Equations of State...................................................................................................260
Compression factor ............................................................................................................260
Virial equations ..................................................................................................................260
Cubic Equations of State ....................................................................................................261
van der Waals ................................................................................................................261
General Forms for Cubic Equations of State .................................................................263
Martin .......................................................................................................................263
Abbott .......................................................................................................................263
Specific Forms for Cubic Equations of State ................................................................264
Redlich-Kwong (1949) .............................................................................................264
Martin .......................................................................................................................265
Soave-Redlich-Kwong (1972) ..................................................................................265
Peng-Robinson (1976) ..............................................................................................267
Harmon & Knapp .....................................................................................................267
Complex Equations of State ...............................................................................................268
Benedict-Webb-Rubin (BWR, 1940) ............................................................................268
Benedict-Webb-Rubin-Starling (BWRS, 1970) ............................................................269
Tilner-Roth (Difluoromethane, R-32) ...........................................................................272
Wagner & Pru (Water, IAPWS-95).............................................................................273
Corresponding states ...............................................................................................................275
2 parameter .........................................................................................................................275
3 parameter .........................................................................................................................276
Lee-Kesler (1975) ..........................................................................................................277

4 Parameter Corresponding States .....................................................................................279
Extended corresponding states ...........................................................................................280
Modified BWRS (NIST form).......................................................................................281
MOLECULAR INTERACTIONS ..............................................................................................282
The Fundamentals ...................................................................................................................282
Force-field concept .................................................................................................................284
Intramolecular potentials.........................................................................................................285
Bond-stretching ..................................................................................................................285
Angle-bending ....................................................................................................................285
Torsional rotation ...............................................................................................................286
Improper out-of-plane potential ..............................................................................................287
Van der Waals and Coulombic potentials ...............................................................................289
Van der Waals ....................................................................................................................289
Coulombic ..........................................................................................................................293
Three-body potentials .............................................................................................................296
Three-body vdW potential .................................................................................................297
Equations Derived From Interatomic Potentials .....................................................................299
Perturbed Hard Spheres ......................................................................................................308
Ree & Hoover (1967) ....................................................................................................308
Carnahan-Starling (1972) ..............................................................................................308
Boublik-Alder-Chen-Kreglewski (BACK) ...................................................................309
PC-SAFT Equation of State ..........................................................................................310
PURE FLUID PHASE EQUILIBRIUM .....................................................................................312
Gibbs Energy of van der Waals Fluid .....................................................................................315
Vapor pressure from EOS .......................................................................................................319
Vapor Pressure Calculation Procedure ...............................................................................321
Implications for Vapor Pressure Equations ........................................................................323
Temperature dependence of H ............................................................................................324
Trouton's Rule .........................................................................................................................326
Types of phase transitions .......................................................................................................327
BEHAVIOR NEAR CRITICAL POINTS ..................................................................................333
P-V-T near a vapor - liquid critical point:...............................................................................334
Physical Observations: ............................................................................................................335
Critical Opalescence ...............................................................................................................336
Universality .............................................................................................................................336
General Behavior ....................................................................................................................337
Law of Rectilinear Diameters .................................................................................................338
Critical Exponents ...................................................................................................................339
vi
Experimental Problems Near Critical Point ............................................................................341

PROPERTIES OF MIXTURES ...............................................................................................343
GENERAL FORMAL DESCRIPTIONS ....................................................................................343
Gibbs-Duhem equation ...........................................................................................................347
Calculation of partial molar properties ...................................................................................350
Property change on mixing .....................................................................................................354
General Definition ..............................................................................................................354
Property Changes on Mixing for Ideal Gases ....................................................................355
Ideal solutions ....................................................................................................................360
Alternative Definition of Ideal Solution ........................................................................361
Activity Coefficient ............................................................................................................363
Activity ...............................................................................................................................363
General Definitions ............................................................................................................364
Excess Properties................................................................................................................365
Relation of Excess Properties to Residual Functions and Equation of State ................369
Fugacity .........................................................................................................................372
Relationships between activity coefficients based upon different reference states. ......377
PHASE EQUILIBRIUM FOR MIXTURES ...............................................................................380
General Phase Equilibrium .....................................................................................................380
Phase Equilibrium Calculation................................................................................................385
Partition Coefficient ...........................................................................................................385
Saturation Boundary Working Equation ............................................................................386
Phase Split Working Equation ...........................................................................................388
Equilibrium Relationships.......................................................................................................391
Vapor Phase Description ....................................................................................................393
Liquid/Solid Phase Description ..........................................................................................394
VLE Equilibrium Descriptions...........................................................................................395
General formulation.......................................................................................................395
Raoult's law ...................................................................................................................397
Henry's law ....................................................................................................................398
Excess Gibbs Models for Liquid Phase..............................................................................399
Binary Mixtures .............................................................................................................399
Redlich-Kister Expansion .........................................................................................399
Van Laar ...................................................................................................................400
Wilson .......................................................................................................................400
T-K Wilson ...............................................................................................................400
NRTL ........................................................................................................................401
UNIQUAC ................................................................................................................401
Scatchard-Hildebrand ...............................................................................................402
Multicomponent Mixtures .............................................................................................403
vii
Calculation of fugacities from equations of state ...............................................................404

General Relationship for Cubic Equations ....................................................................411
Mixing rules for cubic equations of state ......................................................................414
Conventional .............................................................................................................414
Conformal solution ...................................................................................................415
Mixing Rules Based on Excess Properties ...............................................................417
Huron-Vidal .........................................................................................................420
Wong-Sandler ......................................................................................................421
CHEMICAL REACTION EQUILIBRIUM ................................................................................424
Chemical Reaction (Generalized Form)..................................................................................424
Reaction coordinate.................................................................................................................425
Equilibrium criteria .................................................................................................................428
Standard Free Energy Change/Equilibrium Constant ........................................................429
Standard Property Change of Reaction ...................................................................................434
Temperature dependence of equilibrium constant .............................................................436
Alternate Method for Temperature Dependence of Equilibrium Constant ........................438
Free Energies of Formation ................................................................................................441
Standard and Reference State Choices....................................................................................443
Ideal Gas Standard States ...................................................................................................444
Lewis-Randall Reference State .....................................................................................446
Henry's Law Reference State.........................................................................................447
Liquid or Solid Standard States ..........................................................................................448
Infinite Dilution Standard State..........................................................................................452
Summary of the Equilibrium Constant Definitions............................................................455
Relations Between Various K's .....................................................................................456
Reaction Equilibrium by Minimization of Gibbs Free Energy ...............................................459
Method of Lagrange multipliers .........................................................................................461
Application to Single Phase Reactions...............................................................................464
Reaction Equilbrium Using Reaction Coordinate ...................................................................467
Single Reaction ..................................................................................................................467
Gas Phase (Fugacity Coefficient) ..................................................................................468
Liquid Phase (Activity Coefficient) ..............................................................................468
Multiple Independent Reactions.........................................................................................469
Heat Effects Associated with Reactions .................................................................................470
viii
IONIC SOLUTIONS ...................................................................................................................473

Molality ...................................................................................................................................473
Treatment of Solution Thermodynamics............................................................................475
Summary of Conventions for Activities .................................................................................477
Free Energy of Formation in Solution ....................................................................................478
Electrolytes..............................................................................................................................480
Charge Balance ..................................................................................................................481
Dissociation Stoichiometry ................................................................................................481
Gibbs Energy of Electrolyte Solution ................................................................................484
Equilibrium Involving Ionic Solutions ...................................................................................487
Vapor/Liquid Equilibrium ..................................................................................................487
Solid/Liquid Phase Equilibrium .........................................................................................488
Equilibrium Constants for Ionic Solutions .........................................................................490
Apparent Dissociation Constant .........................................................................................491
Free Energies of Ions in Solution .......................................................................................493
Activity Coefficient Models for Electrolyte Solutions ......................................................499
Ionic Strength ................................................................................................................499
Debye Limit Law ...........................................................................................................499
Extended Debye-Huckel Theory ...................................................................................500
Pitzer Model ..................................................................................................................500
Meissner Model .............................................................................................................503
Meissner Parameters for Selected Electrolytes at 25 C ..........................................504
SURFACE EFFECTS ................................................................................................................505
SURFACE ENERGIES ...............................................................................................................505
Surface Tension.......................................................................................................................508
APPLICATION OF FIRST AND SECOND LAWS ..................................................................510
EQUILIBRIUM CONDITIONS..................................................................................................512
PHASE EQUILIBRIUM .............................................................................................................514
Case I: Small liquid drops in a vapor (pure fluid)..................................................................514
Example: Spherical Geometry - Liquid drop ...................................................................516
Case II: Small Vapor Bubbles Surrounded By a Liquid ........................................................518
Example: Spherical geometry - Vapor bubble ..................................................................520
Correlations for Surface Tension ............................................................................................521
ADSORPTION ON SURFACES ................................................................................................522
Terminology ............................................................................................................................523
Two Dimensional Phase..........................................................................................................527
Adsorption Isotherms ..............................................................................................................531
Henrys Law ........................................................................................................................531
ix
Langmuir isotherm .............................................................................................................532

Toth Equation .....................................................................................................................534
Heat of Adsorption ..................................................................................................................534
EXTERNAL FIELDS ................................................................................................................536
Gravitational Fields......................................................................................................................536
Hydrostatic Pressure Gradient ................................................................................................537
Chemical Potential Gradient ...................................................................................................538
Centrifugal Force Fields ..............................................................................................................539
Centrifugal Pressure Gradient .................................................................................................539
Centrifugal Chemical Potential Gradient ................................................................................540
Electric Fields ..............................................................................................................................540
Magnetic Fields............................................................................................................................541
CHEN 623 - Useful Information for Examinations

First Law (Differential and Integral Forms)
Diff. form:
t
k
p
k
p
2
d[ m(U + E + E )] system = ( dQ )i + ( dW )i + ( dm )i H + Ei + Ei ( dm )n c
Integral form:
k
p
k
p
2
[ m(U + E + E )] system = Qi + Wi + (t m) i H + Ei + Ei ( n m) c
Second Law:
d(nS) =
dQrev
; (nS) universe
T
Combined First and Second Law (Differential Forms):
dU = TdS PdV
d(nU) = Td( nS ) Pd(nV) + i dni
dH = TdS + VdP
d(nH) = Td( nS ) + (nV)dP + i dni
dA = SdT PdV
d(nA) = (nS )dT Pd(nV) + i dni
dG = SdT + VdP
d(nG) = (nS)dT + (nV )dP + i dni
H = U + PV
A = U TS
G = U + PV TS = H TS = A + PV
Energy Functions:
Useful Mathematical Relationships:

f
f
MR1. f = f ( x, y ) df = dx + dy
x y
y x
x
z
MR2. =
x y z y
z z w
MR4. =
x y w y x y
z z z w
MR5. = +
x y x w w x x y
z x y
MR3. = 1
x y y z z x
2 f 2 f
=
MR6.
x y y x
Residual Functions:
r = (T , ) ig (T , )
R = (T , P ) ig (T , P )
Z
Ur UR
1 Z d
d
=
= I1 =
= T
RT RT
T (1 / T )
T
Hr
HR
= I1 + Z 1 =
RT
RT
Ar
AR
d
=
+ ln Z = I 2 = ( Z 1)
RT RT
Gr
GR
= I2 + Z 1 =
+ ln Z
RT
RT
S
S
= I1 I 2 =
ln Z
R
R
P rV
PV R
= Z 1 =
RT
RT
Property Changes:
(T2 , P2 ) (T1 , P1 ) = R (T2 , P2 ) R (T1 , P1 ) + ig (T2 , P2 ) ig (T1 , P1 )
(T2 ,V2 ) (T1 ,V1 ) = r (T2 ,V2 ) r (T1 ,V1 ) + ig (T2 ,V2 ) ig (T1 ,V1 )

Mixture Properties:
M = xi M i
where:
M
( nM )
M
Mi =
= M +
xj
ni T ,P,n ji
xi T ,P,xki
x j T ,P,xk j
j
Property Changes on Mixing:
M M M xi M i = xi M i M i
MG
= xi ln i = xi ln i xi
RT
Ideal Solution:
ISM S
IS G
IS A
= M = M = xi ln xi
R
RT
RT
ISM U ISM H P ISM V

=
=
=0
RT
RT
RT
M E M M IS
MM
Excess Properties:
Activity, Activity Coefficient, Fugacity, Fugacity Coefficient:

i = i xi =
fi xii
=
fi i
i =
ln i = ( Z i 1)
dP
=
P
dV
( nZ )
1
ln Z
ni T ,nV ,n
V
ji
RT = xi ln i
E
Note:
i
f
= i = i
xi xi fi i
ln i =
( )
GiE nG
RT
=
RT ni
T ,P,ni j
The superscript denotes a reference state, which usually is taken to be the pure material at the same temperature
and pressure as the mixture.
Phase Equilibrium:
fi = fi
Equilibrium Condition:
i = i
Fugacity coefficient description:
fi = yi i P
Activity coefficient description:
fi = xi i fi
Partition coefficient:
P
y LR P
1
K i i = i Vi i exp
Vi L dP
xi
RT
i P
Pi
Chemical Reaction Equilibrium:

i Ai = 0
G
i
where: , = stoichiometric coefficient of substance i, (i < 0 for reactants, i > 0 for products)
=0
f
f
Gi = Gi + RT ln i = f Gi + RT ln i
fi
fi
when the free elements are used as the

standard states for all substances
Standard free energy of reaction and equilibrium constant:

Standard property change of reaction: r M i M i
r G
= ln K = ln
RT
i
fi
fi

Minimization of Gibbs energy using Lagrange multipliers:
F
f
= Gi + k k
ni
ni
f k = nio ni aij = 0
Ionic Solutions:
mi =
1000ni
n0 M 0
f
f Gi = f Gio + RT ln i o
fi
M + A = + M z+ + A z
r G = RT ln K e = + f G+ + f G f Gu
Ke =
Ionic equilibrium constant:
m
u mu
Mean ionic activity coefficient, mean molality, and ionic strength
= + +
Solubility Product:
m = m ++ m
I=
= + +
1
mi zi2
2 i
S.P. = m + + m
Galvanic Cells: iGi = zFE
Gi = + f G+ + f G + RT ln m
Pressure difference across a curved surface: P = P +

Gravitational field:
dP
Mg
=
dz
V
M gz
fi ( z ) = fi no gravity exp i
RT
2
r
INTRODUCTION
Basic Definitions for Thermodynamics
Thermodynamics: a model of the behavior of collections of particles, based
upon physical observations and mathematical principles, that attempts to
describe the behavior of the universe.
Classical thermodynamics: describes the macroscopic behavior of a

system of particles in terms of macroscopic properties.
Statistical thermodynamics: describes the macroscopic behavior of a

system of particles in terms of microscopic properties (atomic and
molecular interactions).
System: a region of space that is of interest and everything contained within that
region.
Surroundings: all parts of the universe not included in the system.
Boundary: separates the system from the surroundings. The most general
definition of a boundary is a mathematical surface.
Diathermal boundaries: allow interaction between the system and the
surroundings.
Adiabatic (adiathermal) boundaries: prevent interaction between the
system and the surroundings.
NOTE: The term adiabatic is often used to describe situations where there
is no heat transfer, but other energy transfer may occur.
Systems
Homogeneous: all thermodynamic properties of a homogeneous system
vary continuously on a macroscopic scale throughout the system.
Heterogeneous: at least one ot the thermodynamic properties varies
discontinuously on a macroscopic scale at one or more points within the
system.
Isolated: there is no interaction of any type between an isolated system and
its surroundings. (An isolated system is surrounded by an adiabatic
boundary.)
Closed: the amount of material (mass) contained within a closed system
remains constant (excluding nuclear reactions and relativistic effects).
No mass transfer occurs to or from a closed system.
Open: the amount of material (mass) within an open system may vary with
time because mass transfer across the system boundary may occur.
State: the condition of a system. States normally are described in terms of the
physical properties of the system.
State variables: any of the physical properties used to describe the state of the
system. Each state of the system has a unique set of state variables.
Intensive properties: properties whose values can be specified at each point in

a system and which may vary from point to point. Intensive properties are
not additive and they do not require any specification of the quantity of
sample involved.
Extensive properties: properties that are additive in the sense that the value of
the property for the whole system is the sum of the values for each of its
constituent parts. For extensive variables, there is a single aggregate value
for the entire system.
Equilibrium: an isolated thermodynamic system is in equilibrium when none of

its thermodynamic properties are changing with time at a measurable rate.
At equilibrium:
d
=0
dt
where represents any thermodynamic property.

Steady state: an open system is said to be at steady-state when none of the
properties of the system are changing at a measurable rate. At steadystate

= 0
t x
where represents any thermodynamic property.

Time: a measure of the order in which events will occur in nature. Time is not a
legitimate variable in classical thermodynamics.
Law: a statement of the behavior of the physical world for which no contradiction
ever has been observed.
Temperature: a mathematical variable that provides a measure of the "hotness"

or "coldness" of a body, i.e., whether energy will be transferred to or from a
body as heat if the body is placed in thermal contact with another body at a
different temperature.
Energy: a mathematical variable that is independent of time for a closed,

isolated system. This function is particularly useful for describing the
physical behavior of systems.
Heat: energy transferred across a system boundary as the result of a

temperature gradient driving force, excluding effects associated with mass
transfer.
Work: energy transferred across a system boundary due to any driving force
other than a temperature gradient, excluding effects associated with mass
transfer.
THERMODYNAMIC LAWS
Law: a description of the physical behavior of the universe for which no

measurable contradiction ever has been observed.
Note: it is impossible to prove conclusively the validity of scientific laws; they

are summary statements of observations of past physical behavior.
ZEROTH LAW OF THERMODYNAMICS

Statement: If two bodies (closed systems) each are in thermal equilibrium with a
third body, then they are in thermal equilibrium with each other.
Consequence: There exists a mathematical variable (which we call
temperature) that provides a measure of hotness and coldness and that may
be used to determine whether or not two systems are in thermal equilibrium.
Proof:
For simplicity, consider a single-phase fluid so that only two intensive variables
need be specified to specify the state of the system completely.
Let x and y be the independent thermodynamic variables of interest, and A, B
and C the closed systems of interest.
Then, if A and C are in thermal equilibrium, there exists some relation between
xA, xC, yA and yC such that
F1( x A ,y A ,x C ,y C ) = 0
Likewise, if B and C are in equilibrium:
F2 (x B ,y B ,x C ,y C ) = 0
Each of these equations may be solved for yC:
y C = f 1 ( x A ,y A ,x C ) and y C = f 2 ( x B ,y B ,x C )
But, yC is the same in both cases, therefore
f 1 ( x A ,y A ,x C ) = f 2 ( x B ,y B ,x C )
The Zeroth Law requires that A and B also are in equilibrium, therefore we also
have
F3 ( x A ,y A ,x B ,y B ) = 0
This equation is equivalent to the previous result only if f1 and f2 contain xC in

such a way that it cancels from the equation.
The most general forms possible for f1 and f2 therefore are
f1( x A ,y A ,x C ) = g1( x A ,y A ) ( x C ) + ( x C )
f2 ( x B ,y B ,x C ) = g 2 ( x B ,y B ) ( x C ) + ( x C )
So, for bodies in thermal equilibrium,
g1( x A ,y A ) = g 2 ( x B ,y B ) = g 3 ( x C ,y C )
This function then has the same numerical value for each body if the bodies are
in thermal equilibrium.
This variable is called temperature.
Definition:
= g(x,y)
10
NOTE: For systems other than single-phase pure fluids, the temperature is a
function of the variables chosen to specify completely the state of the system
(independent variables).
11
Many physical properties have been used to measure temperatures. Some of

the more common are:
The pressure of a gas at constant density (constant volume gas thermometry)
The density (volume) of a liquid or solid (liquid-in-glass thermometers,
bimetallic strip thermometers)
Electrical resistivity (thermistors, resistance thermometers, e.g. RTD's, etc.)
Electrical potential appearing across the junction of two dissimilar metals
(thermocouple)
Intensity of thermal radiation (optical pyrometer)
Vapor pressure of a pure liquid
Breakdown voltage of an electrical diode (silicon or gallium arsenide
thermometers)
Magnetic susceptibility
Phase transitions (liquid crystal thermometers)
60
Anisotropy of gamma radiation from Co
Amplitude of random noise appearing across a resistor due to the thermal

motion of the electrons within the conductor (Johnson or shot noise)
12
FIRST LAW OF THERMODYNAMICS

Statement: Energy is conserved when heat is taken into account.
We examine here the consequences of Newton's law of motion to obtain a better
understanding of the concept of energy.
du
Newton's Law: F = ma = m
dt
Single Particle
One Dimension
Consider the case where the force on an object depends only upon the position
of the object,
F = f (x )
Use the chain rule of differential calculus and the definition of velocity to write
du du dx
du
=
=u
dt dx dt
dx
13
Then
f (x ) = mu
du
dx
f (x )dx = mu du
Integration yields
( x ) dx
= mu du = 21 mu 2 + Constant of Integration
Rearrange to obtain
1 mu 2
2
f ( x ) dx = E
( = constant )
The combination of Newton's Law and the condition that the force depends only
on position leads to a constant of integration that does not vary with respect to
time, and
E = KE + PE
where:
E = total energy
KE = 21 mu 2 = kinetic energy
14
PE = f ( x ) dx = potential energy
15
Three Dimensions
In three dimensions, force and position are vector quantities:
r = ( x,y,z )
F = F (r ) = Fx (r ),Fy (r ),Fz (r ),
du
F = ma = m
dt
16
The three components of the vectors are given by

Fx = m
du x
du
du dx
= m x = mu x x
dx dt
dt
dx
du y
du y dy
Fy = m
= m
= mu y
dt
dy
dy dt
du y
Fz = m
du z
du
du dz
= m z = mu z z
dz dt
dt
dz
and
Fx dx = mu x du x
1 mu 2
x
2
Fx dx = E x
Fy dy = mu y du y
1 mu 2
y
2
Fy dy = E y
Fz dz = mu z du z
1 mu 2
z
2
Fz dz = E z
17
Adding these results together produces

1m
2
(u
2
x
) (
+ u y2 + u z2 Fx dx + Fy dy + Fz dz = E x + E y + E z
=E
The two terms on the left hand side of the equation can be expressed much more
concisely in terms of vector notation (scalar or dot product):
u x2
+ u y2
+ u z2

= u u

Fx dx + Fy dy + Fz dz = F dr
The energy equation for a single particle in three dimensions is given by:

p
p
1
E = 2 m u u F dr =
F dr
2m
18
Collections of Particles
Thermodynamics applies only to collections of particles, therefore we consider
the implications of the previous result for a collection of discrete, classical
particles.
Total Energy: E = E i
where:
E i is the energy possessed by the ith particle
Substituting the previous result produces:

E = 2 m u i u i Fi r i dr i
( )
where:

F r i is the force acting on particle i
( )
r i is the location of particle i
19
The particle collection has a center of mass at
m i ri
1
rcm = i
= total m i r i
m i
m system i
i
where
total
msystem
= m i
i
is the total mass of the particles in the system.
20
Kinetic Energy Calculation

The position of an individual particle can be described in terms of the position of
the center of mass and of the position of the individual particle relative to the
center of mass:

r i = r cm + R i
where: R i is the displacement of particle i from the location of the center of

mass
Differentiation with respect to time provides a similar expression for velocities:
u i = ucm + U i
The kinetic energy term then can be written as:
1 m
2 i
i
1
u i u i = 2 m i u cm + U i u cm + U i
i
) (
)
21
so that
1 m
2 i
i
1
1
u i u i = 2 m i u cm u cm + m i u cm U i + 2 m i U i U i
i
total
= 21 msystem
u cm u cm
1
+ m i u cm U i + 2 m i U i U i
i
But, the definition of the center of mass can be rewritten as

total
msystem
r cm
= m i r i = m i r cm + R i
i
total
= msystem
r cm
+ m i R i
i
Therefore
m i R i = 0
i
and
m i U i = 0
i
22
The kinetic energy term then becomes

1 m u
2 i i
i

1 total
1
ui = 2 msystemucm ucm + 2 m iUi Ui
i
Therefore, the total kinetic energy of the system contains a term that contains the
motion of the center of mass and a term containing motion relative to the
center of mass, but no terms that contain both types of motion.
This means that the kinetic energy contains a term that is associated with the
macroscopic motion of the system, and a term that results from the motion of
the particles within the system.
23
Potential Energy Calculations

Two types of forces contribute to the potential energy calculations:
1. Internal forces: forces that arise from interactions between particles within
int
the system, F i
2. External forces: forces that arise from interactions of the individual particles
ext
with external force fields, F i
Examples of common external force fields:

gravity
electric fields
magnetic fields
24
Forces are additive, so that

int
ext
Fi ri = F i ri + F i
ri
( )
( )
( )
Now, if the internal force acting on particle i because of the presence of particle j
depends only upon the distance between the particles,
fik ri rk = fik rcm + R i rcm + Rk
))
= fik R i Rk
The total force on particle i resulting from its interactions with all the other
particles in the collection is obtained by summation:
int

Fi = fik Ri Rk
k
25
The total effect for the collection of particles is
ri
Potential Energy =
i r
ref
ri
F i ri d ri
i r
ref
( )
ext
F i ri d ri -
( )
ri
i r
ref
int
F i ri d ri
( )
so that the potential energy term becomes:
ri
i r
ref
F i ri d ri = 21
( )
ri
fik
i k r
ref
rcm
ext
+ F i
i r
ref
Ri Rk d ri
( )
ri d ri +
ri
ext
F i ri d ri
( )
rcm
In this expression, the first and third terms depend upon positions relative to the
center of mass, while the second term depends primarily upon the position of the
center of mass.
26
Combining all the previous results gives
E=
1 mtotal u
2 system cm
1
ucm + 2 mi Ui Ui
i
ri
i r
cm
i r
ref
ri
ext
F i ri d ri 21
( )
rcm
ext
F i ri d ri
fik
i k r
ref
( )
Ri Rk d ri
ext
where F ( rcm ) is the total force acting upon the collection of particles due to
external fields.
27
The total energy expression is

E=
1 mtotal u
2 system cm
ext
ucm F ( rcm ) d rcm
ri
ri
+ 21 mi Ui Ui 21 fik Ri Rk d ri Fext
ri d ri
i
i
i k r
i r
ref
cm
( )
The first two terms deal with the macroscopic velocity and position of the system.
The last three terms deal with the properties possessed by the individual
particles.
The term in square brackets is intractable for calculations of fluids because the
number of particles generally exceeds 1020.
28
The terms inside the square brackets are lumped and defined as the total
internal energy of the system:
total
Usystem
1 mU
2 i i
i
Ui + 21
ri
fik
i k r
ref
Ri Rk d ri
ri
i r
cm
Kinetic energy
Potential energy
ext
F i ri d ri
( )
total
2
E ktotal = 21 m system
u cm
E ptotal
rcm
F rcm d rcm
( )
rref
29
Total energy of the system

total
total
total
U + E k + E p
E system
= Usystem
+ E ktotal + E ptotal = msystem
total
U, Ek and Ep are the internal, kinetic and potential energies per unit mass. (or
per mole).
Note that the internal energy, U, depends only on the state of the system,
therefore the internal energy is a state function.
Consequence of the First Law of Thermodynamics

There exists a function (which we call energy) that is a constant with respect to
time for an isolated system.
(This function is quite useful for describing the physical behavior of practical
systems.)
30
General Energy Balance

By applying the conservation of energy to the entire universe (which is an
isolated system) and dividing the universe into two entities, the system and the
surroundings, which are separated by a boundary), we conclude that:
Net change in total energy of the system =

= net transfer of energy across the boundary
+ conversion of mass to energy within the system
(nuclear reactions)
31
This may be stated in mathematical form in either the differential form of the
general energy balance:
d m U + E k + E p
=
system
dQi +
all heat
transfer
mechanisms
dWi
all work
mechanisms
+ (dm )i
xfer
all
streams
(H + E
i
k
i
+ E ip
all nuclear
reactions
2
c
(dm )nuc
i
or the integral form of the general energy balance:
m U + E k + E p
=
system
Qi +
all heat
transfer
mechanisms
+
all
streams
Wi
all work
mechanisms
p
k
H
+
E
+
E
(dm )xfer
(
i
i
i )
i
2
m nuc
i c
all nuclear
reactions
32
In these equations:
U
= internal energy per unit mass
Ek
= kinetic energy per unit mass
Ep
= potential energy per unit mass
= energy transferred as heat
= energy transferred as work
mxfer = mass transferred across the system boundary

H
= U + PV = enthalpy per unit mass
mnuc = change in mass due to nuclear reactions

c
= velocity of light in vacuum
Note that the use of the enthalpy in the mass transfer term automatically includes
the effect of injection and ejection work.
33
Definitions:
Heat: energy that is transferred across the system boundary because of a
temperature gradient driving force, i.e., a temperature difference between
the system and the surroundings, (excluding energy transfer associated
directly with mass flow across the boundary. The mechanisms for heat
transfer are conduction, convection and radiation.
Work: energy that is transferred across the system boundary because of any
driving force other than a temperature gradient, again excluding energy
transfer associated with mass flow across the boundary.
34
SECOND LAW OF THERMODYNAMICS

Physical Observations
Not all processes that conserve energy occur.
Energy never is transferred as heat from a cold body to a hot body with no
other change in the system or its surroundings.
Certain physical states of an isolated system never can precede other physical
states of that system.
35
Formal Statements of the Second Law

Kelvin
It is impossible to extract heat from a reservoir and convert it wholly into work
without causing other changes in the universe.
Clausius
Heat can never, of itself, flow from a lower to a higher temperature.
Planck
No cyclic process is possible that results in the flow of heat from a single heat
reservoir and the performance of an equivalent amount of work.
The statements of Kelvin and Clausius are equivalent, but the equivalence is
not obvious.
We prove the equivalence by demonstrating that a violation of Kelvin's statement implies a violation of Clausius statement and vice versa.
36
Heat Engine:
A heat engine is a conceptual device that is used to study Second Law effects.
It consists of a device that is capable of exchanging energy as heat with two
reservoirs, one at a higher temperature and one at a lower temperature, and of
exchanging energy as work with the surroundings. The schematic diagram for a
heat engine is shown below.
A reservoir is an entity that is capable of absorbing or delivering any amount of
energy as heat without changing its temperature.
High Temperature
Reservoir
QH
W
QC
Low Temperature
Reservoir
Schematic Diagram of Heat Engine

37
For the discussions at present, we shall continue to use the symbol to denote
temperature, so that H is the temperature of the hotter reservoir and C is the
temperature of the colder reservoir.
Notation:
H = temperature of the hotter reservoir

C = temperature of the colder reservoir
QC = amount of energy transferred as heat from the colder reservoir to the
system
QH = amount of energy transferred as heat from the hotter reservoir to the
system
W = amount of energy transferred as work from the surroundings to the
system
This choice of signs is consistent with that used for the general energy balance,
but not consistent with discussions of Second Law effects found in many other
references. Other references, especially those discussing mechanical
engineering applications, use the opposite sign convention for W.
38
Proof of Equivalence of Kelvin and Clausius Statements:

To prove the equivalence of these two statements, we consider two heat engines
that are coupled and that operate between a reservoir at H and another
reservoir at C.
The general arrangement is shown schematically below.
H
QH
A
A
WA
QCA
WB
QHB
B
QCB
39
H
H
QH
A
A
WA
QCA
WB
QB
B
QCB
The net energy transferred as work for the coupled engine is:
W = WA +WB
The net energy transferred as heat from the hotter reservoir is:
Q H = Q AH + QBH
The net energy transferred as heat from the colder reservoir is:
C
QC = QA
+ QBC
40
Case I: Assume that Engine A violates Kelvin's statement.

Then
C
QA
= 0 and WA < 0
The energy balance for Engine A requires:
Q AC + Q AH +WA = 0
WA = Q AH
The energy balance for Engine B gives:
QBC + QBH +WB = 0
QBC + QBH = WB = WA
If the engines are coupled so that the net work is zero (all work delivered by one
engine is consumed by the other):
WA = WB
Then:
H
Q A = QB + QB
QB = Q A + QB
41
The net energy transfers for the coupled engines in this case are given by:
Q H = Q AH + QBH = QBC
C
QC = QA
+ QBC = QBC
W = WA +WB = 0
When QBC > 0 , a net transfer of energy as heat occurs from the colder (C) to the
hotter (H) reservoir with no other change in the universe. This violates the
Clausius statement.
42
Case II. Assume that Engine A violates the Clausius statement.

Then
WA = 0, Q AC > 0, and Q AH < 0

The energy balance for Engine A requires:
WA + Q AH + Q AC = 0
Q AH = Q AC
The energy balance for Engine B gives:
WB + QBC + QBH = 0
WB = QBC QBH
Operate the engine in such a way that:

C
QA
= QBC = Q AH
43
The net energy transfers for the coupled engines in this case are given by:
C
QC = QA
+ QBC = 0
W = WA +WB = Q H
QH = Q AH + QBH = W
When W < 0 and QH > 0, heat is converted entirely to work, which violates the
Kelvin statement of the Second Law.
44
Carnot Cycle
A Carnot Cycle is a cyclic process that consists of:

two adiabatic reversible processes
two isothermal reversible processes.
Nicolas Sadi Carnot invented these as a tool for analyzing the efficiencies of heat
engines.
1824 Monograph: "Reflections on the Motive Power of Heat, and on Machines
Fitted to Develop That Power"
45
Consequences Of Second Law

We now use the concept of heat engines and Carnot cycles to prove four
implications or consequences of the observations summarized by the Second
Law of Thermodynamics.
Consequence No. 1:
QH
Q
= f (C ,H )
Proof:
Consider two Carnot cycles, one that utilizes an ideal gas as the working
substance and the other using condensing and evaporating steam as the working
substance.
The two working substances (fluids in this case) have very different properties,
therefore the amounts of energy transferred as heat per cycle are most likely
different, but it always is possible to choose numbers of cycles such that:
C
nG QG
= nS QSC
46
QH
G
QH
S
QC
S
C
QG
V
Ideal Gas
Steam
QH
S
QG
WG
C
QG
WS
QC
S
47
The net heat transfers for the combined system are:

Hot Reservoir:
H
H
Qnet
= nGQG
+ nSQSH
Cold Reservoir:
C
C
Qnet
= nGQG
+ nSQSC
and the net work is:
Wnet = nGWG + nSWS
Choose the coupling and direction of operation such that:

C
nSQSC = nGQG
Then:
C
Qnet
=0
48
Application of Second Law:

The Second Law requires that
H
>0
Wnet 0 and Qnet
if no energy is transferred as heat to or from the low temperature reservoir.

Application of First Law:
The First Law requires that:
C
H
Wnet + Qnet
+ Qnet
=0
Substituting the previous results for the net values leads to

H
C
nSWS + nGWG + nSQSH + nGQG
+ nSQSC + nGQG
=0
and
H
H
nSWS + nGWG = Qnet
= nSQSH nGQG
49
The Second Law requires
nSQSH + nGQGH 0
The operation of the two devices can be reversed, that has the effect of reversing
all signs, i.e., multiplying through by -1. The reverse operation leads to
(n Q
H
S S
+ nGQGH 0
Both conditions are satisfied only for the equality, so

H
nSQSH = nGQG
Then:
C
nSQSC = nGQG
and:
nSQSH
nSQSC
H
nGQG
C
nGQG
QSH
QSC
H
QG
C
QG
50
The ratios are the same for both cycles, even though the substances have
substantially different properties.
In addition, the cycles are completely arbitrary, so that only the reservoir
temperatures can be involved as variables.
Therefore
QH
Q
= f (C ,H )
NOTE: This result is completely independent of the properties of the working

substance and the precise details of the Carnot Cycle.
51
Consequence No. 2:
QH
QC
TH
TC
Proof:
P
2
5
1
H
I
6
V
52
We will first show that

f (C ,H ) =
g (H )
g (C )
This will be accomplished by applying consequence 1 twice.

QH
Cycle 2345:
QI
Cycle 1256:
= f (I ,H )
= f (C ,I )
By algebra:
QH
Q
QH QI
I
Q Q
f (C ,H ) = f (C ,i )f (I ,H )
Then
f (C ,H ) =
g (H )
g (C )
f (C ,I )f (I ,H ) =
g (I ) g (H )
g (C ) g (I )
53
No other form will cancel completely in the product.

To determine the form of the function g(), we use the ideal gas for its simplicity
(all substances must have the same result). The equation of state is
PV = R
For the isothermal steps where energy is transferred reversibly as heat:
V4
Q H = W H = P dV =
V3
Likewise:
V4
V3
V
RH
dV = RH ln 4
V
V3
V
Q C = RC ln 6
V1
Combining these results gives:
QH
QC
V
ln 4
V3
= H
C V1
ln
V6
54
The adiabatic (Q=0) steps 123 and 456 must obey the First Law of
Thermodynamics: (differential form)
dU = dW + dQ
For the ideal gas
dW = PdV
dU = CVig d
dQ = 0
CVig d = PdV =
R
dV
V
Then
H
V3
V1
ig d
RdV
C
=
55
For the two adiabatic steps:

123:

V
R ln 3 = CVig ln H
V1
C
456:

V

R ln 6 = CVig ln C = CVig ln H
V4
H
C
So
V
V
V
ln 6 = ln 3 = ln 4
V1
V4
V3
V6 V4
=
V1 V3
and
QH
QC
V
V
ln 4
ln 3
V4
H V3
=
= H
= H
C V1
C V1
C
ln
ln
V6
V6
Therefore consequence 2 is proved.

56
Because the Carnot cycle is universally valid, we use this consequence of the
Second Law to refine the concept of temperature first encountered in the
observations leading to the Zeroth Law of Thermodynamics.
The absolute temperature scale is defined by defining the temperature of the
triple point temperature of water as exactly 273.16 K, and all other temperatures
according to
QH
QC
TH
TC
where T is the thermodynamic temperature.

The equation of state for an ideal gas now is:
PV = RT
Constant volume gas thermometry with real gases provides a practical primary
device to establish the absolute temperature scale according to
T
lim PV
lim (PV )T
T =
=

P 0
R
273.16 K
P 0 (PV )273.16
57
Consequence No. 3:
dS
dQrev
defines a state function
T
Proof:
Carnot Cycle has
QH
QC
=
TH
TC
so that
QH QC
+
=0
TH TC
58
For any arbitrary cycle:
P
1
For each cycle:
QiH QiC
+
=0
TH TC
and the total for all cycles is
QiH QiC
QiH
QiC
+
=T +T =0
T
T
i H
i H
i C
C
The more Carnot cycles that are used to approximate the actual cycle, the more
accurate the approximation.
59
In the limit as the number of cycles goes to , the approximation to the arbitrary
cycle becomes accurate.
Also:
#cycles QiH
lim

#cycles
TiH
i
#cycles QiC
lim

#cycles
TiC
i
dQ H
=
TH
dQ C
= C
T
2
Then
2
dQ H
dQ C
+ C
T
dQ
rev
The symbol denotes an integral along a closed path, i.e., the path begins and
ends at the same point.
60
Then, if we define a new function S according to

dS
dQrev
T
the previous discussion shows that
dS
dQ
rev
=0
This means that S is a state function.

In other words, the value depends only on the state of the system, not upon how
the system reached that state.
61
Consequence No. 4:
S 0 for any allowed process in an isolated system, i.e., for any process that
does not violate the Second Law of Thermodynamics.
Proof:
Adiabatic, reversible path (1 2)

Adiabatic, irreversible path (1 2)
Non-adiabatic, reversible path (2 1)
V
For the adiabatic, reversible path from 1 to 2:
2
S2 S1 =
dQ
rev
=0
Then, S2 = S1
S = 0 for a reversible, adiabatic process.
62
For the irreversible, adiabatic process:

2
1Q 2
= dQ = 0
dS
dQ
in this case
T
Return to state 1 by way of a reversible process that involves energy transferred

as heat. Then
1
S2 S1 =
dQ
rev
63
First Law Application:

Adiabatic, irreversible path:
U 2 U1 = 1W2
Non-adiabatic, reversible path:
U1 U 2 = 2Q1 +2 W1
U is a state function
U 2 U1 = (U1 U 2 )
Then
1W2 = 2W1 + 2Q1
1W2
+ 2W1 + 2Q1 = 0
The net work for the cycle is
Wnet = 1W2 + 2W1 = 2Q1

If 2Q1 > 0, then Wnet < 0, and the cycle from 1 to 2 and return would violate the
Planck statement of the Second Law.
64
To satisfy the Second Law, we must have

1
2 Q1 < 0
dQ
rev
<0
And:
1
S1 S2 =
dQ
rev
<0
S2 > S1
Therefore, for any process allowed by the Second Law:

1 2S
65
Summary Statement of Second Law

a.
The entropy, S, defined by

dS
/ rev
dQ
T
is a state function.
b.
The entropy of an isolated system never decreases; S remains constant

during a reversible process, and increases during an irreversible
process.
NOTE: The universe (system + surroundings) is an isolated system, therefore

the entropy of the universe either increases or remains constant during
any process that is allowed by the Second Law of Thermodynamics.
One implication of the Second Law of Thermodynamics is that there is a
fundamental difference between energy transferred as heat and energy
transferred as work.
66
Irreversible Processes:
For an irreversible process that is allowed, we can have 1Q2 = 0 even though
S = S2 S1 > 0 .
2
/ =0
1Q 2 = dQ
dQ
/
=0
S = dS > 0 because the process is irreversible

1
But, S > 1Q2
dS >
/
dQ
T
/
TdS dQ
where the equality holds for reversible processes and the inequality for
irreversible processes.
/ rev = PdV
For a volume change of the system: dW
The First Law holds for both reversible and irreversible processes, therefore:
/ rev + dW
/ rev
dU = dQ
/ + dW
/
= dQ
(reversible process)
(irreversible process )
67
Second Law conclusions lead to

/ rev = TdS
dQ
/ < dQ
/ rev
dQ
/
dQ < TdS
/ + = dQ
/ rev
dQ
where is always positive.

Therefore, for processes that accomplish a given change in internal energy, dU:
/ rev + dW
/ rev
dU = dQ
/ + dW
/ = (dQ
/ rev ) + dW
/
= dQ
Therefore
/ rev = dW
/
dW
/ = dW
/ rev +
dW
So, for all processes that are allowed by the Second Law of Thermodynamics:
Q Qrev
W Wrev
68
Practical Applications - Efficiencies

Thermodynamic Efficiencies:
Thermal efficiency:
Carnot efficiency:
W
QH
Wrev
QH
= 1
TC
TH
QC
Coefficient of Performance: COP
W
(COP)Carnot =
TC
TH TC
69
Pattern Efficiencies:
For descriptions of irreversible processes in practical machinery, the equality
form of the Second Law does not apply, so a second specification is required.
This is done by defining a pattern efficiency that compares the actual
performance to the performance of a reversible device. Pattern efficiencies are
deermined experimentally from actual perfomance characteristics.
Work-producing machines (W < 0):
W
Wrev
Work-consuming machines (W > 0):
Wrev
W
Note that the Second Law requires that 0 p 1
70
Maximum Work
Consider a case where the system goes from state 1 to state 2 and energy is
transferred as heat to a reservoir. (The temperature of the reservoir remains
constant during the process.)
total
Suniverse
= Ssys + Sres
The differential form of this equation is

total
dSuniverse
= dSsys + dSres
Because the reservoir temperature is constant

dSres =
/
dQ
Tres
Then
total
dSuniverse
= dSsys + dSres = dSsys
/
dQ
Tres
total
/ = Tres dSsys Tres dSuniverse
dQ
71
First Law:
/ + dW
/ dQ
/ = dU dW
/
dU = dQ
/
Substitute the previous result for dQ
total
/ = Tres dSsys Tres dSuniverse
dU dW
total
/ = dU TresdSsys +TresdSuniverse
dW
Integrate this equation to get:
tot
tot
tot
tot
W = (U 2 U1) Tres Ssys
( 2 ) Ssys
(1) +Tres Suni
( 2 ) Suni
(1)
The Second Law of Thermodynamics requires that

total
total
Suniverse
S
(
)
universe (1) 0
for any allowed process. Therefore
tot
tot
W (U 2 U1) Tres Ssys
(2 ) Ssys
(1)
)
72
When useful work is obtained, W < 0. The maximum amount of work that can
obtained from the process in question is
total
total
Wmax = Usystem
Tres Ssystem
total
Note that Ssystem 0 for any adiabatic process.
73
Summary Statement of Combined First and Second Laws

For reversible processes:
/ rev = TdS
dQ
/ rev = PdV
dW
dU = TdS PdV
Only state functions are involved in this result, therefore it must hold for both
reversible and irreversible processes.
The summary statement of the physics involved in the First and Second Laws of
Thermodynamics is:
dU = TdS PdV
We will refer to this as the Physics Summary Statement.
74
THIRD LAW OF THERMODYNAMICS

Formal Statements:
Nernst-Simon Statements of Third Law
The entropy change associated with any condensed system undergoing a
reversible isothermal process approaches zero as temperature
approaches 0 K, where condensed system refers to liquids and solids.
It is impossible for any process, no matter how idealized, to reduce the
entropy of a system to its absolute-zero value in a finite number of
operations.
Lewis-Randall Statement of Third Law
If the entropy of each element in some (perfect) crystalline state be taken
as zero at the absolute zero of temperature, every substance has a finite
positive entropy; but at the absolute zero of temperature the entropy may
become zero, and does so become in the case of perfect crystalline
substances.
75
Consequences of Third Law

It is impossible by any procedure, no matter how idealized, to reduce the
temperature of any system to zero temperature in a finite number of finite
operations.
Heat Capacity
lim C X = 0
T 0
Ideal gas with Fermi statistics (odd total spin):

Ideal gas with Bose statistics (even total spin):
Electrically conducting crystalline solid:
Electrically conducting crystalline solid:
lim CV T
T 0
lim CV T
T 0
lim CV T
T 0
lim CV T 3
T 0
76
Thermal Expansion
1 V
lim = lim = 0
T 0
T 0 V T P
The functional dependence of the thermal expansion is the same as that of the
heat capacity.
Phase Transitions (Vapor/Liquid, Vapor/Solid, Solid/Liquid)
Only 3He and 4He have liquid as an equilibrium phase at T = 0 K. The entropy
change of a vapor/condensed phase transition goes to infinity as T 0 ,
therefore
lim P = 0 , where P is the sublimation or vapor pressure.
T 0
For the helium isotopes, both solid and liquid phases exist at absolute zero, so
the entropies of the solid and liquid phases must be identical at the equilibrium
pressure. Then:
dP
lim
= 0 , where P is the melting (freezing) pressure.
T 0 dT
77
Practical Thermometry
Primary Thermometer:
A device for which the relationship between a measured physical property and
the thermodynamic temperature is known exactly from theory.
Examples:
Constant volume gas thermometry

Optical pyrometry
Susceptibility of paramagnetic salts
Resistance white noise (Johnson noise)
Constant Volume Gas Thermometry Relation:
T2
=
T1
(PV )2
(PV )1
lim
P0
lim
P0
78
Secondary Thermometer:
A device for which the relationship between a measured physical property and
the thermodynamic temperature is not known exactly. Secondary thermometers
must be calibrated in some manner.
Examples:
Platinum resistance (PRT's)

Thermocouples
Liquid-in glass
79
Philosophy of Practical Temperature Scales

Define one fixed point:
(t.p. of H2O T = 273 .16 K)
Use primary thermometers to measure the thermodynamic temperatures of
other fixed points.
Assign temperatures to the other fixed points based upon the best available
measurements.
Define a standard instrument for interpolating between the assigned fixed
points. Also define a standard relationship between the measured property
and the practical temperature.
Abbreviations
ITS:
International Temperature Scale
IPTS:
International Practical Temperature Scale
CCT:
Comit Consultatif de Thermomtrie
CIPM:
Comit International des Poids et Mesures
80
History of Temperature Scales

Early Temperature Scales
Newton (1701):
Ice point
= 0 N
Human body = 12 N
Fahrenheit (1724): Freezing point of salt + water = 0 F

Human Body
= 96 F
Celsius (1742):
Ice Point
=
0 C
Boiling point of water = 100 C
81
International Temperature Scales:

CIPM - 1887: This scale was based upon constant volume gas thermometry
using normal H2
Originally defined from -25 to 100 C
Fixed points:
freezing point of water =

0 C
boiling point of water = 100 C
ITS-27:
Fixed points: Freezing point:
Boiling points:
Melting points:
water
oxygen, water, sulfur
silver, gold
Interpolating instruments:
platinum resistance thermometers
platinum-rhodium thermocouple
optical pyrometer
82
ITS - 48:
Change from melting point to freezing point for Ag, Au
Adjusted the ranges of applicability for the standard instruments
ITS-48 (1960 modification):
Change from freezing point to triple point of H2O.
Boiling point of sulfur changed to freezing point of Zn.
IPTS - 68:
Boiling point of H2O changed to freezing point Sn.
Fixed points added at low temperatures
Values changed for:
Boiling point of O2
Freezing points of Zn, Au, Ag
83
IPTS - 68 (1975 Modification):

Triple point of Ar added as an acceptable fixed point.
EPT - 76:
Provisional scale adopted for 0.5 to 30 K range, utilizing mostly
superconducting transition temperatures as fixed points.
ITS - 90:
Current international temperature scales
Significant changes in many assigned fixed point temperatures, especially at
higher temperatures.
Change in interpolating instrument between 600 and 1050 C from
thermocouples to platinum resistance thermometers.
84
Evolution of International Temperature Scales

Fixed
Point
NHS
ITS-27
ITS-48
IPTS-68
IPTS-68(75)
EPT-76
ITS-90
Au
FP
----
1336.15
1336.15
1337.58
1337.58
---
1337.33
Ag
FP
----
1233.65
1233.95
1235.08
1235.08
---
1234.93
Al
FP
----
---
---
---
---
---
933.473
BP
----
717.75
717.75
---
---
---
---
Zn
FP
----
---
---
---
692.677
Sn
FP
----
---
---
(505.1181)
(505.1181)
---
505.078
In
FP
----
---
---
---
---
---
429.7485
H2O
BP
373
373.15
373.15
---
---
Ga
TP
----
---
---
---
302.9146
H2O
TP
----
---
---
---
273.16
H2O
FP
273
273.15
273.15
---
---
---
---
Hg
TP
----
---
---
---
---
---
234.3156
O2
BP
----
90.18
90.188
90.188
---
---
90.18
692.73
373.15
--273.16
692.73
373.15
--273.16
85
Fixed
Point
NHS
ITS-27
ITS-48
IPTS-68
IPTS-68(75)
EPT-76
ITS-90
Ar
TP
----
---
---
---
(83.798)
---
83.8058
O2
TP
----
---
---
54.361
54.361
---
54.3584
Ne
BP
----
---
---
27.102
27.102
27.102
---
Ne
TP
----
---
---
---
---
24.5591
24.5561
H2
BP
----
----
---
20.28
20.28
20.2734
20.3
H2
BP
----
---
---
17.042
17.042
17.0373
17.0
H2
TP
----
---
---
13.81
13.81
13.8044
13.8033
Pb
SP
----
---
---
---
---
7.1999
---
4He
BP
----
---
---
---
---
4.2221
4.2
In
SP
----
---
---
---
---
3.4145
---
3He
BP
----
---
---
---
---
---
3.2
Al
SP
----
---
---
---
---
1.1796
---
Zn
SP
----
---
---
---
---
0.851
---
Cd
SP
----
---
---
---
---
0.519
---
Reduced pressure boiling point (P = 33,330.6 Pa)
86
Defining Fixed Points For ITS-90

Material
Equilibrium State
Temperature
(kelvins)
He
Vapor Pressure
3-5
e-H2
Triple Point
e-H2
Vapor Pressure
Ne
Triple Point
24.5561
O2
Triple Point
54.3584
Ar
Triple Point
83.8058
Hg
Triple Point
234.3156
H2O
Triple Point
273.16
Ga
Melting Point
302.9146
In
Freezing Point
429.7485
Sn
Freezing Point
505.078
13.8033
17 - 20.3
87
Zn
Freezing Point
692.677
Al
Freezing Point
933.473
Ag
Freezing Point
1234.93
Au
Freezing Point
1337.33
Cu
Freezing Point
1357.77
88
Differences Between ITS - 90 and IPTS - 68
89
Proposed Redefinition of Temperature in SI Unit System

The definition of the kelvin will undergo a fundamental change if the proposal is
accepted. Rather than using the triple point of water to fix the temperature scale
the proposal recommends that the energy equivalent as given by Boltzmann's
equation be used.
Current definition: The kelvin, unit of thermodynamic temperature, is the
fraction 1/273.16 of the thermodynamic temperature of the triple point of
water.
Proposed definition: The kelvin, K, is the unit of thermodynamic
temperature; its magnitude is set by fixing the numerical value of the
Boltzmann constant to be equal to exactly 1.38065X1023 when it is
expressed in the unit s2m2kgK1, which is equal to JK1.
For a physical interpretation of this new definition, consider an ideal gas
concentrated such that the average volume per molecule is 1.38065X1023 m3.
That is the volume of a cube with a side length of about 24 nm. The ratio of the
gas's temperature and pressure would be defined exactly equal to 1 K/Pa.
One consequence of this change is that the new definition makes the definition of
the kelvin depend on the definitions of the second, the metre, and the kilogram.
90
MICROSCOPIC INTERPRETATIONS: TEMPERATURE, ENTROPY, WORK,

HEAT
In reality, all systems (including the particles in an ideal gas) are quantum
systems with discrete energy levels.
The total energy of the a system of particles is given by
E
total
= njE j
where:
j =1
Ej = energy associated with quantum state j

nj = number of particles in quantum state j
Examples:
Boltzmann statistics:
Particle in a box (ideal gas):
Ej
n j exp
kT
Ej =
h 2 nx2 + ny2 + nz2
8mV
2
3
)
91
Temperature is related to the distribution of particles among the available

quantum states.
Heat denotes energy transfer that occurs because the distributions among the
available energy levels are different for two objects that are in thermal contact.
Work denotes energy that is transferred to the system because of changes in the
energy levels in the system.
Entropy is related to the number of different ways that a system can have the
same total energy.
92
Microscopic (Statistical) Viewpoint of Entropy

Entropy is related to the number of different ways that a system of constant
energy may be arranged.
Model system
As a concrete example, consider a set of N particles. Each particle may be in
one of two states; lets call them up and down.
.....
The particles are completely independent they do not interact with one another
in any fashion. There is no external
present. Thus, all configurations of the
. . .field
..
1
2
3
4
5
N
system have identical energy. For convenience, lets say the energy is equal to
zero.
93
Some necessary definitions

Microstate:
the most detailed level of description of a system.
Examples:
Quantum mechanics: quantum state
Classical statistical mechanics: position and momentum of every atom
Our model system: the state of every particle
Macrostate: a set of microstates with something in common
Examples:
Quantum mechanics: same value of the energy
(then the macrostates may be called levels)
Our model system: same total number of particles in up state
94
Microstates and the connection with entropy

How many different microstates are there in our system?
2N
Since this number represents the total number of different ways that the system
may be arranged, and all arrangements have the same energy (i.e., 0), we
expect that it will be related to entropy.
In statistical mechanical terminology, this number represents the
microcanonical partition function for our model system. The term
microcanonical generally means at constant energy, volume, and number of
particles and so is sometimes written more fully as (E,V ,N ) . It is generally
defined as
(E,V ,N ) the number of different microstates having
energy E, at volume V and number of
particles N
95
Boltzmann defined entropy as being proportional to the natural log of the

microcanonical partition function
S (E,V ,N ) = kB ln
In our very simple model system as defined, volume does not really exist, and
energy is always 0, so we may write
(E = 0,N ) = 2N
S = kB ln2N = NkB ln2

Of course, for real atoms in three dimensions, the expression for entropy will be
more complex.
96
Macrostates
For our model system, consider macrostates being defined based on the same
total number of particles in the up state. How many different macrostates are
there?
N +1
For large N, this is considerably smaller than the number of different microstates.
Lets consider a macrostate having nu particles in the up state. How many

different microstates are in this macrostate?
N!
(N nu )!nu !
97
If we sum the number of microstates in each macrostate, over all of the possible
macrostates, we should get back the total number of microstates
N
N!
= 2N
nu =0 (N nu )!nu !
This is true because we know from the binomial theorem that

N
N!
N
r = (1+ r )
n=0 (N n )!n!
for any integer n and real number r.
98
Connection with macroscopic property measurements

Microstate picture.
Statistical mechanics tells us that the average value of any property B (whose
value Bi in any given microstate i may be meaningfully defined) can simply be
calculated from a probabilistic average
B =
total # of
microstates
i =1
Bi pi
where pi is the probability of a microstate.

Likewise, the variance in that property may be found from
B2 (B B
)2
total # of
microstates
i =1
(Bi
)2 pi
We assume that Bi may be calculated. But what is pi ? A fundamental

assumption of statistical mechanics is that for a system at constant
(macroscopic) energy, all microstates are equally likely. So, we have
pi =
99
Macrostate picture.
Alternatively, if macrostates are chosen so that all members of a macrostate
have the same value for the property B, we can use a sum over macrostates to
define the average.
B =
total # of
macrostates
j =1
Bj pj
where p j is the probability of a macrostate. Again assuming that all microstates

are equally likely, we can say
pj =
# of microstates in macrostate j
The variance can be written

B2 (B B
total # of
macrostates
i =1
Bj B
pj
Question to think about: are these macrostate averages and variances equal to
their microstate counterparts defined above?
100
Measuring a property.
Assume that we have an experimental device that will measure the difference
between the number of up and down particles in the system, nu nd (although it
is not sufficiently precise to follow individual particles).
What do we expect this device to read out on average, and how big do we expect
the fluctuations in the reading to be?
For our model system, using the macrostate approach, we have
N
nu nd = (nu nd )
nu =0
N!
(N nu )!nu !
2N
Noting that
nd = N nu
101
we have
N
nu nd = ( 2nu N )
N!
(N nu )!nu !
nu =0
2N
N!
N N
N!
= N nu
N
2 nu =0 (N nu ) ! nu ! 2 nu =0 (N nu ) ! nu !
2
2 N 1 N N
N2
N 2
N
2
2
=0
This answer makes sense, considering that there is no incentive for the particles
to be either up or down.
102
Consider (nu-np) and pi for an example of 10 particles.
10
0.1
5
6
4
0.01
nu - nd
-5
4
2
0.001
-10
0
nu
10
103
The variance in our quantity nu nd is defined as

2
ud
((nu nd )
nu nd
)2
Since we already have shown that nu nd = 0 , we can simplify our lives and
say
2
ud
(nu nd )
104
So
2
ud
= ( 2nu N )
N!
(N nu )!nu !
nu =0
1
2N
2N
4nu2 4Nnu + N 2
nu =0
N!
(N nu )!nu !
N
N
1 N 2
N!
N!
N!
2
= N 4 nu
4N nu
+N
n
!n
!
N
n
!n
!
(
)
(
)
2 nu =0 (N nu )!nu !
nu =0
nu =0
u
u
u
u
1
2N
4 N(N + 1)2N 2 4N N 2N 1 + N 2 2N
= N(N + 1) 2N 2 + N 2
=N
105
The variance in our quantity nu nd is equal to the total number of particles in

the system. This means that the standard deviation, or typical size of a
fluctuation in this variable, is
ud = N
Often, it is not so much the absolute size of a fluctuation that is important, but
rather the size relative to the size of the system. To put it on a relative basis, we
can write
ud
1
=
N
N
22
So for a system with ~10

0 will be ~10
11
particles, the typical fluctuation of nu nd away from
of the total number of particles.

2
For a system with ~10 particles, the typical fluctuation of nu nd away from 0
will be ~10
of the total number of particles.
106
The comparison of the probability distributions for systems of size N = 100 and
N = 10 are shown in the graph below.
10
10
10
20
40
60
80
100
10
-2
-6
-10
-14
10
nu
10
10
10
10
-18
-22
-26
-30
nu
The behavior of relative fluctuations with system size has some implications for
nanotechnology.
107
Microscopic (Statistical) Viewpoint of Energy and Temperature

Model system
Consider our previous model of N particles, where each particle may be in one of
two states called up and down. However, now there is an external field of
strength F pointing in the up direction.
.....
F
1
.....
The field has an energetic effect on each particle, captured by the following
expression
+ , down
ei = F mi
, up
Although each particle interacts with the applied field, we will still assume that
they do not interact with one another in any fashion i.e., they are still
independent.
108
The total energy of the system in any microstate may therefore be written
E = nu ( ) + nd ( )
= nu ( ) + (N nu ) ( )
= (N 2nu )
where nu is the number of particles in the up state and nd is the number of

particles in the down state.
Note that the above expression implies that:
( E )N
= 2 ( nu )N
Temperature
Now well introduce the definition of the thermodynamic temperature (more on
this later)
1 S
T E V ,N
which may be written from a microscopic viewpoint as well
1 ln
kT E V ,N
109
Energy Temperature Relationship for Model System

Since our system has a simple linear relationship between total energy E and the
number of up particles nu, as outlined above, we may write
1 ln
ln
=
=
E N 2 nu
N
Recall that for a given number of up particles (which is here equivalent to a
given energy), the microcanonical partition function is
(E,N ) = (nu ,N ) =
ln
n
So that
=
N
N!
(N nu )!nu !
nu
N!
ln
n
!
n
!
(
)
u
u
Using Stirlings approximation ( lnM ! M lnM M ) for large M, we find
ln
n
u
= ln
1
nu
110
so that
1 N
= ln 1
2 nu
This expression may be solved for nu
nu
1
=
N 1+ e 2
e ( )
or ( )
e
+ e ( )
Noting that
nu 1
E
= 1
N 2 N
we find
E e e 2sinh ( )
=
=
= tanh ( )
N e + e
2 cosh ( )
111
which looks like
112
Lets look at a sketch of entropy as a function of energy, for this system. What is
odd about this graph?
S/kB
-1
E/N
113
Example:
Consider a system with four particles distributed among two energy levels, with
energies E0 = 0 and E1 = 1. In the Boltzmann distribution (the simplest of several
distribution functions), the probability that an individual particle has energy Ei is
E
E
E
exp i
exp i
exp i
kT =
kT
kT
P (E i ) =
=
E
E
E
1
exp k exp 0 + exp 1 1+ exp
kT
kT
kT
kT
all
energy
levels
The particles then are distributed as shown below for several different
temperatures.
E = 1:
E = 0:
kT:
x
xxxx
0+
xx
xxx
xx
= 0.910
+,
xxx
xxxx
x
= 0.910
114
Possible arrangements:
E total = 0 :
E total = 1:
E total = 2 :
0 0 0 0
1 way
4 ways
1 1 0 0
1 0 1 0
1 0 0 1
0 1 1 0
0 1 0 1
0 0 1 1
6 ways
1
0
0
0
0
1
0
0
0
0
1
0
0
0
0
1
115
E total = 3 :
E total = 4 :
1
1
1
0
1
1
0
1
1
0
1
1
0
1
1
1
1 1 1 1
4 ways
1 way
Note that states 3 and 4 cannot be reached by isolated systems moving toward
equilibrium.
116
MATHEMATICAL IMPLICATIONS OF THERMODYNAMIC LAWS

Functions
Function: y is said to be a function of x if there is a unique value of y associated
with every value of x.
Notation: y = f ( x )
where: y is the dependent variable
x is the independent variable
NOTE: the choice of independent variables often is quite arbitrary in
thermodynamics problems.
117
y2
y1
y = f1(x)
1
y = f2(x)
x1
x2
NOTE:
y 1 = f 1 ( x 1) = f 2 ( x 1)
y 2 = f1 (x 2 ) = f 2 (x 2 )
but, in general, f1( x ) f 2 ( x )
118
Observations:
Integrals with values independent of path:
2
dx
= x 2 x1
1
2
dy
= y 2 y 1 = f1( x 2 ) f1( x 1) = f 2 ( x 2 ) f 2 ( x 1)
Path dependent integrals:

2
/ i = si
Path length = ds
1
Area under curve =
dA
/ i
f
i
( x ) dx
119
Terminology:
d is an exact differential if the value of the integral does not depend upon the
choice of paths from 1 to 2.
d/ is an inexact differential if the value of the integral depends upon the choice
of paths from 1 to 2.
Notation: use d/ to denote inexact differentials.
NOTE: d = 0 for an exact differential for any closed path.
120
Practical Significance:
Each state of a system is described by a unique set of state variables. As a
result, the state variables must behave as mathematical functions.
Notes:
The differentials of all state functions are exact differentials.
The energy transferred as heat or work depends upon the choice of paths from
/ and dQ
/ are inexact differentials.
state 1 to state 2, therefore dW
121
Multivariable calculus
A dependent variable may be a function of several independent variables:
z = f ( x1,x 2 ,x 3 ,,x n )
or
F ( x1,x 2 ,x 3 ,,x n ,x n+1) = 0
Total Derivative:
dz = lim
x i 0
{f ( x1 + x1,x 2 + x 2 ,,x n + x n ) f ( x1,x 2 ,,x n )}
f ( x 1 + x 1,x 2 + x 2 ,,x n + x n ) f ( x 1,x 2 + x 2 ,,x n + x n )

+f ( x ,x + x ,,x + x ) f ( x ,x ,,x + x )
1 2
2
n
n
1 2
n
n
= lim
x 0 +
+f ( x 1,x 2 ,,x n + x n ) f ( x 1,x 2 ,,x n )
f ( x + x,y ) f ( x,y )
f
=
lim
Definition of partial derivative:
x y x 0
x
122
Then:
Also:
f
dz = lim
x i 0 i =1 x i
x
n
x i
k i
lim x i = dx i
x i 0
Therefore
z
dz =
i =1 x i x
n
dx i
k i
If there are two independent variables:
z = f ( x,y )
z
z
dz = dx + dy
x y
y
x
123
For physical systems, we often use equations of the form:
f ( x,y,z ) = 0
The choice of independent variables in this case is arbitrary, so we could use any
of:
x = F ( y,z )
y = G ( x,z )
z = H ( x,y )
Then
z ( x,y )
z
z
dz =
dx
+
y dy
x y
x
y ( x,z )
y
y
dy =
dx
+
dz
x z
z x
Combine these by substituting dy from the second equation into the first
equation.
124
Then:
z y
z
y
dz =
dx +
dx +
dz
x y
y x x z
z x
After collecting like terms:
z
z y
z y
dz 1
z = dx x + y x
x
y
z
x
x
x,z could be chosen as the independent variables, therefore the above equation
must hold for arbitrary choices of dx, dz.
z y
1
z = 0
x
x
z
z y
= 0
x y y x x z
y
z
y = z
x
x
z y x
y x z = 1
z
y
x
125
Consider another variable: w = w ( x,y )

Then, begin with
z ( x,y )
z
z
dz = dx + dy
x y
y
x
Divide by dw:
dz z dx z dy
=
+
dw x y dw y x dw
Restrict to the case of constant y:
z
z x
=
w y x y w y
If the original equation is divided instead by dy:
dz z dx z dy z dx z
=
+
=
+
dy x y dy y x dy x y dy y x
126
When this is restricted to constant w:
z
z
z x
=
+
y
y
w
w
x
127
For any state function, f, the value is defined uniquely at any state of the system,
therefore:
df
=0
for any closed path in the state variable space.

Vector Notation:
F = (F1,F2 ,,Fn )
dx = (dx 1,dx 2 ,,dx n )

n
F dx = F i dx i
i =1

=
,
,,
x n
x1 x 2
f f
f
f =
,
,,
x n
x1 x 2
F
Fi 1 Fi +1
F1
F2
Fn1
n
F =
,, x x ,, x

x
x
x
2
n
i
+1
i
1
n1
1
128
From advanced calculus, Stokes Theorem gives:

f
df =
i =1 x i x
df
Then, by Stoke's theorem:
Where
Then
df
)i
F dA
dx i = f dx
Observe that
F d x
k i

d x = f d A
x 0 xn
2 f
2 f
=
;
x i 1 x i +1 x i +1 x i 1 x n+1 x 1
n
2 f

i =1 x i 1 x i +1
2 f
dAi
x i +1 x i 1
But, because df = 0 for any state function for any path and surface, the term in
square brackets in the integrand always must be zero. Therefore:
2 f
2 f
=
x i x k x k x i
Therefore, if f is a state function, the order of differentiation with respect to the
independent variables does not matter.
129
Summary of Math Results

Math 1:
f
df =
i =1 x i x
n
dx i f ( x 1,x 2 ,,x n )
k i
Math 2:
z
z y
=
1
y z

x
x
Math 3:
z y x
y x z = 1
z
y
x
Math 4:
z
z x
=
w y x y w y
Math 5:
z
z
z x
=
+
y
y
w
w
x
Math 6:
2 f
2 f
=
x i x k x k x i
y
=
z x
130
Legendre Transformations
In many practical cases, we will find it convenient to change to a different set of
independent variables.
Math 1
y = f ( x 1,x 2 ,,x n ) dy = Ci dx i
i =1
Define a new function by:

Then:
f
where: Ci =
x i x
k i
i = y Ci x i
n
k =1
k =1
k i
d i = dy Ci dx i x i dCi = Ck dx k Ci dx i x i dCi = Ck dx k x i dCi
Math 1
i = f ( x 1,x 2 ,,Ci ,,x n )
The new function replaces xi with Ci as an independent variable.

Note that multiple transformations are allowed.
131
Applications of Mathematics to Physics Summary

The fundamental differential form of the summary of the First and Second Laws
of Thermodynamics (Physics Summary Statement) for a closed system is:
dU = TdS PdV
Compare to Math 1:
f
df =
dx i
i =1 x i
n
f ( x 1,,x n )
We would prefer U = U(T,P) because pressure and temperature are convenient

from a practical point of view, and the choice of variables is arbitrary from the
mathematical point of view.
Then:
Math 1
U
U
dU =
dT
+
dP
T P
P T
U
U
However, we cannot easily identify
and
with other
T P
P T
thermodynamic quantities.
132
Note also that for the Legendre transformation form, this is:
dU = TdS PdV
C1 = T
C2 = P
x1 = S
x2 =V
The form of the Physics Summary Statement indicates that the "natural"
independent variables for internal energy are entropy and volume. In general,
manipulations will be more convenient when guided by the natural independent
variables.
Result:
dU = TdS PdV
U = U (S,V )
133
Legendre Transformations of Internal Energy:

Legendre transformations of the internal energy provide energy functions that
have other natural independent variables
dU = TdS PdV

U = U (S,V )
C1 = T
C2 = P
x1 = S
x 2 =V
Replace S with T:
1 = U C1x 1 = U TS
d 1 = dU TdS SdT = TdS PdV TdS SdT
d 1 = SdT PdV
Result:
1 = 1 (T ,V )
A (T ,V ) = U TS (Helmholtz Free Energy )
134
Replace V with P:
2 = U C2 x 2 = U ( P )V = U + PV
d 2 = dU +VdP + PdV = TdS PdV +VdP + PdV
d 2 = TdS +VdP 2 = 2 (S,P )
Result:
H (S,P ) = U + PV
(Enthalpy )
Replace S with T and V with P

12 = U C1 x 1 C2 x 2 = U TS + PV = A + PV = H TS
d 12 = SdT +VdP
Result:
12 = 12 (T ,P )
G (T ,P ) = U + PV TS ( Gibbs Free Energy )
135
Alternative Forms of Physics Summary Statement
dU = TdS PdV
U = U (S,V )
dH = TdS +VdP
H = H (S,P )
dA = SdT PdV
A = A (T ,V )
dG = SdT +VdP
G = G (T ,P )
136
Extension to Mixtures and Open Systems:
U total = nU = U total (nS,nV ,n1,,nm )

where:
m = number of chemical species present.
Math 1 requires:
(nU )
d (nU ) =
(nS )
nV ,{nk }
(nU )
d (nS ) +
(nV )
(nU )
d (nV )+
i =1 ni nS,nV ,n
m
nS,{nk }
dn i
k i
In the first two terms, {ni} held constant implies that n also is held constant.
Then
(nU )
(nS )
{ }
nV , ni
U
=
S V ,n
and
(nU )
Notation: Define: i
n i nS,nV ,n
(nU )
(nV )
{ }
nS, ni
U
=
V S,n
where i is the chemical potential
k i
Then:
d (nU ) = Td (nS ) Pd (nV ) + i dn i

i =1
137
Physics Summary Statements for Open Systems:

m
d (nU ) = T d (nS ) P d (nV ) + i dn i

i =1
m
d (nH ) = T d (nS ) + (nV ) dP + i dn i

i =1
m
d (nA ) = (nS ) dT P d (nV ) + i dn i

i =1
m
d (nG ) = (nS ) dT + (nV ) dP + i dn i

i =1
where:
nU = nU (nS,nV ,n1,n2 ,,nm )
nH = nH (nS,P,n1,n2 ,,nm )
nA = nA (T ,nV ,n1,n2 ,,nm )
nG = nG (T ,P,n1,n2 ,,nm )
138
Thermodynamic Definitions
Combine Math 1 with the physics summary statements to identify partial
derivatives of energy functions with physical variables:
Temperature:
(nU )
T =
(nS ) nV , n
{ i}
(nH )
=
(nS ) P, n
{ i}
U
=
S n,V
H
=
S n,P
Pressure:
(nU )
P =
(nV )
(nA )
=
(nV )
{ }
nS, ni
{ }
T , ni
U
=
V n,S
A
=
V n,T
139
Volume:
H
G
V =
=
P S,n P T ,n
Entropy:
A
G
S =
=
T V ,n T P,n
Chemical Potential:
(nU )
i =
n i nV ,nS,n
k i
(nH )
=
n i nS,P,n
k i
(nA )
=
n i T ,nV ,n
k i
(nG )
=
n i T ,P,n
k i
140
Maxwell Relations
The Maxwell Relations follow from Math 6 applied to the differential forms of the
Physics Summary Statements:
dU = TdS PdV
T
P
V S
S V
dH = TdS +VdP
T
V
P S
S P
dA = SdT PdV
S
P
V T
T V
(MxA)
dG = SdT +VdP
S
V
=
P T
T P
(MxG)
141
Partial Molar Properties

Begin with the differential form of the Gibbs summary statement for an open
system:
m
d (nG ) = (nS ) dT + (nV ) dP + i dn i

i =1
(nG )
i =
n i T ,P,n
k i
(nS )
i
=
T P,n
n i T ,P,n
k i
(nV )
i
=
P T ,n
n i T ,P,n
k i
Definition:
(nX )
Xi
n i T ,P,n
where:
X i is the partial molar quantity
k i
(Partial molar properties are very useful for describing mixture properties.)
142
Property Change Calculations

General Approach
For practical applications of the First and Second Laws of Thermodynamics, the
change in physical properties accompanying a change of state is required. For
any physical property, , the change is calculated using
= ( 2 ) (1) =
where:
may be any state function, but most commonly is U, H, A, G or S.

is the change in the property
(i) is the value of property for state i
For pure fluids (or mixtures at fixed composition) the convenient independent
variables are either (T,P) or (T,V) as the independent variables.
2
Math Relation 1: ( 2 ) (1) =

dT
+
dX
T X
X T
where X denotes either P or V.

143
Because the physical properties are state functions, we may choose any path
between state 1 and state 2 to evaluate the integral. The most convenient path
for the calculation is to vary only one of the independent variables at a time:
T2
(T2 ,X 2 ) (T1,X 1) =
dT +
T X
T1
X2
X1
dX
X T
2
or
X2
(T2 ,X 2 ) (T1,X 1) =
X1
dX +
X T
1
T2
T1
dT
T X
2
However, to calculate the values of these integrals we must relate the partial
derivatives in the integrals to properties that are measurable.
144
Manipulation of Thermodynamic Variables

Thermodynamic variables can be divided into two classes:
Physical Observables: variables that can be measured in the laboratory
Examples: P, V, T, CP, CV.
Intangibles: variables that cannot be measured or observed directly
Examples: U, H, A, G, S.
Because the intangibles cannot be measured directly, they must be expressed in
terms of the physical observables through manipulations of the thermodynamic
variables, usually in the form of partial derivatives.
These manipulations are made easier using a systematic approach as shown
below.
145
Common Physical Observables:

In addition to the basic variables P, V and T, there are several derivatives that
can be measured in the laboratory:
Thermal expansion coefficient:
1 V
V T P
Isothermal compressibility:
1 V
V P T
Isentropic compressibility:
1 V
V P S
Bulk modulus (isothermal):
P
BT V
V T
Bulk modulus (adiabatic):
P
BS V
V S
Thermal pressure coefficient:

Heat capacities:
CX
1 P
P T V
dQ
dT
Constant X
146
Heat Capacity at Constant Volume:

Definition:
Qrev
CV
T V
Begin with differential form of First Law:
/ rev + dW
/ rev = dQ
/ rev PdV
dU = dQ
Rearrange:
/ rev = dU + PdV
dQ
Divide by dT:
/ rev dU
dQ
dV
=
+P
dT
dT
dT
Restrict to constant volume:
Therefore:
Qrev
U
V
=
+
P
T V T V
T V
U
CV =
T V
147
Use the Physics Summary Statement in the form:

dU = TdS PdV
Divide by dT and restrict to constant V

U
S
V
=
T
T V
T V
T V
Therefore:
U
S
CV =
=
T
T V
T V
148
Heat Capacity at Constant Pressure:

Definition:
Qrev
CP
T P
Begin with differential form of First Law
/ rev + dW
/ rev = dQ
/ rev PdV dQ
/ rev = dU + PdV
dU = dQ
Divide by dT and restrict to constant pressure
Qrev
U
V
=
+
P
T P T P
T P
Note that
H
U
V
P
Q
H = U + PV
=
+P
+V
= rev
T P T P
T P
T P T P
Therefore:
H
CP =
T P
149
Use the Physics Summary Statement in the form:

dH = TdS VdP
Divide by dT and restrict to constant P

H
S
P
=
T
V
T P
T P
T P
Therefore:
H
S
CP =
=
T
T P
T P
150
Relations Between Heat Capacities - (CP - CV)

Use relations between heat capacities and temperature derivatives of entropy
S
S
CP CV = T
T
T P
T V
Apply Math Relation 5 to the first term, then
S
S
CP CV = T
+
T
V
V
T
V
S
T
T P
T V
Apply the Maxwell Relation derived from the Helmholtz energy

S V
P V
CP CV = T
=
T
V T T P
T V T P
Therefore
151
TV 2
P V
P
2
CP CV = T
= TV
= TV BT =
T V T P
T V
T
152
Relations Between Heat Capacities - (CP /CV):

Use relations between heat capacity and entropy, the cyclic relation (Math
Relation 3), and the Maxwell relations derived from the Helmholtz and Gibbs
energies
S P
V P
S
T P
P T T S T P T S
CP
=
=
=
S
S
V

P V
CV
T

T V
V T T S T V T S
Use the chain rule for partial derivatives (Math Relation 4) in the numerator and
the cyclic relation in the denominator, so that
V P V
V P
T P V S T S
T P T S
CP
=
=
P V
CV
P V V
V T T
T V T S
T
P
S
153
Therefore
CP V S BS T
=
=
=
CV P
BT S
V T
154
Systematic Approach to Manipulations Involving Derivatives:
Roman letters (a,b,c) denote the observables (P,V,T),
Greek letters (,,) denote the intangibles (U,H,A,G,S).
The usual goal is to reduce a given derivative to an expression containing only

observables.
155
Divide the partial derivatives into six classes according to the six possible
combinations of the variables:
Class
Form
a

b c
b c
a

b
156
Procedure for Manipulation of Variables

Class 1 Derivatives:
General form:
a

b c
Example:
V T
Procedure: The only useful relation for this class is the cyclic relation (Math
Relation 3):
a b c
= 1
b c c a a b
Example:
P
P
=
V T
T V
P
T
=
V P
V
Note that this also leads to the conclusion that
=
=P
BT
157

General form:
b c
Example:
P T
Procedures:
If is S, then use the relations to the heat capacities and the Maxwell relations
directly.
If is U, H, A or G, then begin with the relevant form of the physics summary
statement, divide through by the differential of interest, and eliminate dS using a
Maxwell Relation if necessary.
Examples involving S:
CP
S
=
T P
T
S
P
=
V T T V
CV
S
=
T V
T
S
V
=
P T
T P
158
Example 2.1:
P T
Begin with
dH = TdS +VdP
Divide through by dP:
dH
dS
dP
=T
+V
dP
dP
dP
Restrict to constant T:
H
S
=
T
+V
P T
P T
Apply Maxwell Relation:
H
V
=
T
+V
P T
T P
V
=V T
T P
=V [1T ]
159
Example 2.2:
V T
Begin with
dH = TdS +VdP
Divide through by dV:
dH
dS
dP
=T
+V
dV
dV
dV
Restrict to constant T:
H
S
P
= T
+V
V T
V T
V T
Apply Maxwell Relation:
H
P
P
=
T
+V
V T
T V
V T
Note that the relations are more complex when a variable is used that is not a
"natural" independent variable.
160
a
General form:
b
T
Example:
P H
Procedure: Use the cyclic relation (Math Relation 3) to obtain two Class 2
derivatives:
a
a
=
b
b b a
Example: (Joule-Thompson coefficient)
1 V
T
T H
=
=
T
V
P H
H P P T CP T P
161

General form:
c
H
Example:
A P
Procedure: Introduce a new observable variable through Math Relation 4 to

produce two Class 2 derivatives:

a
=

a
c c
c
Example:
H
H T
=

=
A P T P A P
CP
V
S +P
T P
S is acceptable as a variable here because we will show later how to calculate S

from observables. (Derivatives of S are not acceptable.)
162

General form:
b
H
Example:
P A
Procedure: Introduce a new observable and use Math Relation 5 to obtain one
Class 3 and two Class 2 derivatives:

c
=
+

b b c c b b
Example:
H
H
H T
=
+
P A P T T P P A
H
H T A
=
P T T P A P P T
V
T A
=V T
C
P
T P
A P P T
163
where:
A
V
=
S
T
T
P
P
dA = SdT PdV
A
T
V
=
S
P T
P T
P T
Then
H
V
T A
=V
T
P
A P P T
P A
T P
V
CP P
P T
V
=V T
T P
V
S +P
T P
164
General form:
Example:
G A
Procedure: Use Math Relation 4 to introduce a new observable thereby

obtaining two Class 5 derivatives:

a
=
Example:
P A
H
H P
=

=
G A P A G A G
P A
165
From the previous example
V
CP P
P T
H
V
=V T
V
P A
T P
S +P
T P
Also:
G
G
G T
=
+
P A P T T P P A
T A
T A
=V + ( S )
=V
+
S

A
P
A
P
P
T
P
T
V
SP
P T
=V +
V
S +P
T P
166
so that
V
CP P
P T
V
V T
T P
V
S +P
T P
H
=
V
G A
SP
P T
V+
V
S +P
T P
167
Residual functions
An alternative method for calculating physical property changes utilizes ideal gas
calculations and the differences between the real material and an ideal gas.
Define the concept of a residual function:
residual (T ,X ) = (T ,X ) ig (T ,X )
Because the independent variable X may be either P or V, there actually are two
definitions of residual functions.
168
Density Form (Definition)
r (T , ) (T , ) ig (T , )
where:
r (T , ) = density residual function
(T , ) = value of for real material at T ,

ig (T , ) = value of for an ideal gas at T ,
Pressure Form (Definition)
r (T ,P ) (T ,P ) ig (T ,P )
where:
R (T ,P )= density residual function
(T ,P ) = value of for real material at T ,P

ig (T ,P )= value of for an ideal gas at T ,P
Note that the pressure and density forms of the residual functions are not
necessarily equal because they involve comparisons to different ideal gas states.
169
The density form of the residual function compares the real fluid at T, P, with
the ideal gas at
T ig = T
ig =
P ig = ig RT ig = RT =
P
Z
P
Z
=
RT
The pressure form of the residual function compares the real fluid at T, P, with
the ideal gas at
T ig = T
P ig = P
ig
P ig
P
=
=
= Z
RT RT
170
Summary Table
Temperature
Pressure
Density
Real Fluid
Ideal Gas
T ig
P ig
ig
Density Form
(P/Z)
Pressure Form
171
The property change between state 1 and state 2 is calculated using

( 2 ) (1) = (T2 ,P2 , 2 ) (T1,P1, 1)
= (T2 ,P2 , 2 ) ig (T2 , 2 ) + ig (T2 , 2 )
ig (T1, 1) + ig (T1, 1) (T1,P1, 1)
= r (T2 , 2 ) + ig (T2 , 2 ) ig (T1, 1) r (T1, 1)

or
( 2 ) (1) = (T2 ,P2 , 2 ) (T1,P1, 1)
= (T2 ,P2 , 2 ) ig (T2 ,P2 ) + ig (T2 ,P2 )

ig (T1,P1) + ig (T1,P1) (T1,P1, 1)
= R (T2 ,P2 ) + ig (T2 ,P2 ) ig (T1,P1) R (T1,P1)
Both of these forms are equivalent.
For practical calculations, the independent variables are chosen for convenience
in calculating the property change of interest.
Note that only ideal gas calculations involve a change of temperature, therefore
only ideal gas heat capacities are required.
172
Methods for Calculation

The residual functions are related by the same expressions as the energy
functions:
Density Form
H r = U r + P rV
Ar = U r TS r
G r = H r TS r = U r + P rV TS r
Pressure Form
H R = U R + PV R
AR = U R TS R
GR = H R TS R = U R + PV R TS R
Therefore, only two relationships must be derived for the five U H A G S

residuals.
173
The values for the real fluid and the ideal gas become equal in the limit as the
pressure and density go to zero, therefore
lim
R (T ,P ) = 0
P 0
lim
r (T , ) = 0
0
and
Then
(T , ) (T ,0 ) = (T , ) =
r
r
d =
ig

d
T
T
and
P
R (T ,P ) R (T ,0 ) = R (T ,P ) =
ig

R
dP
dP =
P
P T
P T
T
174
Residual Expressions (Density Forms)

Pressure
P r (T , ) = P (T , ) P ig (T , ) = Z RT RT = ( Z 1) RT
Dimensionless form:
P rV
= Z 1
RT
175
Internal Energy
Calculate the residual internal energy at any density by integrating the partial
derivative along the isotherm from zero density (where the residual is known to
vanish) to the density of interest
(T , ) =
r
U
ig
d = d d
T
T
MATH 4 gives:
U
U V
U
=
=
T
T
T
T
1
2

Use the physics summary statement for internal energy and MaxA to relate the
partial derivatives to observable properties
dU = TdS PdV
U
S
V
P
=
T
P
=
T
P
V T
V T
V T
T V
176
so that the residual internal energy is
U r (T ,V ) =
ig
d
P
P
P T
P 2
T V
T V

It also is useful to derive a dimensionless form that is written in terms of the

compression factor, Z. Begin with the equation of state
P=
ZRT
ZR RT
P

=
+
T V
V
V
V
P RT
Z
= +
T V T
V
T V
Then
RT 2 Z
RT 2 Z
P
T
P = P +
P =
T V
V
T V
V T V
so that
U
RT 2 Z 1
RT 2 Z
= V T 2 = T
V
T
177
For the ideal gas
ig
=1
Z ig
T = 0
Also, , inverse temperature is a more convenient variable than temperature in

many of equations of state. Note that
Z T1
1 Z
Z
= 2 1
=
T T1 T
T T
so that the residual internal energy (density form) is
(T , ) =
2
RT
R Z
Z
d = 1 d

T
178
This may be put in dimensionless form by dividing through by RT
Z d 1 Z
Ur
T
Z
1
=
= 1 d ln
d = 1
T
RT
T
T T
NOTATION:
For simplicity of notation in subsequent calculation, define a dimensionless
integral as follows
1 =
Z
T
T
d 1
=
1
T
179
Helmholtz Energy
One more explicit calculation is required. We choose the Helmholtz energy
because it has the variable of integration (density) as a natural independent
variable.
A (T , ) A (T ,0 ) =
r
r
A
d
T
The definition of the residual function provides

r
A = AA
ig
Ar
Aig
A
=
T
T
T
Use the physics summary statement for Helmholtz energy to relate the partial
derivatives to other properties
dA = SdT PdV
= P
V T
180
so that one form for the residual Helmholtz energy is

V
A (T ,V ) = RT ( Z 1) dV
r
Convert to density as the variable

1 P
A
ZRT
A V
=
=
P
=
=
(
)
2
V
2
T
T
T
For the ideal gas, Z
ig
= 1, therefore
Aig
RT
=

Then
A (T , ) =
r
r
A
d =
T
ZRT RT
d
( Z 1)
=
RT
181
The dimensionless form is
A ( T,)
d
= (Z 1)
RT
NOTATION:
This form leads to the definition of a second dimensionless integral
2 =
Z 1
d
182
Enthalpy
r
H =U +P V
H r U r P rV
=
+
= 1 + ( Z 1)
RT RT RT
Entropy
U r Ar
S r U r Ar
A = U TS S =
=
= 1 2
T
R
RT
r
Gibbs
r
G = H TS = A + P V
Gr
= 2 + ( Z 1)
RT
183
Summary of Density Forms
Ur
= 1
RT
Ar
= 2
RT
Hr
= 1 + Z 1
RT
Gr
= 2 + Z 1
RT
P rV
= Z 1
RT
Sr
= 1 2
R
1 Z d
1 =
T (1/ T )
2 =
Z 1
d
184
Residual Functions (Pressure Form)

Because nature forces the use of temperature and density as the independent
variables in the equation of state, the pressure forms of the residual functions are
calculated most easily using the density forms just derived and a calculation of
property changes in the ideal gas.
The residual function definitions are
R (T ,P, ) = (T ,P, ) ig (T ,P, Z )
r (T ,P, ) = (T ,P, ) ig (T ,P / Z , )
Subtracting the second equation from the first produces
R (T ,P, ) = r (T ,P, ) + ig (T ,P / Z , ) ig (T ,P, Z )

Methods to calculate r are shown in the previous section, and the difference
term ig (T ,P / Z , ) ig (T ,P, Z ) is an ideal gas calculation.
185
Volume
V R =V V ig =
ZRT RT
RT
= ( Z 1)
P
P
P
PV R
= ZR = Z 1
RT
Dimensionless form:
Internal Energy
Because entropy and volume (density) are the natural independent variables for
internal energy, the change in internal energy for the ideal gas is calculated most
easily from
ig
(T , ) U (T , Z ) =
ig
U ig
d
where
U ig
U ig V
1 U ig
= V = 2 V

T
T
T
T
186
and
U
S
P
dU = TdS PdV
=
T
P
=
T
P
V T
V T
T V
For the ideal gas

P
so that
ig
RT
=
V
P ig
R
=
T
V V
RT RT
P
T
P
=
=0
T V
V
V
Therefore
ig
(T , ) U (T , Z ) =
ig
and
U ig
d = 0
U R (T ,P, ) = U r (T ,P, )
187
Helmholtz Energy
Density also is the most convenient variable for calculations involving the
Helmholtz energy
ig
(T , ) A (T , Z ) =
ig
A ig
d
where
A ig
A ig V
1 A ig
= V = 2 V

T
T
T
T
and
dA = SdT PdV
= P
V T
188
For the ideal gas

P
ig
Aig
Aig
RT
RT
RT
=

V
V
V T
so that
ig
(T , ) A (T , Z ) =
ig
A ig
d
T
RT
d = RT ln Z = RT ln
= RT lnZ
Then
AR (T ,P, ) = Ar (T ,P, ) RT lnZ
189
Calculate the remaining functions using the definitions.

Enthalpy
H R = U R + PV R = U r + P rV H R = H r
Entropy
SR
r
r
U R AR U A RT lnZ
=
=
S R = S r + R lnZ
T
T
Gibbs Energy
G R = AR + P RV = Ar RT lnZ + PV r G R = G r RT lnZ
190
Summary of Pressure Forms

PV R P rV
=
RT
RT
= Z (T , ) 1
UR Ur
=
RT RT
= 1 (T , )
HR Hr
=
RT RT
= 1 (T , ) + Z (T , ) 1
AR Ar
=
lnZ
RT RT
= 2 (T , ) lnZ (T , )
GR Gr
=
lnZ
RT RT
= 2 (T , ) + Z (T , ) 1 lnZ (T , )
SR Sr
=
+ lnZ
R
R
= 1 (T , ) 2 (T , ) + lnZ (T , )
191
Ideal Gas Changes

When the residual function approach is used to calculate property changes, the
changes in ideal gas properties
ig (T2 , 2 ) ig (T1, 1)
or
ig (T2 ,P2 ) ig (T1,P1)
also are required. To obtain expressions for the ideal gas changes, we use the
general form
T2
ig
(T2 ,X 2 ) (T1,X 1) =
ig
T1
ig
T dT +
X2
X1
ig
X dX
where X represents either or P.
192
Internal Energy
For the internal energy, derive the expression using density as the second
independent variable
T2
ig
(T2 , 2 ) U (T1, 1) =
ig
T1
U ig
T dT +
U ig
d
For the internal energy of the ideal gas, the derivatives are
U ig
ig
=
C
T
V
U ig
1 U ig
1 P ig
ig
= 2 V = 2 T T P = 0

T
T
V
so that the change in internal energy is
ig
T2
(T2 , 2 ) U (T1, 1) = CVig dT

ig
T1
193
This result depends only upon the temperature, therefore the result is the same if
the pressure is the second independent variable
ig
T2
(T2 ,P2 ) U (T1,P1) = CVig dT

ig
T1
If the result is made dimensionless using the final temperature
ig
(T2 ) U (T1) =
ig
RT2
T2
1
T2
CVig
dT
R
T1
This leads to the definition of a third dimensionless integral

T2
ig
3
Then
1
(T1,T2 ) = T
2
T1
CVig
1
dT =
R
T2
T2
C ig
P 1 dT
T1
U ig ( 2 ) U ig (1) ig
= 3 (T1,T2 )
RT2
194
Enthalpy
The change in the ideal gas enthalpy is calculated using the relation between the
enthalpy and the internal energy
H ig = U ig + P igV = U ig + RT
This result depends only on temperature, so
H ig ( 2 ) H ig (1) U ig ( 2 ) U ig (1) R (T2 T1)
=
+
RT2
RT2
RT2
T1
= ig
T
,T
+
(
)
1 2
3
1 T
2
Alternate expression
H ig (T2 ) H ig (T1) =
T2
CPig dT
T1
195
Entropy
Using the density as the second independent variable
T2
ig
(T2 , 2 ) S (T1, 1) =
ig
T1
S ig
T dT +
S ig
d
For the entropy of the ideal gas, the derivatives are
S ig
CVig
T = T
S ig
1 S ig
1 P ig
1
R
=
2 V T
2 T V
2
T
so that the change is
2
T2
ig
C ig
V
(T2 , 2 ) S (T1, 1) =
ig
dT
T1
T2
R
d =
T1
CVig
dT R ln 2
T
1
196
If the pressure is the second independent variable

T2
ig
(T2 ,P2 ) S (T1,P1) =

ig
T1
S ig
T dT +
P2
P1
S ig
P dP
The derivatives are

S ig
CPig
T = T
P
S ig
V ig
R
=
=
T T P
so that the change is

T2
S ig (T2 ,P2 ) S ig (T1,P1) =
C ig
P
T1
P2
dT
P1
T2
R
dP =
P
T1
CPig
P
dT R ln 2
T
P1
197
The dimensionless form is
ig
T2
(T2 ,P2 ) S (T1,P1) = CPig dT

ig
R T
ln
T1
P2
P1
Define a fourth dimensionless integral

T2
ig
4
(T1,T2 ) =
CPig dT
=
R T
T1
T2
C ig dT
V +1
T1
Then
S ig ( 2 ) S ig (1) ig
P
2T2
= 4 (T2 ,T1) ln 2 = ig
T
,T
ln
(
)
2 1
4
R
P1
1T1
198
Helmholtz Energy
Use the relation of the Helmholtz energy to the internal energy and entropy
Aig ( 2 ) Aig (1) = U ig ( 2 ) T2S ig ( 2 ) U ig (1) T1S ig (1)

Then
Aig ( 2 ) Aig (1) U ig ( 2 ) U ig (1) S ig ( 2 ) T1S ig (1)
=
+
RT2
RT2
R
T2R
U ig ( 2 ) U ig (1) S ig ( 2 ) S ig (1) T1 S ig (1)
=
1
RT2
R T2 R
R
=
ig
3
T1,T2 ig
4
P2 T1 S ig (1)
(T1,T2 ) + ln P 1 T R
1
2
ig
3
T2 2 T1 S ig (1)
(T1,T2 ) + ln T 1 T R
1 1
2
T1,T2 ig
4
199
Gibbs Energy
Use the relation of the Gibbs energy to the enthalpy and entropy
G ig ( 2 ) G ig (1) = H ig ( 2 ) T2S ig ( 2 ) H ig (1) T1S ig (1)

Then
G ig ( 2 ) G ig (1) H ig ( 2 ) H ig (1) S ig ( 2 ) T1S ig (1)

=
+
RT2
RT2
R
T2R
H ig ( 2 ) H ig (1) S ig ( 2 ) S ig (1) T1 S ig (1)
=
1
RT2
R
R
T2 R
=
ig
3
T1 ig
P2 T1 S ig (1)
(T1,T2 ) + 1 T 4 (T1,T2 ) + ln P 1 T R
2
1
2
ig
3
T1,T2 ig
4
P2 T1 S ig (1)
(T1,T2 ) + ln P 1 T 1+ R
1
2
ig
3
T2 2 T1 S ig (1)
(T1,T2 ) + ln T 1 T 1+ R
1 1
2
T1,T2 ig
4
200
General Formulae for Property Changes

Combine the previous results to obtain formulae for the general cases.
Internal Energy
Begin with the basic difference equation
U ( 2 ) U (1) = U r ( 2 ) U r (1) +U ig (T2 , 2 ) U ig (T1, 1)

= 1 (T2 , 2 ) RT2 1 (T1, 1) RT1
+ig
3 (T1,T2 ) RT2
Dimensionless form
U ( 2 ) U (1)
T
= 1 ( 2 ) 1 1 (1) + ig
3 (T1,T2 )
RT2
T2
201
Enthalpy
H ( 2 ) H (1) = U ( 2 ) + RT2 Z (T2 , 2 ) U (1) + RT1 Z (T1, 1)

Dimensionless form
H ( 2 ) H (1) U ( 2 ) U (1)
T
=
+ Z (T2 , 2 ) 1 Z (T1, 1)
RT2
RT2
T2
= 1 (T2 , 2 )
T1
1 (T1, 1)
T2
+ig
3 (T1,T2 ) + Z (T2 , 2 )
T1
Z (T1, 1)
T2
Algebraic rearrangement and simplified notation gives
H ( 2 ) H (1)
T
= 1 ( 2 ) + Z ( 2 ) 1 1 (1) + Z (1) + ig
3 (T1,T2 )
RT2
T2
202
Entropy
S ( 2 ) S (1) = S R ( 2 ) S R (1) + S ig (T2 ,P2 ) S ig (T1,P1)

Dimensionless form
S ( 2 ) S (1) S R ( 2 ) S R (1) S ig (T2 ,P2 ) S ig (T1,P1)

=
+
R
R
R
R
= 1 (T2 , 2 ) 2 (T2 , 2 ) + lnZ (T2 , 2 )
1 (T1, 1) 2 (T1, 1) + lnZ (T1, 1) + ig
4 (T1,T2 )
Rearrange to obtain
P2 Z (1)
S ( 2 ) S (1)
= 1 ( 2 ) 1 (1) 2 ( 2 ) 2 (1) + ig
T
,T
ln
4 ( 1 2)
P Z ( 2 )
R
1
203
Helmholtz Energy
A ( 2 ) A (1) = U ( 2 ) T2S ( 2 ) U (1) T1S (1)

Dimensionless form
A ( 2 ) A (1) U ( 2 ) U (1) T2S ( 2 ) T1S (1)
=
RT2
RT2
RT2
=
U ( 2 ) U (1) T2S ( 2 ) T2S (1) +T2S (1) T1S (1)
RT2
RT2
U ( 2 ) U (1) S ( 2 ) S (1) T1 S (1)

=
1
RT2
R
T2 R

T1
ig
= 1 ( 2 ) 1 (1) + 3 (T1,T2 ) 1 ( 2 ) 1 (1)
T2

2 ( 2 ) 2 (1)
+ ig
4
P2 Z (1)
T1 S (1)
(T1,T2 ) ln P Z 2 1 T R
1 ( )
2

204
Rearrange to obtain
T1
A ( 2 ) A (1)
S (1)
= 2 ( 2 ) 2 (1) + 1 1 (1)
RT2
R
T2
+ig
3
T1,T2 ig
4
P2 Z (1)
(T1,T2 ) + ln P Z 2
1 ( )
Gibbs Energy
G ( 2 ) G (1) = H ( 2 ) T2S ( 2 ) H (1) T1S (1)
205
Dimensionless form
G ( 2 ) G (1) H ( 2 ) H (1) T2S ( 2 ) T1S (1)
=
RT2
RT2
RT2
H ( 2 ) H (1) T2S ( 2 ) T2S (1) +T2S (1) T1S (1)
=
RT2
RT2
H ( 2 ) H (1) S ( 2 ) S (1) T1 S (1)
=
+ 1
RT2
R
T2 R
T1 S (1)
T1
ig
= 1 ( 2 ) + Z ( 2 ) 1 (1) + Z (1) + 3 (T1,T2 ) 1
T
T
R
2
2
P2 Z (1)
ig
1 ( 2 ) 1 (1) 2 ( 2 ) 2 (1) + 4 (T1,T2 ) ln

P
Z
2
(
)
Rearrange to obtain
G ( 2 ) G (1) T1
S (1)
= 1 1 (1)
+ 2 ( 2 ) 2 (1)
RT2
R
T2
+ig
3
T1,T2 ig
4
P2 Z (1)
T
(T1,T2 ) + ln P Z 2 + Z (2 ) T1 Z (1)
( )
206
Properties relative to a reference state

Because the internal energy and entropy are defined by differential equations, an
arbitrary choice of one boundary conditions is required to prepare a table.
Generally take
S = 0
H = 0
G = 0
at
(T
,P ,
The functions cannot all be chosen to be zero at the reference point because
H = U + (PV ) = U + Z RT U = Z RT
G = A + (PV ) = A + Z RT A = Z RT
where
Z = Z T ,
The table entries for the various properties are calculated according to
= +
207
Begin with internal energy
U = U U
) +U
U
U U U
=
+
RT
RT
RT
Using the previous results
U
T ig
T
= 1 (T , )
1 + 3 T ,T
Z
RT
T
T
H
U
=
+ Z (T , )
RT RT
P Z
S S S S
ig
=
+
= 1 1 2 + 2 + 4 T ,T ln
R
R
R
P Z
A
U
S
=
RT RT R
G
U
S
=
+Z
RT RT R
where:

1 = 1 (T , ) ; Z = Z (T , ) ; 1 = 1 T , ; Z = Z T ,
)
208
Ideal Gas Reference State

If the reference state is an ideal gas at T ,P , then 1 = 0; 2 = 0; Z = 1, and
U
T
ig
= 1 + 3 T ,T
RT
T
H
T
ig
= 1 + Z + 3 T ,T
RT
T
S
P
= 1 2 + ig
T
,T
lnZ
ln
4
R
P
A
TT
P
ig
ig
= 2 + 3 T ,T + 4 T ,T
lnZ ln
RT
T
P
G
T
P
ig
ig
= 2 + 3 T ,T 4 T ,T + Z
lnZ ln
RT
T
P
209
Change of reference state

All tables are based upon reference states, but there are many choices for the
reference state. Some commonly used reference states are
Tref
Pref
0.01 C
PHvap
O
60 F
14.696 psia
60 F
14.73 psia
15 C
1 bar
0 C
1 atm
0 F
1 atm
25 C
1 atm
-40 C
0K
vap
1 bar
Because so many choices are available, a method is required for converting

values based upon one reference state to another reference state.
210
Let:
= value of a property at (T,P) based upon a reference state at (T,P)
= value of the property at the reference state (T,P)
= value of the property at (T,P) based upon a reference state at (T*,P*)
* = value of the property at the new reference state (T*,P*)
In each case
(
(T ,P ) = * + (
(T ,P ) = +
The differences (-) and (-*) are calculated using the procedures
developed previously. Subtracting the first equation from the second yields
) (
(T ,P ) = (T ,P ) + * + *
Table
Value
Property
Change
Property
Change
211
Internal Energy
Begin with the basic relation for each case
U U
U (T ,P ) U
=
+
RT
RT
RT
U (T ,P ) U * U U *
=
+
RT
RT
RT
Subtracting the first expression from the second provides

U U U * U U U * U U
=
+
RT
RT
RT
RT

where
U U
T
= 1 (T , )
1 T , + ig
3 T ,T
RT
T
U U *
T*
= 1 (T , )
1 (T *, * ) + ig
3 (T *,T )
RT
T
212
Subtraction produces
U U * U U
T*
T
,
1 (T *, * )
(
)

1
T
RT RT
+ig
3
T
(T *,T ) 1(T , ) 1 T , + ig3 T ,T
T
T
T*
ig
=
1 T ,
1 (T *, * ) + ig
3 (T *,T ) 3 T ,T
T
T
T
T*
=
1 T ,
1 (T *, * ) + ig
3 T *,T
T
T
For the most common choice of standard state values

H = 0
H* = 0
S = 0
S* = 0
G = 0
G* = 0
U = -ZRT
U* = -Z*RT*
A = -ZRT
U* = -Z*RT*
213
Then
U * U ( Z *RT *) Z RT
T T *
=
=
Z
Z*
RT
RT
T
T
so that
U U U * U U ' U * U U
=
+
RT
RT
RT RT
T T *
T T * * ig
=
Z
Z *+
1
1 + 3 T *,T
T
T
T
T
Note that this also can be written as
U U U * U
=
+
RT
RT
U R T ,P
RT
)U
(T *,P * ) + U
RT
ig
(T *,P * ) U ig (T ,P )
RT
214
Entropy
The table entries are calculated using
S (T ,P ) S S S
=
+
R
R R
=
S (T ,P )
S
+
R
R
S R T ,P
R
S (T ,P ) S * S S *
=
+
R
R R
S * S R (T ,P ) S
=
+
R
R
)+S
(T ,P ) + S
*
ig
ig
(T ,P ) S ig (T ,P )
R
(T ,P ) S ig (T * ,P * )
R
215
Subtracting the first from the second produces
S S S* S S
=
+
R
R
(T
,P
) S (T ,P ) + S (T
R
ig
,P S ig T * ,P *
where
S* S
=0
R
S R T ,P
R
S R T * ,P *
R
) = (T
) (
, 2 T , + lnZ
) = (T , ) (T , ) + lnZ
1
S ig T ,P S ig T * ,P *
R
) = (T ,T ) ln P
P
ig
4
216
Enthalpy
Use the relation between enthalpy and internal energy
H (T ,P ) U (T ,P )
=
+ Z (T ,P )
RT
RT
H (T ,P ) U (T ,P )
=
+ Z (T ,P )
RT
RT
Then
H H U U
=
RT
RT
217
Helmholtz Energy
Begin with the relation between the Helmholtz energy, the internal energy and
the entropy:
A (T ,P ) U (T ,P ) S
=
RT
RT
R
A (T ,P ) U (T ,P ) S
=
RT
RT
R
Then
A A U U S S
=
RT
RT
218
Gibbs Energy
Begin with the relation between the Helmholtz energy, the internal energy and
the entropy:
G (T ,P ) U (T ,P )
S
=
+Z
RT
RT
R
G (T ,P ) U (T ,P )
S
=
+Z
RT
RT
R
Then
G G U U S S
=
RT
RT
R
219
Alternate Form for Change of Reference State

The adjustment from one reference state to another also can be calculated as
follows. The values in each table can be expressed as
= +
(T ,P, )
and
= * +
(T ,P, )
where:
= value relative to reference state

= value relative to reference state *
= value assigned to the property at reference state
* = value assigned to the property at reference state *
Subtracting the first equation from the second produces
=+
)+
220
Geometric Interpretation
T
221
Equilibrium Criteria
Entropy and Energy Functions
Equilibrium Criterion for Entropy
Consider an isolated system. This system will be at constant volume and
constant internal energy. All processes that may occur have
(dS )
total
U total ,V total
Over a long period of time, any process that may occur eventually will occur. The
equilibrium state (the state from which the isolated system will not depart now
matter how long we wait) therefore is characterized by a state for which the
change of entropy in moving to any adjacent state is
(dS )
total
U total ,V total
Any such change would violate the second law of thermodynamics, therefore the
system remains in the equilibrium state.
At fixed internal energy and volume, entropy is at a maximum for the
equilibrium state.
222
Equilibrium Criterion for Internal Energy

The equilibrium state is the one state from which the system does not move for
specified (fixed) values of Stotal and Vtotal.
First Law:
total
/ + dW
/
dUsystem
= dQ
Because the system is at constant volume,

Therefore,
/ =0
dW
total
/
dUsystem
= dQ
The Second Law allows
total
/ TdSsystem
dQ
total
so that, for any event allowed by the Second Law, dUsystem
Then, if a state has
(dU
total
system
S total ,V total
S total ,V total
0 for any change to an adjacent state,
the system cannot leave that state.

At fixed entropy and volume, the internal energy is at a minimum for the
equilibrium state.
223
Equilibrium Criterion for Helmholtz Energy

Here we consider
(dA
total
system
total
T ,Vsystem
Begin with the definition of the Helmholtz energy

total
total
total
Asystem
= Usystem
TSsystem
Then
total
total
total
total
total
/ + dW
/ TdSsystem
dAsystem
= dUsystem
TdSsystem
Ssystem
dT = dQ
total
/ TdSsystem
The Second Law requires that dQ
. Therefore events that may occur
at constant volume must have

total
total
/ TdSsystem
dAsystem
= dQ
0
(dA
total
system
total
T ,Vsystem
0 for any change to an adjacent state,
the isolated system cannot leave that state.

At fixed temperature and volume, the Helmholtz energy is at a minimum for
the equilibrium state.
224
Equilibrium Criterion for Enthalpy

Here we consider
(dH
total
system
total
Ssystem
,P
Begin with the definition of the enthalpy

total
total
total
Hsystem
= Usystem
+ PVsystem
Then, the First Law leads to

total
total
total
total
dHsystem
= dUsystem
+ PdVsystem
+Vsystem
dP
total
/ + dW
/ + PdVsystem
= dQ
Volume changes may be required to maintain the system at constant pressure,

which result in energy being transferred as work in the amount of
total
/ = PdVsystem
dW
225
total
/ TdSsystem
.
Therefore events that may occur at constant pressure and entropy must have
total
/ 0
dHsystem
= dQ
(dH
total
system
total
Ssystem
,P
for any change to an adjacent state, the isolated system cannot leave that state.
At fixed entropy and pressure, the enthalpy is at a minimum for the
equilibrium state.
226
Equilibrium Criterion for Gibbs Energy

Here we consider
(dG
total
system
T ,P
Begin with the definition of the Gibbs energy

total
total
total
total
Gsystem
= Usystem
+ PVsystem
TSsystem
Then, the First Law leads to

total
total
total
total
total
total
dGsystem
= dUsystem
+ PdVsystem
+Vsystem
dP TdSsystem
Ssystem
dT
total
total
/ + dW
/ + PdVsystem
= dQ
TdSsystem
Volume changes may be required to maintain the system at constant pressure,

which result in energy being transferred as work in the amount of
total
/ = PdVsystem
dW
total
/ TdSsystem
.
227
Therefore events that are allowed to occur at constant pressure and temperature
must have
(dG
total
system
T ,P
(dG
total
system
T ,P
for any change to an adjacent state, system cannot leave that state.
At fixed temperature and pressure, the Gibbs energy is at a minimum for
the equilibrium state.
228
Summary of Equilibrium Criteria for Entropy and the Energy Functions
(dS )
total
U total ,V total
(dU
total
system
(dH
total
system
total
system
(dA
(dG
total
system
S total ,V total
total
Ssystem
,P
total
T ,Vsystem
T ,P
0
0
At equilibrium, the entropy is maximized and the energy functions are

minimized.
229
Types of Equilibrium
The variation of entropy near equilibrium points may have several general
characteristics, as shown below.
Stable Equilibrium
Neutral Equilibrium
Metastable
Equilibrium
Unstable Equilibrium
230
First Derivatives (T, P, i)

Consider a closed system with no external fields present, so that only PdV work
is involved in the statement of the First Law. As shown below, the system
contains two chambers, A and B, separated by a frictionless, thermally
conductive, semipermeable piston. The system is isolated from its surroundings.
For this system:
S total = S Atotal + SBtotal

total
U total = U A
+ UBtotal = constant
total
dU A
= dUBtotal
V total =VAtotal +VBtotal = constant
dVAtotal = dVBtotal
nitotal = niA + niB = constant
dniA = dniB
231
The Physics Summary Statement written for each chamber gives

total
total
dU A
= TA dS A
PA dVAtotal + iAdn Ai
i
dUBtotal = TB dSBtotal PB dVBtotal + iB dnBi

i
Solve each equation for the entropy:

total
dS A
1
iA A
total PA
total
=
dU A +
dVA
dn i
TA
TA
i TA
dSBtotal
1
iB B
total PB
total
=
dUB +
dVB
dn i
TB
TB
i TB
232
Then
dS total = dSAtotal + dSBtotal

1
iA A
total PA
total
=
dU A +
dVA
dni
TA
TA
T
i A
1
iB B
total PB
total
+
dUB +
dVB
dni
TB
TB
T
i B
iA iB A
1
1 total PA PB total
=
dU A + T T dVA T T dni
T
T
i
A
A
B
B
B
A
At the equilibrium state
(dS total )U total ,V total = 0
{ }
A
Also, U Atotal . VAtotal and ni are independent variables, therefore the equilibrium
condition is satisfied in general only if all terms in square brackets are zero.
233
Then:
1
1
=0
TA TB
TA = TB
1
1
=0
PA PB
PA = PB
iA = iB
Ai
Bi
=0
The Second Law of Thermodynamics requires that, at equilibrium, the

temperature, pressure and chemical potential of each chemical species be
constant throughout the system.
Note that no external fields are present and there is no mechanism for
doing any kind of work other than PdV work.
234
Second Derivatives (CX, T)

At equilibrium, the internal energy is at a minimum at fixed entropy and volume,
therefore
(dU )
total
S total ,V total
0 and
(d U )
2 total
S total ,V total
The Physics Summary Statement for total internal energy has total entropy and
total volume as the natural independent variables.
U
U
dU =
dS +
dV
S V
V S
2U
2U
2U
2
2
d U = 2 (dS ) + 2
dS
dV
+
dV
(
)
(
)
(
)
2
S V
S V
V S
2
Consider the temperature as a function of entropy and volume

T = T (S,V )
T
T
dT =
dS
+
dV
S V
V S
235
But, the Physics Summary Statement also gives the thermodynamic definition
U
T =
S V
so that
2U
2U
dT = 2 dS +
dV
V
S
S V
Squaring this result produces
(dT )2
2U
= 2
S
2U 2U
2U
2
(dS ) + 2 2
(dS ) (dV ) +
S V S
V S
(dV )2
Rearrange to obtain
(dS )2
2U
= 2
S
2U
2
(dT ) 2 2
S
2U
2U
V S (dS ) (dV ) 2
2U
V S
(dV )2
236
Substitute into the expression for d2U

2
2 2 2
2 2 2
U U
U
U
2
d 2U = 2 2 (dT ) 2
(dV )2
S S
S V S
2U 2U
2U
2U
2 2
(dS ) (dV ) + 2
(dS ) (dV ) + 2 (dV )2
S V S
S V
V
2U
= 2
S
2 2 1 2 2
U
U
2 U
(dV )2
dT
+
( ) 2 2
V S V S
The squared differentials dT and dV always are positive, therefore the

coefficients also must be positive to satisfy the equilibrium condition. Therefore
2U
2
S
2 2 1 2 2
U
U
U
>0
> 0 and 2 2
V S V S
237
The derivatives involved are related to observables

2U
2
S
CV
T
S
=
=
=
S V T V
T
2U
P
=
2
V S
V
2U 2U
P
=
=
S V V S
S V
238
Then
2U 2U
2 2
V S
2U
P
S P P
=
V S
V s T V S V S V
By Math 4
P
P
=
V s T V
S V
By MaxA
P
S P
=
V s V T S V
and, by Math 5
P
=
V T
239
Thermal stability condition
2U
2
S
>0
CV
> 0, CV > 0
T
Mechanical Stability Condition
2 2 1 2 2
U
U U
>0
2
2
V S V S
< 0, T > 0
V T
240
Gibbs Phase Rule

Consider a mixture that contains N different chemical species.
The number of phases that coexist at equilibrium is denoted by .
The variables required to describe this situation are:
P = pressure within phase

T = temperature within phase
= density within phase

x i = mole fraction of species i within phase
The total number of variables involved is
x i
No. per phase
Total
Variable
Total
(N+3)
However, not all of these variables are independent. Phase equilibrium

conditions, reaction equilibrium conditions, equations of state and mass balances
all provide relations between these variables.
241
Equilibrium Conditions:
P = P +1
= 1,2,, 1
T = T +1
= 1,2,, 1
= 1,2,, 1
i = 1,2,,N
N ( 1)
= 1,2,,
= 1,2,,
m = 1,2,,r
i +1
Equations of State
F T , ,P = 0
Mass Balances
N
x i = 1
i =1
Reactions
equilibrium
Km
Total Number of Constraints

(4 + N ) N 2 + r
242
number of degrees of freedom
number of independent variables
number of variables that must be specified to describe a specific

state of the system
number of variables - number of constraints
[(N + 3) ]
[ (N + 4 ) N 2 + r ]
= N +2 r
Gibbs Phase Rule
F = N + 2- -r
where:
N = number of chemical species

= number of coexisting phases
r = number independent chemical reactions
Duhem's Theorem
For any closed system formed initially from given masses of prescribed chemical
species, the equilibrium state is determined completely when any two
independent variables are specified.
243
Assumptions Made in Deriving the Forms shown above for the Gibbs
Phase Rule and Duhem's Theorem
The pressure is equal in every equilibrium phase. For example, this
assumption does not hold for osmotic equilibrium.
Specification of two variables other than composition (e.g., T and P) is
sufficient to specify the state of the system. This assumption does not hold if
several work mechanisms are present simultaneously.
244
Comments On Energy Functions

Internal Energy
The internal energy appears in the formulation of the First Law of
Thermodynamics
Stationary closed system: U = Q +W
245
Enthalpy
Because enthalpy has entropy and pressure as the natural independent
variables, it is useful for processes that occur at constant pressure. (W is work
other than PV work.)
Stationary closed system (constant P): H = Q +W
Enthalpy also is useful for the mass transfer term in the energy balance equation
because it automatically includes the injection work.
Steady-state flow process: H = Q +W
Maximum useful work:
H 2 H1 = Q +W
2
Q T dS
1
Therefore
2
W H2 H1 TdS
246
Helmholtz Energy
For the change of a system from state 1 to state 2
A2 A1 = U 2 U1 (T2S2 T1S1)
First Law for a closed stationary system: U = Q +W

Then
A2 A1 = Q +W T2S2 +T1S1
Consider the special case where
Heat is transferred only from a reservoir at T.
System change is isothermal with: T1 = T2 = T
Then
A2 A1 = Q +W T (S2 S1)
247
Also
2
Q T dS = T (S2 S1) Q T (S2 S1) 0

1
W = A2 A1 +T (S2 S1) Q
W A2 A1
The maximum useful work available from an isothermal process is
Wmax = A 2 A1
248
Gibbs Energy
For the change of a system from state 1 to state 2
G2 G1 = U 2 U1 + P2V2 P1V1 (T2S2 T1S1)
First Law for a closed stationary system: U 2 U1 = Q +W

Then
G2 G1 = Q +W + P2V2 P1V1 (T2S2 T1S1)
For a constant temperature and pressure process

Q T (S2 S1)
T (S2 S1) Q 0
G2 G1 = Q +W + P (V2 V1) T (S2 S1)
W = (G2 G1) P (V2 V1) Q T (S2 S1)

(G2 G1) P (V2 V1)
249
But, W = P (V2 V1) +W ' , where P (V2 V1) is the work done on the system by
the surroundings because of a change of system volume, and W' is all other work
done on the system. Then
W ' P (V2 V1) (G2 G1) P (V2 V1) W ' (G2 G1)
Then, the maximum useful work possible with a constant temperature and
pressure process is
W 'max = G2 G1 = G
250
Summary
The entropy (S) of an isolated system is maximized at equilibrium.
Energies (U,H,A,G) are minimized at equilibrium, subject to the constraint
that the natural independent variables are held constant.
Equilibrium conditions:
P = P
T =T
i = i
Thermal Stability Criterion
CV > 0
Mechanical Stability Criterion
P
T > 0;
<0
V T
251
PROPERTIES OF PURE FLUIDS

In the previous derivations, we see that the only information about individual
materials required to calculate all the UHAGS is:
Equation of state:
f (P,V ,T ) = 0
Ideal gas heat capacity:
CPig = CPig (T )
The equation of state contains the information about interactions between the
molecules.
The ideal gas heat capacity contains information about the energy levels within
the molecules.
Many references provide coefficients for one of the following forms for the ideal
gas heat capacity:
CPig = A + BT + CT 2 + DT 3
CPig = a + bT + cT 2 + dT 2
252
IDEAL GAS HEAT CAPACITIES

The ideal gas heat capacity is determined completely by the characteristics of the
individual molecules.
Each degree of freedom for translation contributes
1R
2
to the ideal gas heat
capacity at constant volume.

Each degree of freedom for rotation contributes
1R
2
to the ideal gas heat
capacity at constant volume.

NOTES
A degree of freedom for translation requires freedom to move along an
independent axis in a Cartesian coordinate system.
A degree of freedom for rotation requires a significant moment of inertia about a
given independent axis of rotation. Multiple atoms must be involved to satisfy
this requirement.
253
Monatomic molecules:
Translation: three degrees of freedom
Rotation:
zero degrees of freedom
CVig = 23 R
CPig = CVig + R = 23 R + R = 52 R
Diatomic molecules:
Translation: three degrees of freedom:
Rotation:
two degrees of freedom:
CVig = 23 R + R = 52 R
CPig = CVig + R = 52 R + R = 72 R
Other energy mechanisms include internal vibrations and rotations in larger
molecules such as hydrocarbons.
254
EQUATIONS OF STATE
General P, V, T Behavior
Ideal Gas
255
Real Fluid
256
Water
Need to develop equations of state that describe all the behavior shown above.
257
Brief History of Equations of State

1662:
Boyle's Law: PV = constant

(fixed temperature and mass)
1787:
Charles' Law: V proportional to T

(fixed temperature and mass)
1801:
Dalton's Law of Partial Pressures: In a mixture, each gas behaves as

though it alone occupied the entire volume of the vessel.
1802:
Gay-Lussac: Verification of Charles's Law.
1822:
Cagniard de la Tour: Discovery of the critical state.
1834:
Clapeyron: Combined Boyle's and Charles's laws into PV = R(t+267).
1863:
Andrews: Extensive investigation of the critical state.
1873:
van der Waals: Dissertation on the continuity of the gas and liquid
states. The equation of state and the concept of corresponding states.
258
1880:
Amagat's Law: The volume of a mixture of gases equals the sum of the
volumes of the component gases, each at the temperature and pressure
of the mixture.
1901:
Onnes: Development of the virial equation of state as an empirical

relation.
1901:
G. N. Lewis: The concept of fugacity
1927:
Ursell: Statistical-mechanical development of the virial equation.
1937:
Mayer: Further theoretical development of the virial equation of state.
1940:
Benedict, Webb and Rubin: introduced BWR equation of state.
1949:
Redlich & Kwong: an improved two parameter equation of state.
1955:
Pitzer: the acentric factor as a corresponding states parameter.
1970's: Soave, Peng & Robinson: cubic equations optimized for phase
equilibrium calculations
1980's: Helmholtz equations of state
259
Important Equations of State

Compression factor
Z
PV
RT
PV = ZRT
where Z is the compression factor, compressibility factor or real gas factor.

Z is dimensionless, and it describes how the fluid differs from an ideal gas.
Virial equations
There are two forms of the virial equation:
Density (Leyden) form:
Z = n n = 1+ B + C 2 + D 3 +
n=0
( 0 = 1)
Pressure (Berlin) form:
Z = nP n = 1+ bP + cP 2 + dP 3 +
n=0
( 0 = 1)
In general, the density form is the more useful of the two. The pressure form is
useful at low pressures (< 5 bar) or at very high reduced temperatures (>2).
260
Cubic Equations of State

Cubic forms of the equation of state are very popular for practical calculations,
because the cubic form is the simplest volume dependence that is capable of
describing vapor-liquid phase equilibrium
van der Waals
The first cubic form for an equation of state was proposed by van der Waals in
his Ph.D. dissertation (1873). The parameter a is nonzero because of attractions
between molecules, and the parameter b is nonzero because each molecule
occupies a finite volume.
Original form:
a
P
+
(V b ) = RT
V2
Alternative forms:
P=
RT
a
2;
V b V
RT 2 a
ab
V 3 b +
V + V
=0
P
P
P
261
Compressibility Factor:
Z vdw =
V
a
1
a
V b RTV 1 b RT
The equation of state also may be written with the compressibility factor as the
variable:
Z 3 (1+ A ) Z 2 + BZ AB = 0
where
A=
B=
bP
RT
aP
(RT )2
262
General Forms for Cubic Equations of State

Martin
P=
RT (T ) (T ) / V
V
(V + ) (V + )
Abbott
P=
(V )
RT
V b (V b ) V 2 + V +
263
Specific Forms for Cubic Equations of State

Redlich-Kwong (1949)
Ref.: O. Redlich & J. N. S. Kwong, Chem. Review, 44, 233 - 244 (1949)
P=
RT
a
V b V (V + b ) T
where
R 2Tc2.5
a = a
Pc
a =
RTc
b = b
Pc
2 1
b = 3 = 0.086640
= 0.427480
3
2 1
1
and
Z RK =
V
a
1
a
V b RT 1.5 (V + b ) 1 b RT 1.5 (1+ b )
264
Martin
P=
RT
a
V b (V + c )2
Soave-Redlich-Kwong (1972)
Ref.: G. Soave, Chem. Eng. Science, 27, 1197-1203 (1972).
P=
RT
a
V b V (V + b )
or
Z SRK =
V
a
1
a
V b RT (V + b ) 1 b RT (1+ b )
where
a = 0.42747R 2Tc2 / Pc
b = 0.08664RTc / Pc
)(
= 1+ 0.480 + 1.574 0.176 2 1 Tr
265
M. S. Graboski and T. E. Daubert, in a series of papers in Ind. & Eng. Chem.,

Proc. Des. & Dev., [17, 443-448 (1978); 17, 448-454 (1978); 18, 300-306
(1979)], presented more precise values for the numerical coefficients, and a
separate expression for hydrogen:
)(
= 1+ 0.48508 + 1.55171 0.15613 2 1 Tr
= 1.202exp ( 0.30288Tr )
for hydrogen
266
Peng-Robinson (1976)
Ref.: D. Y. Peng & D. B. Robinson, Ind. & Eng. Chem., Fundamentals, 15,
59-64 (1976)
P=
a (T )
RT
V b V (V + b ) + b (V b )
or
Z PR =
where
a (T )V
a (T )
V
1
V b RT V (V + b ) + b (V b ) 1 b RT 1+ 2b (b )2
a (Tc ) = 0.45724R 2Tc2 / Pc
b (Tc ) = 0.07780RTc / Pc
a (T ) = a (Tc ) (Tr , )
(Tr , ) = [1+ 0.37464 + 1.54226 0.26992
)(
1 Tr
Harmon & Knapp

P=
RT
a
2
V b V + bcV + b 2 (c 1)
267
Complex Equations of State

Benedict-Webb-Rubin (BWR, 1940)
Ref.: M. Benedict, G. B. Webb & L. C. Rubin, [J. Chem. Phys., 8, 334-345
(1940); 10, 747-758 (1942)], [Chem. Eng. Progress, 47, 419 (1951); 47,
449-454 (1951)]
3
RT
C0 1
1 a c 1+ / V

P=
+ B0RT A0 2 2 + (bRT a ) 3 + 6 +
exp
2
2 3
V
T V
V
V
T V
V
Parameters: A0 , B0 , C0 , a, b, c, ,
268
Benedict-Webb-Rubin-Starling (BWRS, 1970)

Ref.
K. E. Starling, Thermodynamic Properties for Light Petroleum

Systems, Gulf Publishing (1973).
P=
RT
C
D
E 1
1
+ B0RT A0 02 + 03 04 2 + bRT a 3
V
T V
T
T
T V
+ a + 6 +
T V
c 1+ / V 3
T 2V 3
) exp
V2
Parameters: A0 , B0 , C0 , D0 , E 0 , a, b, c, ,
Compare with BWR
P=
RT
C 1
1 a
+ B0RT A0 02 2 + (bRT a ) 3 + 6 +
V
T V
V
V
c 1+ / V 3
T 2V 3
) exp
V2
Parameters: A0 , B0 , C0 , a, b, c, ,
269
NBS/NRC Steam Tables (1984)

Ref.: L. Haar, J. S. Gallagher and G. S. Kell, NBS/NRC Steam Tables,
Hemisphere Publishing, 1984
The working function is an expression for the Helmholtz energy
A ( ,T ) = Abase ( ,T ) + Aresidual ( ,T ) + Aideal gas ( ,T )

where
+ +1
b 1
Abase ( ,T ) = RT ln 1
2

4 1 b
b
4 2 1 4
B
+
RT
+b
+ ln
2
P0
b
T
T
b = b1 ln + bk 0
T0 k =0,1,3,5 T
T
B = Bk 0
T
k =0,1,2,4
270
g T
Aresidual ( ,T ) = i
i =1 k (i ) T0
36
(i )
1 e
k (i )
(i )
+ gi i
(i )
exp i i
i i2
i
i
T Ti
i =
Ti
i =
Aideal
18
C1
i 6
T
,
=
RT
1+
+
C
lnT
+
C
T
(
)

gas
2
R
i R
T
i
=3
R
TR =
T
100 K
271
Tilner-Roth (Difluoromethane, R-32)

Ref.: R. Tilner-Roth and A. Yokozeki, J. Phys. Chem. Ref. Data, 26, 1273-1328
(1997).
Dimensionless Helmholtz free energy
A
Aig Ar
=
+
= ig + r
RT RT RT
where, in terms of the reduced variables, =
T
; = c
T
c
the ideal gas and residual terms are given by

ig
= ln
+ a0ig
+ a1ig
19
i =1
i =9
+ a2ig ln
+ aiig ln 1 exp ( ni )
i =3
r = ai d i t i + ai d i t i exp ei
There are seven terms in the ideal gas formulation and nineteen terms in the
residual formulation.
272
Wagner & Pru (Water, IAPWS-95)

Ref.: W. Wagner and A. Pru, J. Phys. Chem. Ref. Data, 31, 375-535 (2002).
Using forms and the reduced variables defined on the previous page, the ideal
gas and residual terms are given by
ig
= ln
r
+ n1o
+ n2o
+ nio ln 1 exp ( i )
i =4
51
= ni + ni d i t i exp c i
i =1
di ti
+ n3o ln
i =8
54
)
56
2
2
+ ni exp i ( i ) i ( i ) + ni bi
i =55
i =52
di ti
where
2
= + Bi ( 1)
ai
1/ ( 2 i )
2
= (1 ) + Ai ( 1)
2
2
= exp Ci ( 1) Di ( 1)
273
Properties from Helmholtz Functions:

A
P = 2
T
A
S =
T
U = A +TS
H =U +
G = A+
274
Corresponding states
2 parameter
At the critical point
2 P
P
= 0 and 2 = 0
V Tc
V T
c
Therefore, two constraints are imposed on the parameters of the equation of

state. For two parameter equations, the values of the parameters are fixed in
terms of the critical properties. The equation of state then can be written as
functions of reduced variables
f (Pr ,Vr ,Tr ) = 0
where
Pr =
P
;
Pc
Vr =
V
;
Vc
Tr =
T
Tc
The mathematical form is the same for every substance.

275
3 parameter
Ref.: K. S. Pitzer, R. F. Curl, et al., Ind. & Eng. Chem., 50, 265-274 (1958).
The acentric factor was introduced as a third parameter for corresponding
states. The compressibility factor was correlated in the form
Z = Z 0 + Z1
where
log10 Prvap
1
Tr =0.7
This correlation was presented as charts to be used for graphical determination

of the properties.
Because they can be derived directly from Z and its first derivative with respect to
temperature, the energies (U, H, A, G) and the entropy (S) also may be
represented using the same form.
276
Lee-Kesler (1975)
Ref.: B. I. Lee & M. G. Kesler, AIChE J., 21, 510-527 (1975).
Lee & Kesler developed an equation that provides a numerical representation of
the Pitzer-Curl three parameter corresponding states. The formulation utilizes
equations for two fluids: 1.) a composite of simple fluids (argon, krypton, xenon);
and 2.) a large molecule reference fluid (iso-octane).
Z = Z (0) +
(r ) Z (0 ) = Z (0 ) + Z (1)
Z
(r )
(r ) = 0.3978

PrVr
B
C
D
c4

Z=
= 1+
+
+
+
+ 2 exp 2
Tr
Vr Vr2 Vr3 Tr3Vr2
Vr
Vr
B = b1 b2 / Tr b3 / Tr2 b4 / Tr3
C = c1 c 2 / Tr + c 3 / Tr3
D = d1 + d 2 / Tr
277
Lee-Kessler Parameters
Constant
Simple Fluid
Reference Fluid
b1
0.1181193
0.2026579
b2
0.265728
0.331511
b3
0.154790
0.027655
b4
0.030323
0.203488
c1
0.0236744
0.0313385
c2
0.0186984
0.0503618
c3
0.0
0.016901
c4
0.042724
0.041577
d1
0.15548810-4
0.4873610-4
d2
0.62368910-4
0.074033610-4
0.65392
1.226
0.060167
0.03754
278
4 Parameter Corresponding States

For polar fluids, the dipole moment of the molecule () often is used as a fourth
parameter in equations of state.
279
Extended corresponding states

A more sophisticated form of corresponding states, which incorporates
information from statistical mechanics calculations and from extensive
experimental values for a reference fluid, often is referred to as Extended
Corresponding States. In this representation, the compressibility factor and
Helmholtz energy are expressed in terms of reduced variables in the form
V T
Z i (V ,T ) = Z o
,
h
i ,o fi ,o
V T
Air (V ,T ) = fi ,o Aor
,
hi ,o fi ,o
where:
fi ,o =
fi ,o and hi ,o are transformation parameters given by

Toc
Tic
(Tr ,Vr ) and
hi ,o =
Voc
Vic
(Tr ,Vr )
Here the functions (Tr ,Vr ) and (Tr ,Vr ) are shape factors.
The subscripts i and o refer to the fluid of interest and the reference fluid
respectively.
280
Modified BWRS (NIST form)
P = RT + 2 N1T + N 2T 0.5 + N 3 + N 4T 1 + N 5T 2
(
(N T + N T
(N T )
(N T + N T
(N T + N T
(N T + N T
(N T + N T
(N T + N T
(N T + N T
)
)
+ 3 N 6T + N 7 + N 8T 1 + N 9T 2 + 4 N10T + N11 + N12T 1 + 5N13

+ 6
+ 9
+3
+ 5
+ 7
+ 9
14
19
20
22
24
26
+ 11
28
+ 13
30
15
) + (N
7
1
8
1
2
T
+
N
T
+
N
T
16
17
18
2
2
2
2
21
23
25
27
29
31
) exp ( )
) exp ( )
) exp ( )
) exp ( )
) exp ( )
+ N T ) exp ( )
2
32
281
MOLECULAR INTERACTIONS
The Fundamentals
Need forces (potentials) to predict molecular motions.
All forces of relevance here, e.g. interactions among electrons and nuclei, are
electrostatic in nature.
Fundamental to everything is the Schrdinger equation (any physical chemistry
textbook)
H = i
where
(R,r,t ) is the wave function

H = K + U =
i2 + U is the Hamiltonian
2m i
Time-independent form
H = E
282
Born-Oppenheimer approximation: Electronic motion is very fast compared to

nuclear motion so that an average can be taken over the electrons for a given set
of nuclear coordinates.
{Hel +Unuc } (r;R ) = E (R ) (r;R )

By solving this for different R, you obtain the function E(R). This is the energy of
the system as a function of nuclear configuration, also known as the potential
energy surface.
The potential energy surface is everything you need to know to describe the
motion of the nuclei in the system.
In principle, the problem is solved!
In practice:
except in the simplest cases, the Schrdinger equation cannot be solved
exactly
even with accurate approximations, the computational cost of solving it is
high
283
Force-field concept
Define potentials (forces) using empirical formulas.
Atoms (or groups of atoms) are the fundamental units. Their nuclei (centers)
become the focal points for the empirical mathematical expressions.
Intra- and intermolecular contributions exist.
Example: interactions characteristic of butane and methane
284
Intramolecular potentials
Bond-stretching
Example equation
Ubond = k (r r0 )
Angle-bending
Example equation
Uang = k ( 0 )
285
Torsional rotation
Example equation
3
Utor = k i 1 cos ( 0i )
i =1
286
Improper out-of-plane potential
Generally used for a set of three atoms connected to an sp2 hybridized central
atom (amide N, sp2 C).
Example equation
Uoop = k 2
287
Combinations of the above (a.k.a. cross-terms) are also included in modern

force-fields.
Example of a full intra-molecular potential energy expression (MSI CFF family)
2
3
4
Evalence = k 2 (b bo ) + k 3 (b bo ) + k 4 (b bo )
b
2
3
4
+ k 2 ( o ) + k 3 ( o ) + k 4 ( o )
+ k1 (1 cos ) + k 2 (1 2 cos ) + k 4 (1 cos 3 )
2
+ k 2 ( o )
+ k (b bo ) (b ' b 'o ) + k (b bo ) ( o )
b,b '
b,
+ k (b bo ) (1 cos ) + k ( o ) ( ' 'o )

b,
b,
288
Van der Waals and Coulombic potentials

Van der Waals
Consider two atoms of a neutral, monatomic species (e.g. Ar)
+
instantaneous
fluctuation (dipole)
here
induced
dipole
here
Although the time-averaged dipole for each atom is zero, the net potential is not.
The potential energy is attractive, and is given by (Reed and Gubbins,1973)
Uatt =
c6
r6
c8
r8
c10
r 10
The first term is generally dominant.

289
When the atoms get too close, the energy becomes repulsive, due to nonbonding overlap between electron clouds.
Since the physics of repulsion is not as straightforward as that of attraction,
different forms have been used to represent the repulsive component of the vdW
interaction.
Two common, mathematically convenient forms are
U rep = +
c12
r 12
and
U rep = +
c9
r9
A form with more physical basis is
Urep = +Be br
(Reed and Gubbins, 1973)
The exponential repulsion has been shown to better predict VLE properties of
hydrocarbons (Errington and Panagiotopoulos, J. Phys. Chem. B 103, 6314,
1999).
290
Van der Waals interactions always exist between any two chemical groups,
although they are not always the dominant contribution.
VdW interactions are usually handled in a pairwise fashion between sites on
different molecules.
They are usually turned off (or scaled down) for the so-called 1-2, 1-3, and 1-4
intra-molecular interactions.
4
2
1
291
The combination of the r -6 attraction and the r -12 repulsion produces the
Lennard-Jones potential (probably the most-studied model fluid!).
ULJ
12 6
= 4
r
r
Example: comparison of LJ and exponential-six potentials for argon
Energy (J)
15x10
-21
Exponential-6
Lennard-Jones
10
parameters from
Reed and Gubbins,1973
r ()
292
Coulombic
Coulombs Law: the potential energy between two point charges is given by (any
physics text)
UCoul =
1 q1q 2
4 0 r
or
UCoul
e 2 z1z 2
=
4 0 r
with
e = 1.602 x 10-19 C
0 = 8.8542 x 10-12 C2/(N m2)

Obviously, ionic species have net charges that must be accounted for in this way.
Even in neutral molecules, there are generally regions that are electron-rich and
regions that are electron-poor. These regions can be represented by local
charges.
293
Here is an example of the complexities that can arise in a model of the simplest
of molecules, N2 (Allen and Tildesly,1987).
- + - + 3 2 1 2 3
with
z1 = -2.3794
z2 = +5.2366
z3 = -4.0469
This model captures the quadrupole moment for N2.
As in the case of vdW forces, a pairwise additivity assumption is generally made
for Coulombic forces.
For convenience (especially for MD), the locations of the charges are usually
chosen to coincide with the vdW force centers. The N2 model above is one
exception.
294
Example of a full force-field expression

2
3
4
E potential = k 2 (b bo ) + k 3 (b bo ) + k 4 (b bo )
b
2
3
4
+ H 2 ( o ) + H 3 ( o ) + H 4 ( o )
)}
+ V1 1 cos 10 +V2 1 cos 2 20 +V3 1 cos 3 30
+ K 2 2 + Fbb ' (b bo ) (b ' b 'o ) + F ' ( o ) ( ' 'o )
b b'
'
+ Fb (b bo ) ( o )
b
+ (b bo ) (V1 cos +V2 cos 2 +V3 cos 3 )

b
+ (b ' b 'o ) (V1 cos +V2 cos 2 +V3 cos 3 )

b'
+ ( o ) (V1 cos +V2 cos 2 +V3 cos 3 )

Aik Bik
qi qk
+ K ' cos ( o ) ( ' 'o ) +
+ 9 6
r
rik

i >k
i >k rik
ik
295
Three-body potentials
The assumption of pairwise vdW interactions is an approximation.
For example, the interaction between the two blue atoms is certainly different in
the two configurations,
but within the pairwise approximation, it is assumed to be the same.

For an assembly of atoms, we can write formally
UTOT = uij + w ijk +
i <j
i < j <k
i < j <k <l
v ijkl +
This expansion is rigorous when summed to all orders. However, evaluating the
higher-order terms becomes computationally expensive.
Lets examine the importance of 3-body contributions.
296
Three-body vdW potential

A three-body vdW correction term was derived by Axilrod and Teller (Reed and
Gubbins,1973).
2
r12
1
r23
3
r13
U TOT = upairwise +w 123

w 123 = c123
3cos 1 cos 2 cos 3 + 1
(r12r13r23 )3
For acute triangles, w123 is positive.

For most obtuse triangles, w123 is negative.
(The three-body potential tends to stabilize near-linear configurations.)
297
In a typical condensed phase, the overall contribution of the three-body term is

positive and constitutes a correction on the order of 10% to the total energy
(Allen and Tildesley,1987).
This correction is generally deemed not sufficiently important to justify the (very
costly) rigorous sum of the three-body terms. Instead, the correction enters
through an effective two-body potential (Allen and Tildesley,1987). That is, the
parameters for the LJ two-body potential are chosen to reproduce the properties
of condensed phases, not isolated gas-phase pairs.
298
Equations Derived From Interatomic Potentials

Statistical mechanics provides insight into the mathematical forms of equations of
state that describe the macroscopic behavior of fluids based upon the
interactions between molecules (interatomic potential). For example, the second
virial coefficient is related to the interatomic potential as follows
B=
2 Na
u (r ) 2
1 exp
r dr
kT
Because the interatomic potential appears in the exponential argument, only

certain select forms lead to integrals that may be evaluated analytically.
Some commonly used potentials are discussed below.
299
Ideal Gas:
The ideal gas has no intermolecular forces, therefore the potential is
u (r ) = 0
0<r <
300
Point of Repulsion at Center of Molecules

Two such potentials are
u (r ) = ar
and the Born potential

r
u (r ) = a exp

r
301
Hard Spheres
The hard sphere potential is
u (r ) =
0
0 <r <
<r <
302
Square-Well Potential
The square-well potential is
u (r ) =
0
0 <r <
< r < g
g < r <
303
Sutherland Potential
The Sutherland potential is
u (r ) =
r
0 <r <
<r <
304
Yukawa Potential
The Yukawa potential is
u (r ) =
r
exp

0 <r <
<r <
305
Bireciprocal
The general bireciprocal form is

u (r ) = a b
r
r
The Lennard-Jones potential is a special case of the bireciprocal potential

12 6
uLJ (r ) = 4
r
r
306
Kihara Potential
The Kihara potential is
u (r ) = d 12 d 6
4 r d r d
0<r <d
d r <
307
Perturbed Hard Spheres

Ree & Hoover (1967)
PR =
RT
1+ 4y + 10y 2 + 18.36y 3 + 28.3y 4 +
V
where PR is the pressure due to repulsive interactions and y =
b
4V
Carnahan-Starling (1972)
Carnahan and Starling combined the repulsive form suggested by hard spheres
with simple attractive contributions to obtain useful equations of state.
CS w/ van der Waals attractive term:
RT
P=
V
RT
CS w/ Redlich-Kwong attractive term: P =
V
1+ y + y 2 y 3 a
2
3
(1 y )
V
1+ y + y 2 y 3
a
(1 y )3 T (V + b )V
Many other forms of perturbed hard sphere equations have been proposed.
308
Boublik-Alder-Chen-Kreglewski (BACK)
Z = Z hb + Z a
where Z hb is the contribution to the compressibility factor arising from repulsive
interactions:
2
2
2
3
3
+
1
+
3
+
1
(
)
Z hb = 1+
(1 )3
and Z a is the contribution to the compressibility factor arising from attractive

interactions:
1
Z a = mDnm
T *
nm
( * )m
The parameters and variables are
= shape factor (due to Boublik)

= 0.74048 *
* =
V
V
Dnm = universal numerical constants (24 of these are used in the BACK
formulation)
309
PC-SAFT Equation of State

Perturbed Chain Statistical Associating Fluid Theory
This approach considers separately the contributions to Z that come from hard
spheres, assembly into chains, dispersion (van der Waals) forces and specific
interactions (e.g., hydrogen bonding):
r
r
r
r
Ar = Ahs
+Adisp
+Achain
+Aassoc
(The colors in this equation correspond to the colors of the arrows in the figure.)
310
Potential for Hard Sphere and Dispersion Contribution
3
u (r ) =

0
r < ( s1); s1 = 0.12
( s1) r <
< r <
r
Fluid specific parameters for nonassociating fluids:
= segment diameter (length dimensions)

= depth of potential well (energy dimensions)
m = number of segments per chain
Fluid specific parameters for association contribution
Ai Bk = volume of association
Ai Bk = energy of association
311
PURE FLUID PHASE EQUILIBRIUM

The stability criteria resulting from the Second Law are that the entropy is
maximized and U, H, A and G are minimized at equilibrium. When the energy
functions are minimized, the natural independent variables are held constant.
For calculations of phase equilibrium, we consider one mole of fluid subject to
constraints of constant temperature and pressure, therefore the equilibrium
configuration of the system is that configuration that has the lowest Gibbs energy.
The appropriate form of the Physics Summary Statement is
dG = SdT +VdP
For changes that occur at constant temperature (along an isotherm)

dG =VdP
(constant temperature)
Calculate the Gibbs energy along an isotherm relative to the Gibbs energy at a
reference pressure, P, at the same temperature.
G G =
V dP
(constant temperature)
P
312
Equation of state behavior
The behavior of V as a dependent variable is not a proper integrable

mathematical function because multiple values of V exist for certain single values
of P. Pressure cannot be used as the variable of integration, so the expression
for the Gibbs energy must be transformed to obtained a proper integral.
313
Note:
d (PV ) = PdV +VdP VdP = d (PV ) PdV
Then:
dG =VdP = d (PV ) PdV

and
G G =
PV
V dP =
d (PV )
P V
= PV P V
P dV
P dV
314
Gibbs Energy of van der Waals Fluid

Reduced form of van der Waals equation
Pr =
8Tr
3
2
3Vr 1 Vr
In terms of reduced variables, the Gibbs energy expression given above is

PrVr
G G = PcVc
Pr Vr
d (PrVr ) PcVc
Vr
Vr
Pr dVr
For the van der Waals fluid

PcVc = Z cvdw RTc =
3
RTc
8
Substitution into the Gibbs energy produces
G G 3
=
RTc
8
PrVr
Pr Vr
d (PrVr )
Vr
Vr
Pr dVr
315
The first integral is

PrVr
Pr Vr
d (PrVr ) = PrVr P V
The second integral is

Vr
Vr
Vr
Pr dVr
8Tr
Vr
Vr
3V 1
dV
1
dVr
8
1
r
r
+ 3
3 2 = Tr ln
3Vr 1
3
V
3Vr 1
Vr Vr
r
Vr
The reduced Gibbs energy then is
3Vr 1 9 1
G G 3
1

= Pr Vr Pr Vr Tr ln
RTc
8
3Vr 1 8 Vr Vr
316
The Gibbs energy as a function of volume is
V
The Gibbs energy as a function of pressure is
P
317
For fluid densities (specific volumes) between the volume of the vapor and the
liquid at the intersection on the G-P diagram, the fluid has a lower total Gibbs
energy when divided into two phases of different densities than it has as a single
phase at the same pressure.
The equilibrium criteria state that the equilibrium condition has the lowest Gibbs
energy at constant T and P, so the equilibrium condition has two phases for a
range of densities at one pressure (the intersection point on the plot shown
above.
The molar Gibbs energy (I for a pure fluid) of the liquid and vapor phases must
be equal at the equilibrium condition.
318
Vapor pressure from EOS

Compare the molar Gibbs energy at two points, 1, and 2, along the PV isotherm
G ( 2 ) G = P2V2 P V
G (1) G = P1V1 P V
V2
P dV
V1
P dV
Subtraction produces
G ( 2 ) G (1) = P2V2 P1V1
V2
P dV
V1
In the case of two coexisting phases, the Gibbs energies and pressures are
equal, therefore
G ( 2 ) G (1)
= P eq V2sat
V1sat
V2
P dV = 0
V1
319
For vapor-liquid equilibrium
Gv GL = P sat V Vsat VLsat
VVsat
P dV = 0
VLsat
Equilibrium States
Gv GL > 0
equilibrium state is compressed liquid
Gv GL < 0
equilibrium state is superheated vapor
Gv GL = 0
equilibrium state is two phase (vapor+liquid)
320
Vapor Pressure Calculation Procedure

1.
Estimate the vapor pressure, Pest
2.
Solve the equation of state for VL, VV.
3.
Calculate
4.
> 0 ), using
Adjust Pest
(subject to the constraint that Pest
< 0, Pest
< P
VV
GV GL = P (VV VL ) P dV = 0, Pest
= P
VL
>
0,
P
>
P
est
Pest
(new ) = Pest
(old )
5.
GV GL
VV VL
Repeat steps 2 through 4 until convergence is achieved.
Note: The formula for the new estimate used in step 4 is based on the
observation that
d (GV GL )
=VV VL
dPest
321
Clapeyron equation
One of the equilibrium criteria for two phases coexisting in equilibrium is
G = G
where the superscripts and denote the properties of the two coexisting
phases.
For a path along the saturation curve
dG = dG
Apply the Physics Summary statement (dG=-SdT+VdP) to each phase
S dT +V dP = S dT +V dP
(V V )dP = (S S )dT
This leads to the Clapeyron Equation
dP S S
H H
=
=
dT
V V
T V V
This is a general result that applies to transitions in pure materials (e.g. vapor
pressures, sublimation pressures, melting pressures, solid-solid, etc.)
322
Implications for Vapor Pressure Equations

Case I:
Assumptions:
LV H is independent of temperature
vapor is an ideal gas
vapor volume is much larger than liquid volume
The Clapeyron equation yields

lnP =
LV H
B
+ constant = A
RT
T
Case II:
Assumptions:
LV H = LV H 0 + ( LV H1)T
vapor is an ideal gas
vapor volume is much larger than liquid volume
The Clapeyron equation yields

lnP =
LV H 0 LV H1
B
+
lnT + constant = A + C lnT
RT
RT
T
323
Temperature dependence of H
Relate the heat of a phase transformation to other measurable quantities. For
enthalpy considered as a function of temperature and pressure. math relation 1
leads to
( H )
( H )
d ( H ) =
dT
+
dP
T P
P T
The coefficients can be related to observables
H H
( H )
=
T
T P
H H
( H )
=
P
P T
= CP CP = CP
V
V
V T
= V T
T P
T P
V
= V T
T P
324
Then
V
d ( H ) = CP dT + V T dP
T P
and
d ( H )
V dP
= CP + V T
T P dT
dT
V H
= CP + V T
T P T V
= CP +
H H
T
T

T P
or
d ( H )
H
== CP +
dT
T
lnV

1
lnT
325
Trouton's Rule
This rule is based upon the observation that the entropy of boiling is
approximately the same for all fluids:
Sboiling 88 J/K mol

Note also that
Hboiling = Tbp Sboiling

This observation may be understood by noting that the ratio of the vapor and
liquid molar volumes is of the same order of magnitude for all fluids.
A similar, but less general, relation exists for entropies of melting:
Smelting 8 16 J/K mol

Note that some substances have entropies of melting as large as 40 J/Kmol
326
Types of phase transitions

For various real substances, the Gibbs surfaces in P,T space exhibit a variety of
behaviors.
General behavior:
The equilibrium phase has the lowest Gibbs energy at fixed T,P. At the
intersections of the surfaces, both phases can exist in equilibrium. Metastable
states also may exist in the vicinity of the intersection.
327
Recall that
G
= S
T P
=V
P T
2 G
CP
S
=
2
T P
T
T P
2 G
V
=
= V T
2
P
P T
T
328
Then
329
In this case, the first derivatives are discontinuous at the transition. This is not
always the case.
Ehrenfest proposed a classification scheme that refers to tranisions of order n,
where the nth derivatives of G with respect to T and P are the lowest derivatives
that are discontinuous at the phase transition.
The actual situation is more complex. The types of behavior actually observed
for CP are shown below.
First Order:
CP
330
Second order:
Third Order:
CP
3a
3b
3c
331
Examples:
First Order:
Solid/Liquid
Vapor/Liquid
Solid/Vapor
Solid/Solid (Crystal Structure Changes)
Second Order:
Superconducting Transition
Lamda:
Helium /Helium (Superfluid transition in liquid 4He)
Order/disorder in -brass
Order/disorder in quartz
Third Order:
Curie points of ferromagnets
332
BEHAVIOR NEAR CRITICAL POINTS

The term critical region refers to the region in state variable space where a fluid
goes from conditions where multiple phases exist to conditions where only a
single phase exists. At the transition point, all properties of the individual phases
become identical.
Approximate range:
0.99 < Tr < 1.01

0.60 < r < 1.40
Types of critical points involved with fluid phase behavior:

Vapor - Liquid
Liquid - Liquid
Vapor - Liquid - Liquid (Tricritical point)
The critical region was first observed by Andrews (1869) for carbon dioxide.
Note the difference between the critical point and an azeotrope:
Phases become identical (all properties are the same) at a critical point.
Phases have the same composition but different densities at an azeotrope.
333
P-V-T near a vapor - liquid critical point:

2P
2 < 0
V T
2P
2 = 0
V T
P
<0
V T
2P
2 < 0
V T
P
=0
V T
(T > Tc)
(T < Tc )
V
Equation of state isotherms are shown. Mathematically, to pass smoothly from
behavior A (two phases can be present for some conditions) to behavior B (one
phase only for all pressures) requires that at some temperature between TA and
TB:
2 P
P
and 2 = 0
= 0
V T
V T
Note also that:
KT =
1 V
V P T
at the critical point
334
Physical Observations:
Behavior of the meniscus (interface between phases) for a pure fluid:
> c
Increasing Temperature
< c
= c
335
Critical Opalescence
Density fluctuations (large) in the fluid phases lead to significant light scattering.
The scattering causes the fluid to turn black, to turn milky, or to glow depending
upon the fluid and the pattern of illumination.
Universality
Long range order and correlation occurs in the critical region. This order extends
over many molecules, hence the specific nature of the intermolecular force
becomes unimportant. Therefore the general behavior of all fluids will be the
same.
Other transitions, such as the Curie point for ferromagnetism also involve the
same types of long range order, therefore the critical behavior of magnets is
similar to that of fluids.
Theoretical calculations are the most tractable for the Ising model for
ferromagnets; there is an analytic solution for the 2 dimensional case, but a
numerical solution is required for 3 dimensions.
The renormalized group theory treatment introduced by Kenneth Wilson, et al., is
the most current theoretical model.
336
General Behavior
Supercritical Fluid
CP
Vapor
Liquid
Liquid + Vapor
Two Phase Region
Heat Capacity at Constant Volume:

Cv 2 ~ T Tc
Cv ~ T Tc
CP
Critical
Isochore
337
Densities
P Pc ~ V Vc
T ~ T Tc
CP
T =
= c
Tc
= 21 (v + L )
~ Tc T
Law of Rectilinear Diameters

The mean of the saturated vapor and liquid densities varies linearly with the
temperature excursion from the critical temperature, i. e.,
1
2
( v + L ) = c + k1(T Tc )
This often provides the best way to determine experimental values for the critical
density. The temperature at which the meniscus disappears is measured by
visual observation, and measured vapor pressures are extrapolated to the critical
temperature to get the critical pressure.
338
Critical Exponents
CV ~ T Tc
~ T Tc
T ~ T Tc
P Pc ~ V Vc
d 2P
dT 2
~ T Tc
~ Tc T
339
Critical Exponent Values

Exponent Property
Classical 3-D Ising Renormalized Experimental

Value
Model Group Theory
Values
Cv
0.125
0.109
~0.12
1/2
0.312
0.325
0.32 - 0.38
1.250
1.241
~1.25
3/2
5.05
4.82
4.5 - 5.0
0.125
0.109
0.21
d 2P
dT
~1.25
340
Experimental Problems Near Critical Point

Long time required to achieve equilibrium
Impurity effects: small amounts of impurities drastically alter the physical
properties, because the critical temperature and pressure change with
composition.
Gravity Effects: the very large values of T in the critical region mean that the
variation of pressure with height due to hydrostatic head causes very large
density gradients within the system.
Moldover, Sengers, Gammon and Hocken (1979) determined that gravity effects
produced errors greater than 1 % in a cell of 1 cm height within the following
ranges of temperature and density:
PVT experiment: density is the measured variable
At c:
T -Tc
T =
= 1-Tr < 6 10-4
Tc
At Tc :
-c
=
= 1 r < 0.08
c
341
Calorimetry: heat capacity is the measured variable
T -Tc
= 1-Tr < 3 10-4
Tc
At c :
T =
At Tc :
-c
=
= 1 r < 0.1
c
Water:
PVT: |T-Tc| < 0.4 K
CV: |T-Tc| < 0.2 K
Methane:
PVT: |T-Tc| < 0.1 K
CV: |T-Tc| < 0.05 K
342
PROPERTIES OF MIXTURES
GENERAL FORMAL DESCRIPTIONS
Usually use T,P as the independent variables for mixture calculations. Then
M total = M total T ,P,n1,n2, ,nm
where:
M total = total property of the mixture

n i = number of moles of specie i present
m = number of chemical species present in the mixture
Also:
M total = nM
where:
M = molar property of a mixture

m
n = n i = total number of moles of mixture

i =1
343
h
Mathematical Note: A function is homogeneous of order h if f ( x ) = f ( x )
At constant T,P,
M total is homogeneous of order 1 with respect to the variables {n i } .

Implications of homogeneity
M total = M total (n1,n2 ,,nm )
M total = M total ( n1, n2 ,, nm )

Note: T,P are not considered to be independent variables here because of the
restriction to constant T,P
Rewrite as:
nM = nM ( n1, n2 ,, nm )
Differentiate with respect to :

m (nM ) ( n )
m
d ( nM )
i
= nM =
= ni
d
i =1 (
i )
i =1
(nM )
n
(
)
i
344
The previous result is true for any value of the parameter . Choose = 1 to
obtain
(nM )
(nM )
=
n
(
)
i
i T ,P,n k i
T ,P,n k i
Result:
m
(nM )
nM = n i
= ni M i
n
i =1
i T ,P,n k i i =1
m
Notation:
Mi =
molar property of pure fluid i
Mi =
partial molar property of specie i in the mixture
M=
bulk molar property of the mixture
345
Observations:
lim
xi 1
( x k i
0)
lim
xi 0
( x k i
where:
Note:
Mi =Mi
Mi = M
i
1)
M
i is the partial molar volume at infinite dilution
The properties of the mixture are known if the partial molar properties of
all species are known.
346
Gibbs-Duhem equation
Any mixture property depends upon the temperature, pressure, and the number
of moles of each chemical species present
M total = M total (T ,P,n1,n2 ,,nm )

Mathematics relation 1 gives
m (nM )
(nM )
(nM )
d (nM ) =
dT +
dP +
dn i
i =1 n i T ,P,n
T P,n i
P T ,n i
k i
m
(nM )
(nM )
=
dT +
dP + M i dn i
T
P
i =1
P,n i
T ,n i
Also, nM = n i M i
i =1
i =1
i =1
requires that d (nM ) = n i dM i + M i dn i
347
Equate the two expressions for d(nM) to obtain

m
m
m
(nM )
(nM )
dT +
dP + M i dn i = n i dM i + M i dn i
T
P
i =1
i =1
i =1
P,n i
T ,n i
Eliminating common terms and rearranging produces

m
(nM )
(nM )
dT +
dP n i dM i = 0
T
P
i =1
P,n i
T ,n i
For those partial derivatives where the number of moles of every species is held
constant, n also is constant, so the previous result may be written as
m
M
M
n
dT + n
dP n i dM i = 0
T
P
P,n i
T ,n i
i =1
Divide through by n to put this equation on a molar basis:
348
m
M
M
dT +
dP x i dM i = 0
T P,n i
P T ,n i
i =1
m
x i dM i = 0
i =1
(constant T ,P )
This result is known as the Gibbs-Duhem Equation.

The Gibbs-Duhem equation provides a consistency test for thermodynamic
properties of mixtures. It often is used in phase equilibrium studies to calculate
the composition of a phase that is not amenable to direct measurement of
composition.
349
Calculation of partial molar properties

The definition of a partial molar property is
(nM )
Mi =
n i T ,P,n
k i
However, in most cases the information about the mixture properties is given as
a function of composition (mole fraction)
M = M ( x1,x 2 ,,x m )
An alternative method for calculating partial molar properties using partial
derivatives with respect to mole fraction can be derived as follows, beginning with
the definition of the partial molar property.
(nM )
Mi =
n i T ,P,n
k i
M
= M +n
n i T ,P,n
k i
350
This derivative is related to partial derivatives with respect to mole fraction by
M
n
i T ,P,n
M
=
j =1 x j
T ,P,x
m
k i
kj
x j
n
i T ,P,n
k i
The mole fraction is related to the amount of each species by
xj =
nk
m
nk
n
1 nk
n n i n
nj
j =1
Then
x k
n
i n
nk n
n 2 n i n
Because the {nI} are independent variables

nk
n
i n
0
= ik =
1
i k
i =k
351
The second partial derivative on the right is

n
n
i n
m nk
m
=
nk =
n i k =1 k =1 n i n
= ij = 1
i
j =1
Then
x k
n
i n
=
i
1 nk nk n ik nk
n ni n 2 ni
n n2
so that
M
n
i T ,P,n
k i
M
=
k =1 x k T ,P,x
m
M
=
k =1 x k T ,P,x
j k
1 M
=
n x i T ,P,x
j k
x k
n
i T ,P,n
j i
ik nk
n n 2
k =1 x k T ,P,x
m
j i
nk
j k
n2
352
and
M
n
n i T ,P,x
j i
M
=
x i T ,P,x
M
xk
x k T ,P,x
k =1
m
j i
j k
Substitution into the original equation produces
(nM )
Mi =
n
i
T ,P,nk i
M
=M +
x
i T ,P,x k i
M
xk
x k T ,P,x
k =1
m
Other methods for calculating M i exist, but in most cases they involve algebraic
elimination of xi and summations from which one or more terms are excluded.
The result given above is much more convenient for computer calculations for
mixtures with many species present. The notation here also is simpler and less
likely to cause confusion.
353
Property change on mixing

General Definition
The concept of a property change on mixing is compares the properties of a
mixture to the molar average of the properties of the pure components at the
same temperature and pressure.
m
mM (T ,P,{x i }) M (T ,P,{x i }) x i M i (T ,P )
i =1
i =1
i =1
i =1
= x i M i (T ,P,{x i }) x i M i (T ,P ) = x i M i M i
where:
m M (T ,P,{x i }) = property change on mixing
M (T ,P,{x i }) = molar property of the mixture at T, P and {xi}

M i (T ,P ) = molar property of pure substance i at T, P
M i (T ,P,{x i }) = partial molar property of substance i in the mixture at T, P

and {xi}
The property changes of interest include mV, mU, mH, mA, mG and mS
354
Property Changes on Mixing for Ideal Gases

The property changes on mixing for the ideal gases will provide reference points
for more general discussions of mixture properties.
Begin with three separate ideal gases, each at T, P. Then mix, with no energy
transferred as heat during the mixing process. The process is shown
schematically below.
Before mixing, at T, P:
PVAtotal
nA =
RT
PVBtotal
nB =
RT
PVCtotal
nC =
RT
355
After mixing, at T, P:
n = nA + nB + nC
total
Vmixture
nRT
RT RT PVAtotal PVBtotal PVCtotal
=
= (nA + nB + nC )
=
+
+
P
P
P RT
RT
RT
=VAtotal +VBtotal +VCtotal
In terms of molar volumes

total
Vmixture
= nV = nAVA + nBVB + nCVC
Divide through by the number of moles

V =
nA
n
n
VA + B VB + C VC = x AVA + x BVB + x CVC = x iVi
n
n
n
Then
ig
ig
ig
V
=V
x
V
m
i i =0
Therefore the volume change on mixing for ideal gases is zero.

356
Note also that no PdV work is done during the mixing process because the
volume remains constant.
The change in total internal energy resulting from the mixing process is
calculated from the First Law
total
ig
= Q +W = 0
mU
Therefore
ig
mU = 0
The enthalpy of mixing for ideal gases follows directly from the internal energy
and volume.
ig
ig
ig
mH = mU + PmV = 0
357
Because the particles in an ideal gas do not interact with each other, we may
calculate the entropy change for each component as though it expanded from its
original total volume to the total volume of the mixture.
Note:
total
Vmixture
Vitotal
nRT
n
1
P
=
= =
ni RT ni x i
Then
total
ig
mSi
and
total
Vmixture
1
= n i R ln total = n i R ln = n i R lnx i
xi
Vi
nig
mS = R (nA lnx A + nB lnx B + nC lnx C )
Divide through by n to obtain
ig
mS = R ( x A lnx A x B lnx B x C lnx C ) = R x i lnx i
so that the dimensionless form is
m
ig
mS
= x i lnx i
R
i =1
358
Use the definitions and the previous results to calculate the values for the
Helmholtz and Gibbs energies:
) (
ig
U T ig
m
m
mS
ig
A
m
=
= x i lnx i
RT
RT
i =1
ig
mG
RT
H ) T ( S )
(
=
= x lnx
ig
m
ig
m
RT
i =1
359
Ideal solutions
We use the results derived for mixing of ideal gases to define a concept of ideal
solutions, which are mixtures for which the properties changes of mixing are
identical to those for mixing of ideal gases, even though the pure substances are
not ideal gases.
is
mU
=0
RT
m
is
mS
= x i lnx i
R
i =1
P is
mV
=0
RT
m
is
mA
= x i lnx i
RT
i =1
is
mH
=0
RT
m
is
mG
= x i lnx i
RT
i =1
360
Alternative Definition of Ideal Solution

The Gibbs energy of an ideal gas mixture is
G
ig
ig
mG
+ x i Giig
i =1
The Gibbs energy change on mixing for an ideal gas is
is
mG = RT x i lnx i
Combining the previous expressions gives
G ig = x i Giig + RT x i lnx i = x i Giig + RT lnx i
and
nG ig = ni Giig + RT lnx i = nk Gkig + nk RT lnx k
so that
Giig
nG ig
=
ni
T ,P,nk i
= Giig
+ RT lnx i + RT nk
k =1
lnx k )
(
ni
361
The partial derivative in the last term is
(lnx k ) 1 x k
1 nk
1
=
=
=

ni
x k ni
x k ni n x k
1
ik nk
=
n n 2 nx ( ik x k )
k
The summation in the last term is

m
m
(lnx k ) m nk
=
nk
( ik x k ) = ik x k
n
nx
k =1
k =1
k =1
k =1
i
k
m
=
1
ik
m
(lnx k )
k =1
n
=0
k
m
n
k =1
i
x k = 1
k =1
m
so that
Giig = Giig + RT lnx i

Use this form as the basis for an alternative definition of the ideal solution
G isi = G i + RT lnx i
362
Activity Coefficient
Preserve the same general form for real mixtures by including the activity
coefficient in the partial molar volume.
G i = G i + RT ln i x i
where I is the activity coefficient.
Activity
The partial molar Gibbs energy also can be written in the form
G i = G i + RT ln i
where I is the activity.
363
General Definitions
In the general case, the definition of the property change on mixing must
accommodate reference states that differ from the final state of the mixture:
m
M
=M
x i M i
i =1
= x i M i M i
i =1
Usually the reference state (denoted by ) is chosen to be of the same T, P and

in the same state as the mixture, but this is not always possible.
A more general definition of the ideal solution then follows as
G is
i = G i + RT lnx i
and
G i = G i + RT ln ix i = G i + RT ln i
364
Excess Properties
Define excess properties based upon the difference between the property
changes on mixing for the real solution and for the ideal solution.
M E (T ,P,{x i }) = mM (T ,P,{x i }) ismM (T ,P,{x i })

Note that both the excess properties and the property changes on mixing are
functions of temperature, pressure and composition.
The partial molar excess properties are related to the real mixture and ideal
solution values by
M Ei = M i M isi
365
For the Gibbs energy
G i = G i + RT ln ix i
G isi = G i + RT lnx i
( )
GEi
= G i G isi = RT ln i
Therefore
GEi
= ln i
RT
366
Note that all information about the real mixture is available if (GE/RT) is known,
because all other excess properties and partial molar excess properties can be
obtained from the excess Gibbs function using the following relations
G
S =
T P
E
G
=
P T
S Ei
GEi
=
T P
VE
i
GEi
=
P T
H E = GE +TS E
H Ei = GEi +TS Ei
AE = GE PV E
AEi = GEi PV iE
U E = GE PV E +TS E
U Ei = GEi PV iE +TS Ei
367
In terms of the activity coefficients

GE m
= x i ln i
RT i =1
m
PV E
ln i
= xi
RT
i =1 lnP T
m
HE
ln i
= xi
RT
i =1 lnT P
m
SE
= xi
R
i =1
AE m
= xi
RT i =1
ln i

ln i +
lnT
ln i
ln
+

i
lnT
m
UE
= xi
RT
i =1
ln i
ln i
+
lnT
lnP
P
T
368
Relation of Excess Properties to Residual Functions and Equation of State

For the case where all reference states are taken as the same phase at the same
temperature and pressure, the Gibbs energy change on mixing is
mG G x i Gi x i G i Gi
=
=
RT
RT
RT
{ (
) (
) (
{ (
)}
1
ig
ig
ig
x i G i G ig
+
G
G
+
G
Gi
i
i
i
i
RT
1
x i G i G ig
+ RT lnx i + G ig
Gi
i
i
RT
GRi GR
is
i
mG
= x i
+
x
lnx
=
+ x i
i
i
RT
RT
RT
)}
E
GRi GR
is
i
mG G
=
RT
RT
RT
RT
Therefore:
GE
= x i
RT
GRi GiR
RT
RT
369
By the definition of a residual function:

Pure species:
GiR
RT
Gi Giig
RT
VR
i
RT
dP =
dP
( Z i 1) P
Mixture:
R
G
G G
=
RT
RT
ig
VR
RT
dP =
( Z 1)
dP
P
Partial Molar Gibbs function:
GiR
RT
Gi Giig
RT
VR
i
RT
dP = Z i 1
dP
P
370
Then
P
P
P R
R
R
R
m
m
V R V R
G
Gi
Gi
V
V
i
i
i
= x i
dP
dP = x i i
dP
= x i
RT
RT
RT
RT
RT
RT
i =1
i =1
0
0
0
V V
i
x i i
i =1 RT
dP
Also
G Ei
RT
V V
i
i
RT
dP = ln i
371
Fugacity
For an ideal gas at constant temperature
dG ig = V ig dP = RT
dP
= RT (d lnP )
P
Integration from P to P yields
( ) = ln P
G ig (P ) G ig P
RT
Define fugacity to obtain the same form for the real fluid as for the ideal gas
dG = RTd (lnf )
Then
G (P ) G P
RT
( ) = ln f

f
Using these forms
f
dGR = dG dG ig = RTd (lnf ) RTd (lnP ) = RTd ln
P
372
and
( )
R
f
GR G P
f
=
ln + ln
P
RT RT
P
In the limit as the pressure goes to zero

R
lim G
P0 RT
lim
P0
f
=0
P
ln
Define fugacity coefficient as

=
f
P
where
lim
P0
=1
373
Then, use the following forms.

Pure Substance:
dGi = RTd lnfi
lim fi
P0
=1
P
Mixture:
dG = RTd lnf
lim
P0
f
=1
P
Component in the mixture:
dGi = RTd lnfi
lim
P0
fi
=1
xiP
374
Relations between activities, fugacities, activity coefficients and fugacity

coefficients
fi
f i
x i i
fi
i
=
=
x i f i i
fiis = x i f i
375
1
x
376
Relationships between activity coefficients based upon different reference

states.
Consider activity cases based upon two different reference states, one denoted
by and the other by . The Gibbs energy change on mixing as described by
each choice of reference states is
m
G x i Gi Gi
=
RT
RT
m
G x i Gi Gi
=
RT
RT
So
x i Gi Gi
=
RT
RT
RT
m
G
m
G
Note:
E ,
m
G is,
GE , m
m G G
=
+
=
+ x i lnx i
RT
RT
RT
RT i =1
E ,
m
G is,
GE , m
m G G
=
+
=
+ x i lnx i
RT
RT
RT
RT
i =1
377
Finally
GE . GE , m
G m
G m
= xi
RT
RT
RT
RT
i =1
Gi Gi
RT
also
m
m
i
G E . G E , m
= x i ln i x i ln i = x i ln
RT
RT
i
i =1
i =1
i =1
Then
ln
Gi Gi
=
RT
i = i xi
Gi
= i exp
Gi
= i exp
Gi
RT
Gi
RT
378
These results are consistent with the definitions
i
i
fi
x i f i
fi
f i
fi
x i f i
fi
f i
where: fi = fugacity of component i in the mixture
f i = fugacity of pure component i at the reference state denoted by .

f i = fugacity of pure component i at the reference state denoted by .
Note that analogous developments could be based upon molal concentrations
(often used for electrochemical applications) or mass fractions (often used for
polymer solutions or mixtures of undetermined molecular weight) instead of mole
fraction.
379
PHASE EQUILIBRIUM FOR MIXTURES

General Phase Equilibrium
Equilibrium condition is that the total Gibbs enery of the system is at a minimum
for a given T, P. Consider G(x) at fixed T, P.
Example:
m
is
mG
= x i lnx i
RT
i =1
is
G
For ideal solutions,such mixtures, m is negative for all compositions.
RT
The behavior as a function of composition for a binary mixture is shown on the

following page.
380
Ideal Solution:
1
x
The chord connecting the values for any two compositions gives the total Gibbs
energy for a two-phase mixture, where the two phases have the compositions of
the end points of the chord.
381
Binary Mixtures:
Totally miscible:
1
x
At all overall compositions, mG < 0, and G(x) has a lower value than any linear
combination of other compositions, therefore such a mixture always exists as a
single phase at this T, P.
382
Totally immiscible:
1
x
At all overall compositions, mG > 0, therefore

m
x i Gi < G ( x )
i =1
The system will exist as two separate pure phases.

383
Partially immiscible (or partially miscible):
1
x
For xA< x < xB, the tangent AB has a lower Gibbs energy than G(x). This system
will exist as a single phase for x < xA and x > xB, but as a two-phase mixture with
phase compositions xA and xB for xA< x < xB.
mG < 0
Mixtures are completely miscible if: 2 mG

for all 0 x 1
> 0
2
x
384
Phase Equilibrium Calculation

Phase equilibrium calculations may be done by direct minimization of the Gibbs
energy for a given T, P, but a more common method is to use the equilibrium
relationship between the phases and the conditions imposed by material balance
requirements.
Partition Coefficient
The partition coefficient describes the ratio of compositions in phases that
coexist at equilibrium
Ki
x i
x i
( { } { })
= K i T ,P, x i , x i
The equilibrium conditions resulting from the First and Second Laws of
Thermodynamics provide methods for calculating Ki for mixtures.
385
Saturation Boundary Working Equation

A condition that often is of practical interest is to determine the boundary
between the single- and multiple-phase equilibrium conditions.
Begin with the requirement that the mole fractions in a phase must sum to unity
m
xi = 1
i =1
The composition of the saturated phase is known (the specified overall

composition), and the composition of the incipient phase is unknown.
Begin with the expression for the incipient phase
m
x i
i =1
= 1 or
xi = 1
i =1
Use the equilibrium relation in the form of the partition coefficient to eliminate the
mole fractions of the unknown phase.
Ki =
x i
x i
xi
i =1
= K i x i = 1
i =1
386
Determine the saturation condition by finding the T or P (whichever is not

specified originally) that satisfies the working equation
K i x i
i =1
x
= 1 or i = 1
i =1 K i
m
387
Phase Split Working Equation

Use the material balances to describe the state when two coexisting phases are
present. The overall composition is known but the compositions of the coexisting
phases are unknown.
Total material balance:
+ = 1
Species material balance:
x i + x i = x i
nj
=
n
j
where:
x i is the mole fraction of specie i in phase
x i is the overall mole fraction of specie i in the mixture

Use the partition coefficient and the total material balance to eliminate phase
from the species material balance
)(
x i + K i x i 1 = x i
388
Rearrange to obtain
x i =
xi
1+ (K i 1)
Working equations:
xi

=1
i =1 1+ (K i 1)
m
K i xi

=1
i =1 1+ (K i 1)
m
(K i 1) x i

=0
i =1 1+ (K i 1)
m
389
Solve the working equation equation for , then compute the phase mole
fractions using
x i =
xi
1+ (K i 1)
and
x i = K i x i
390
Equilibrium Relationships
The stability criteria include
i = i Gi = G i fi = f i
Alternative descriptions of the fugacity of a substance in the mixture
Fugacity coefficient:
fi = x i i P
Activity coefficient:
fi = i x i f i
391
Computational Approaches
Gamma-Phi (-)
Use the fugacity coefficient description for one phase and the activity coefficient
description for the other:
x i i P
x i i f i
x i
x i
i f i
=
i P
Equation of State
Use the fugacity coefficient description for both phases:
x i i P
x ii P
x i
x i
i
=
i
392
Vapor Phase Description

For the vapor phase, the most common representation is the fugacity coefficient
notation
fiv = y i vi P
where
1
RT
lnvi =
( Z i 1) dP
P
If
Z = 1+
BP
RT
provides an accurate description of Z (usually true for low pressure calculations),

then
P
B
B P
v
ln i i dP = i
RT
RT
393
Liquid/Solid Phase Description

For liquids and solids, the activity coefficient notation often is used. For liquids,
fiL
= iL x i f iL
= iL x i iv Pi v
1
exp
RT
Vi dP
Pi v
For solids
fis = is x i f is
where
sv P sv exp 1
i i
RT
f is =
v v
1
P
exp
i i
RT
Vi dP
Pi sv
T Titp
P
Pi s

L
s
Vi dP + Vi dP
Pi v

Pi s
T > Titp
394
VLE Equilibrium Descriptions

General formulation
The general relationship for representing vapor-liquid equilibrium (VLE) using the
gamma-phi (-) notation is
1
y i iLi Pi
Ki
=
exp
v
xi
i P
RT
Vi dP
Pi
where
Pi
dP
i = exp ( Z i 1)
P
0
dP
iv = exp Z i 1
P
0
395
Common Assumptions
1.
1
exp
RT
V dP 1
i
Pi
2.
i
1
v
3.
iL = 1
(ideal solution)
4.
iLi Pi
1
exp
RT
V dP = constant
i
Pi
396
Raoult's law
If assumptions 1, 2 and 3 are valid,
1
y i iLi Pi
Ki
=
exp
v
xi
i P
RT
P
Vi dP = i
P
Pi
Note also that
1
iLi
exp
v
i
RT
Vi dP = 1 Raoult's Law
Pi
(This condition does not require that 1, 2 and 3 above be satisfied individually.)
Raoult's Law is
fiL (RL ) = x i P i and
K iRL
y i P i
=
=
xi
P
This relation often provides a good approximation for estimating phase behavior.
397
Henry's law
If the fugacity is linear with composition, then
fi = i x i
This result is known as Henry's law, and it provides a good representation of the
fugacity of a species at nearly infinite dilution.
For vapor-liquid equilibrium calculations, it applies when assumption 4 pertains,
so that
yi
Li
Ki =
= v
x i i P
where
Li
= iLi Pi
1
exp
RT
V dP
i
Pi
or, in the general case,
fi
lim
i =
x i 0 x i
398
Excess Gibbs Models for Liquid Phase

Normally, the parameters for these models are determined from experimental
data. There are methods available (UNIFAC [UNIquac group-Functional Activity
Coefficient], ASOG [Analytical Solution of Groups], etc.) for predicting model
parameters based on contributions to the excess Gibbs energy from various
chemical groups.
Binary Mixtures
Redlich-Kister Expansion
The Redlich-Kister expansion has the form
GE
2
3
= x 1x 2 A + B ( x 1 x 2 ) + C ( x 1 x 2 ) + D ( x 1 x 2 ) +
RT
Special Cases
A=B=C=D=0
ideal solution
B=C=D=0
symmetric
C=D=0
two-suffix Margules
D=0
three-suffix Margules
399
Van Laar
This form was derived from the van der Walls equation:
GE
x 1x 2
=
1
1
RT
x1 +
x
A12
A21 2
Wilson
This expression is not capable of describing liquid-liquid equilibrium behavior
GE
= x 1 ln ( x 1 + 12 x 2 ) x 2 ln ( 21x 1 + x 2 )
RT
T-K Wilson
This modification of the Wilson equation is capable of describing liquid-liquid
equilibrium.
x +V x / V
V x / V + x 2
GE
= x 1 ln 1 2 2 1 + x 2 ln 1 1 2
RT
x 1 + 12 x 2
21x 1 + x 2
400
NRTL
NRTL is the acronym derived from Non-Random-Two-Liquid theory.
G
GE
12G12
= x 1x 2 21 21 +
RT
x 1 + G21x 2 G12 x 1 + x 2
UNIQUAC
UNIQUAC is the acronym derived from UNIversal QUAsi-Chemical Activity
Coefficient model.
qz
GE
= x 1 ln 1 + 1 ln 1 q1 ln (1 + 2 21)
RT
x 1 2 1
q z
+x 2 ln 2 + 2 ln 2 q 2 ln (1 12 + 2 )
2
2
x2
401
Scatchard-Hildebrand
Note that the form is the same as van Laar, but the parameters, , are
determined for pure substances, allowing for prediction of mixture behavior
GE
=
RT
(1 2 )2
1
1
RT
+
V1x 1 V2 x 2
402
Multicomponent Mixtures
Wilson
GE
= x i ln x k ik
k
RT
i
T-K Wilson
GE
= xi
RT
i
NRTL
GE
= x i ji G ji x j / Gki x k
RT i j
k
UNIQUAC
GE
z
= x i ln i + qi x i ln i qi x i ln k ki
k
RT
xi 2 i
i i
i
Scatchard-Hildebrand
GE
1
=
x iVi i
RT RT i
x
V
/
V
ln
x
k k
i
k ik
k
k
403
Calculation of fugacities from equations of state

A difficulty here is that our previous expressions relating the fugacity to the
equation of state involve pressure as the variable of integration. This is feasible
for the vapor phase, but, as seen with the pure fluid vapor pressures, it is not
feasible for the liquid phase. An expression utilizing the volume as the variable of
integration must be derived.
Begin with
m
(nM )
(nM )
d (nM ) =
dT +
dP + M kdnk
T
P
k =1
P,nk
T ,nk
Divide by dni
d (nM ) (nM )
dT (nM )
dP m
dnk
=
+
+
M
dn i
dn i
T P,nk dn i P T ,nk dni k =1
dT (nM )
dP
(nM )
=
+
+Mi
P
T
dn
dn
P,nk
T ,nk i
i
404
Restrict to constant nk, T and nV
(nM )
(nM )
=
n
P
T ,nk
i T ,nV ,nk i
P
+Mi
n
i T ,nV ,nk i
Therefore
(nM )
(nM )
Mi =
n
P T ,nk
i T ,nV ,nk i
P
n
i T ,nV ,nk i
Now take
M = ln
M i = lni
We showed previously that

P
ln =
( Z 1)
dP
P
405
Convert the variable of integration using the compressibility factor equation of

state
P=
ZRT
V
RT
ZRT
ZR
dZ 2 dV +
dT
V
V
V
dP dZ dV dT
=
+
P
Z
V
T
dP =
For any isothermal situation, the last term is zero, and the integral becomes
P
dP
ln = ( Z 1)
=
P
( Z 1) dZ
Z
dV
dZ
dV
( Z 1)
( Z 1) = dZ
V
Z
V
1
Then
V
dV
ln = (Z 1) ln Z (Z 1)
406
Multiply by n
V
n ln = n ( Z 1) n lnZ
dV
dV
( Z 1) = nZ n n lnZ n ( Z 1)
V
V
The partial derivative is
(nZ )
(n ln )
=
1 lnZ
n
n
i T ,nV ,nk i
i T ,nV ,nk i
V
dV
(nZ )
n Z

1
Z n i T ,nV ,n
V
n i T ,nV ,n
k i
k i
Note that
(nZ )
Z
=
Z
+
n
n
n
i T ,nV ,nk i
i T ,nV ,nk i
Therefore
n
Z
Z
1 (nZ )
=
1
n
Z
n
i T ,nV ,nk i
i T ,nV ,nk i
407
Substitution into the previous expression yields

V
dV
(nZ )
(n ln )
Z 1 (nZ )
=
lnZ
1
n
Z n i T ,nV ,n
V
n i T ,nV ,n
i T ,nV ,nk i
k i
k i
(nM )
This is the actual form of the
term.
i T ,nV ,nk i
Also
P
ZRT
nZRT
=
=
n
n V
n nV
i T ,nV ,nk i i
T ,nV ,nk i i
T ,nV ,nk i
=
RT (nZ )
nV n i T ,nV ,n
k i
408
(nM )
The term of the form
is
P T ,n
k
(n ln )
P
T ,nk
=
P
n ( Z 1) nV ( Z 1)
dP

n
Z
1
=
=
(
)

P
P
RT Z
0

T ,nk
Then, combining the two previous results yields
P
(nln )
RT (nZ)
n(Z 1)V
=

P T,nk n i T,nV,nki nV n i T,nV,nki ZRT

=
Z 1 (nZ)
Z n i T,nV,n
k i
409
Collecting all the results produces

lni =
( Z 1) (nZ )
Z
lnZ
n
i T ,nV ,nk i
V
(nZ )
dV ( Z 1) (nZ )
1
n
n
V
Z
i
i T ,nV ,nk i
T ,nV ,nk i
which, after canceling the first and last terms, becomes
(nZ )
dV
lni =
1
lnZ
n i T ,nV ,nk i
V
nZ

n i
T ,nV ,nk i
1
lnZ
410
Alternative notation
dV
lni = Z i 1
lnZ
where:
(nZ )
Z i =
n i T ,nV ,nk i
General Relationship for Cubic Equations
The more common cubic equations can be expressed in a general form as
follows
lni =
bi
a
1 ai b i V + b
V b
Z
+
1+ ln
( Z 1) ln

b
a b V + b
V
bRT ( )
411
where
Z=
V
aV
V b RT (V + b ) (V + b )
2
aR 2Tc,i
ai =
Pc,i
bi =
bRTc,i
Pc,i
RK =
SRK
PR
1
T
)(
= 1+ 0.48508 + 1.5517 0.1561 2 1 Tr
)(
= 1+ 0.37464 + 1.54226 0.26992 2 1 Tr
412
The numerical values of , , a and b for the Redlich-Kwong, Soave-RedlichKwong and Peng-Robinson equations of state are given in the table below.
RK
SRK
PR
1 2
1+ 2
9 2 1
2 1
3
1/3
1/3
1
1/3
9 2 1
1/3
2 1
3
0.45724
0.07780
413
Mixing rules for cubic equations of state

The relations between the cubic equation parameters for the mixture and the
composition and parameters for the pure fluids are known as mixing rules.
These provide the key to accuracy in descriptions of mixture behavior.
An excellent reference for detailed information on this subject is:
H. Orbey and S. I. Sandler, Modeling Vapor-Liquid Equilibria: Cubic
Equations of State and Their Mixing Rules, Cambridge University Press,
1998
Conventional
The form used most frequently are known as the Lorentz-Berthelot mixing rules,
which have the following form
bm = x i b i
i
am
= x i ai = ai x i x
i
ai = aii a (1 k i )
where:
k i is the binary interaction parameter
414
Conformal solution
For this description, the assumption is that the intermolecular potential is a
universal function, with reducing parameters fij and hij, so that
uij (r ) = fij u0 r / hij1/ 3
h = x i x j hij
i j
f =
1
x i x j fij hij
h i j
In this approach, the Peng-Robinson equation assumes the form
c
cd
+d +2
V
RT
Z=
RT
b
V b
(V + b ) + (V b )
V
415
where the pure fluid values are
bii = 0.07780RTc,i / Pc,i

2
c ii = aii PR = 0.45724 PR R 2Tc,i
/ Pc,i
d ii =
aii PR
= 0.45724 PR RTc,i / Pc,i
RTc
The mixture values are:
and the cross values are:
bm = x i x j bij
bij = 1 ij
bii1/ 3 + b1/jj 3
c m = x i x j c ij
c ii c jj
i j
i j
d m = x i x j d ij
i j
c ij = 1 k ij bij
d ij = 1 mij
bii b jj
1/ 3
3 d ii
+ d 1/jj 3
416
Complicated mixing rules are required when using cubic equations of state to
represent the VLE behavior of strongly interacting molecules such as water and
alcohols.
Mixing Rules Based on Excess Properties
For highly non-ideal solutions, the phase behavior descriptions obtained from
equations of state can be improved significantly by incorporating known
information about the behavior of the liquid phase. For many systems, low
pressure VLE measurements at one or more temperatures provide activity
coefficient data.
The excess Gibbs function is given by
i
GE
= x i ln i = x i ln = x i lni x i lni
RT
i i
i
i
i
Also:
x i lni = ln
i
and:
ln = Z lnZ ( Z 1)
dV
V
417
Therefore
V
G
dP
x
= Z lnZ ( Z 1)
i
RT
P i
dP
Z lnZ ( Z 1)
i
i
i
The interest here is in cubic equations of state, which follow the general form
Zk =
V
a
fk (T ,V )
V b bRT
k = RK, SRK, PR, etc.
For this form, the excess Gibbs energy becomes

Z
1 b / V
GE
= Z x i Z i x i ln x i ln
RT
1
b
/
V
Zi i
i
i
i
i
ai
a
+
C
V
x
C (Vi )
(
)
i
bRT
bi RT
where
V
C (V ) =
fk
(T ,V )
dV
V
418
E
Note that GEOS
varies with pressure. Most of the models used for G are
independent of pressure, so that

E
GEOS
= GE
can be used at only one pressure. There are two potential choices
GE =
lim
P0
E
GEOS
Infinite pressure: GE =
lim
P
E
GEOS
Zero pressure:
The available activity coeficient data usually are at low pressures, but there is no
zero pressure root for the cubic equations for reduced temperatures above 0.8 to
0.85, depending on the equation.
As the pressure becomes infinite:
lim
P
V =b
The infinite pressure limit yields an equation relating a and b to the activity
coefficient data. The function C assumes a numerical value, C*, in the limit,
which varies with equation of state.
419
Huron-Vidal
Vidal and co-workers were first to use the infinite pressure limit, resulting in the
Huron-Vidal mixing rules
b = x i bi
i
ai G
a = b xi +
b
C
*
i i
References:
Vidal, Chem. Eng. Sci., 33, 787 (1978)
Huron and Vidal, Fluid Phase Eq., 3, 255 (1979).
The Huron-Vidal mixing rules work well for some systems, but not for others,
especially at higher pressures and temperatures (approaching the critical region
or the cricondentherm).
420
Wong-Sandler
Wong and Sandler [AIChE J., 38, 671 (1992)] proposed an alternative set of
mixing rules following this approach, but recognizing that the excess Helmholtz
energy exhibits much less variation with pressure than does the excess Gibbs
energy.
At low pressures
GE (T ,LowP,x ) = AE (T ,LowP,x ) + PV E AE (T ,LowP,x )

Furthermore, because the excess Helmholtz energy depends only weakly upon
pressure
AE (T ,P = ,x ) AE (T ,LowP,x ) GE (T ,LowP,x )
The excess Helmholtz energy is related to the equation of state through
V
A
Z
dV
= x i ln ( Z 1)
xi
RT
Z
V
i
i
i
dV
( Z i 1) V
421
Wong and Sandler also used the mixing rule for second virial coefficients
B = x i x k Bik
i k
to obtain the following expression

b
a
= xi xk
RT
i k
aik
ik RT
The Wong-Sandler mixing rules are

E
a
1 G
ai
=
+
x
i
bRT C * RT i
bi RT
a
a
= xi xk b
RT
RT ik
i k
In the original formulation, the cross term is
a
1
ai
a
=
b
+
b
i

(1 k i )
RT i 2
RT
RT
422
The Wong-Sandler mixing rules were reformulated by Orbey and Sandler [AIChE
J., 41, 683 (1995)] to simplify the requirements for data. The reformulated cross
term is
ai a
a
1
=
b
+
b
(
)
(1 k i )
RT i 2
RT
and a modified NRTL expression is used for the excess Gibbs function
x k gki ki
= xi k
x g i
RT
i

GE
where: gki = bk exp ( ki )
This formulation is useful, because infinite dilution activity coefficients at a single

temperature are sufficient to obtain the parameters for the cubic equation.
Furthermore, in the absence of data, methods for estimating infinite dilution
activity coefficients (such as UNIFAC or ASOG) may be used.
423
CHEMICAL REACTION EQUILIBRIUM

Chemical Reaction (Generalized Form)
1 A1 + 2 A2 + + m1 Am1 + m Am
where:
m = number of chemical species involved
i = stoichiometric coefficient for species i

Ai = chemical compound or element (species i)
Alternate General Form:
i Ai 0
In both cases,
i < 0 for species on left

i > 0 for species on right
424
As the reaction occurs,
ni i
=
n j j
because of the stoichiometry of the reaction.
Reaction coordinate
Rearrange the previous result to obtain:
ni n j nk
=
=
=
i
j
k
In the limit of infinitesimal changes, ni dni. Use the above result to define the
reaction coordinate (or extent of reaction), :
dni dn j dnk
d =
=
=
=
i
j
k
425
Then:
dni = i d ni n oi = i
Stoichiometry and compositions (single reaction):
ni = n oi + i
nT = ni = n oi + i = nTo + i
i
n oi + i
ni
xi =
=
nT nTo + i
i
= 1 defines a mole of reaction
426
Multiple Simultaneous Reactions

For multiple reactions we have a system of equations:
ij Ai 0
where:
( j = 1, 2, 3,, r )
i denotes chemical species

j denotes individual reaction
r = number of independent reactions
There is a reaction coordinate, j, for each reaction.

Stoichiometry and compositions (multiple rx):
427
ni = nio + j ij
j
nT = ni = nio + j ij = nTo + j ij
i
i j
nio + j ij
xi =
ni
j
= o
nT nT + ij
j
j
Equilibrium criteria
From the Second and First Laws of Thermodynamics we derived:
(dG )
total
T ,P
=0
so that Gtotal = nG is at a minimum when the system is at equilibrium.
428
(nG) is a function of composition for constant T,P. Because each composition

can be written as a function of the reaction coordinate, , (nG) becomes a
function of .
At equilibrium,
where:
nei = n oi + i e
nG
= value of at equilibrium
= 0 for inert species
Minimum
Standard Free Energy Change/Equilibrium Constant

The general form of the Physics Summary Statement for open systems with T,P
as the independent variables is:
d (nG ) = (nS ) dT + (nV ) dP + i dni

i
From the definition of the reaction coordinate
dni = i d i dni = i i d
i
429
So:
d (nG ) = (nS ) dT + (nV ) dP + i i d

i
Math Relation 1:
(nG )
(nG )
(nG )
d (nG ) =
dT
+
dP
+
P
d
T
P,
T ,
T ,P
430
Comparison of the previous two equations yields

(nG )
= i i

T ,P
Equilibrium criteria of minimum in nG at constant T,P requires

(nG )
= 0 i i = 0

T ,P
Also, because
i = G i
the equilibrium condition requires:
i i = i G i = 0
431
In our previous discussions we had
dG i = RTd lnfi
fi
+ RT ln o = G oi + RT ln i
fi
so that
G i = G oi
where:
G oi , f io refer to the free energy and fugacity, respectively, at a standard
state.
Note: For reaction equilibrium calculations, the standard state usually is taken
to be an ideal gas at unit pressure.
i G oi + RT i ln i = 0
G i = G oi + RT ln i
iG i = 0
Note:
i ln i = ln ( i ) i = ln ( i )
i
where:
( i ) i = (1)
i =1
( 2 ) ( 3 )
2
432
Then:
i G oi = RT ln ( i ) i = RT lnK eq
i
where:
K eq ( i )
i
fi i
= o = equilibrium constant
i f i
The Standard Free Energy of Reaction then is defined by

r G o RT lnK eq = i G oi
Notes:
o
Keq, G i are functions only of temperature

The standard states need not be identical for every chemical species present,
but for each species, the standard state temperature must be the equilibrium
o
temperature and the same standard state must be used to calculate G , f
i
o
and f i .
433
Standard Property Change of Reaction
Definition:
r M o = i M oi
where: r M o = standard property change of reaction.
M oi = value of property M for pure species i at the standard state.

Examples:
r H o = i H oi
is the standard heat of reaction
r G o = i G oi
is the standard free energy of reaction
r S o = i S oi
is the standard entropy change of reaction
r C po = i C po i
is the standard heat capacity change of reaction
Note: All standard property changes of reactions are functions only of

temperature.
434
Standard property changes of reaction obey the same thermodynamic relations

as the properties discussed previously.
r Ao = r U o T r S o
r U o = r H o r (PV )
r S =
d r G
dT RT
d r H o
dT
d r G o
dT
) = H
r
RT 2
)=C
r
o
p
435
Temperature dependence of equilibrium constant
d
dT
r G o
r H o
RT =
RT 2
d lnK eq
r G
= lnK eq
RT
dT
) = r H o
RT 2
This result is known as the van't Hoff equation.

Integrate the van't Hoff equation
K eq (T2 )
K eq (T1)
to obtain
d lnK eq =
T2
r H o
RT
dT
T1
K eq (T2 ) 1
ln
=
K
T
(
)
eq 1 R
T2
r H o
T
dT
T1
436
or
T2
1 r H
K eq (T2 ) = K eq (T1) exp

dT
R T2
T1
Also
r H
(T ) = r H (To ) + r CPo dT
o
To
Necessary information: r G o , r H o at one temperature

r CPo (T ) for all substances
This information gives K eq at any temperature. An equation of state also is

required to calculate the various fugacities that appear within K eq .
437
Alternate Method for Temperature Dependence of Equilibrium Constant

Normally, r H o is a function of temperature, so the value of the free energy of
formation at temperatures other than To is calculated as follows:
r G (T ) = r H (T ) T S (T )
where
r H
(T ) = r H (To ) + r Cpo dT
o
To
and
T
r S o (T ) = r S o (To ) +
r C po
T
dT
To
438
Combining the above produces

r G (T ) r H (To ) 1
=
+
RT
RT
T
o
Co
r p
To
r C p
1
dT r S o (To ) +
dT
R
T
To
H (To ) r S (To ) 1
= r
+
RT
R
T
o
Co
r p
To
dT
r C po
RT
dT
To
Substituting
r S o (To ) r H o (To ) r G o (To )
=
R
RTo
RTo
produces
439
r G (T ) r H (To ) r H
=
RT
RT
o
(To ) r G (To ) + 1
RTo
Co
r p
dT
To
G (To ) r H (To ) 1 1 1
= r
+
+
RTo
R
T To T
o
To
r C po
RT
dT
To
Co
r p
dT
r C po
RT
dT
To
440
Free Energies of Formation

Consider the special case of a property change of reaction when the reaction
forms a compound from its constituent elements.
o
f M o = M substance
constituent
elements
i M oi
The subscript, f, denotes properties of formation.

All reactions can be described as combinations of formation reactions,
r M o = i f M oi
Because of the known relations between thermodynamic proporties, only the

f M o values for two properties (usually f H o and f G o ) need be tabulated.
441
Then:
r G o (To ) = i f G oi (To )
r H o (To ) = i f H oi (To )
r Ao = r U o T r S o
r U o = r H o r (PV )
r S o =
Go
d r
dT RT
d r H o
dT
d r G o
dT
) = H
r
RT 2
)=C
r
o
p
442
Necessary information: f G o and f H o at one temperature, ideal gas heat

capacities and the equation of state. This information allows calculation of K eq
and the fugacities contained in equilibrium constant.
Standard and Reference State Choices
In this section, the term standard state denotes the base states for calculating
the standard free energy, standard entropy and standard enthalpy of reaction.
The term reference state denotes the base states for calculating the fugacity of
a species in the mixture. In many cases, the standard and reference states are
different physical states.
Notation:
f io denotes standard states
f i denotes reference states

The general equilibrium relation is
i
K eq
fi
= o
i f i
r G o
= exp
RT
443
Common Standard States

Ideal gas at T, P
PURE liquid or solid at T, P
Infinite dilution
Common Reference States
Fugacity coefficient: Ideal gas at T, P
Lewis- Randall: Pure liquid or solid at T, P
Henrys Law: Solute behavior at infinite dilution
Ideal Gas Standard States

For the ideal gas standard state:
f io = P o
444

The fugacity coefficient notation is based upon an ideal gas reference state,
where the ideal gas is at the same pressure as the system. The fugacity of
substance i in the mixture is
fi = y i i P
The equilibrium constant then is
ig
K eq
fi i
y i i P i P
= o = o = o y i i
P i
i f i
i P
( )
= o ( y i ) i i
P i
i
( )
P
= K y o i
P i
where
i
K y = (yi )
i
and
= i
i
445
Lewis-Randall Reference State

The fugacity of the substance in the mixture is
fi = x i iLR f iLR = x i iLR fi (T ,P )
where fi (T ,P ) is the fugacity of pure substance i at the same temperature and

pressure, and in the same phase as the mixture. Then
i
ig
K eq
fi
= o
i fi
=
i
where
i
x i iLR
K x = (xi )
i
x i iLR f iLR
=
o
P
i
f iLR
o
i
P
and
= Kx
i
f iLR
Po
( )
i
iLR
1
i Pi
=
exp
o
P
RT
fi (T ,P )
o
i P
V dP
i
Pi
446
Henry's Law Reference State

fi = x i iHL i (T )
Henrys constant is based upon the behavior of the solute at infinite dilution in the
mixture
i =
lim
x i 0
fi
x
i
Then
ig
K eq
fi
= o
i fi
x i iHL i
=
Po
i
i i
= o x i iHL
i P i
( )
i i
= K x o iHL
i P i
447
Liquid or Solid Standard States

For liquid or solid standard states, the standard state is the fugacity of the pure
material at the standard state pressure
( )
f io = f i P o

fi = y i i P
448

i
L/S
K eq

fi
y P
= o = i io
i f i
i f i P
( )
( )
( )
= P f i P o
= P f i P o
(
i
y i i
( )
P
= Ky
o
i f i P
( )
(
)
i
( y i ) i i
= K y P f i P o
( )
i
i
i
i
i
( )
449


L/S
K eq
LR
LR
f
x f
= oi = i i o i = x i iLR
i fi
i fi P
i
( )
( )
= K x iLR
i
and
f i (P )
( )
fi Po
i
f (P )
i o
i fi P
1
= exp
RT
( )
LR
i
f
i o
i fi P
( )
Vi dP
Po
P
450

fi = x i iHL i (T )
mixture
i =
lim
x i 0
fi
x
i
Then
L/S
K eq
fi
= o
i fi
x i iHL i
=
o
i f i P
( )
i
= Kx
o
i f i P
( )
i
iHL
i
i
=
o
i f i P
( )
i
x i iHL
i
( )
451
Infinite Dilution Standard State

In some cases, such as ionic solutions, it is convenient to use a standard state
for the solute already in solution
f oi
= i =
fi
x
i
lim
x i 0

fi = y i i P
K eq
fi i
y i i P i
P
= o =
= y i i
i f i
i i
i i i
= ( y i ) i i
i i i
i
( )
P
= K y i
i i i
( )
452


K eq
x i iLR f iLR
fi i
= o =
i
i fi
i
=
i
LR i
xi i
= Kx
i
( )
f iLR
i i
LR i
i
f (P )
i
i i
453

fi = x i iHL i (T )
mixture
i =
lim
x i 0
fi
x
i
Then
K eq
fi
= o
i fi
x i iHL i
=
i i
= x i iHL
i i i
= Kx
i
( )
HL i
i
454
Summary of the Equilibrium Constant Definitions

ig
K eq
fi i
= o
i P
L/S
K eq
K eq

fi
=
o
i f i P
( )
fi
=
i i
i
K P = (Pi )
i
K y = (yi )
i
K x = (xi )
i
K c = (c i )
i
equilibrium constant based upon ideal gas standard

states
equilibrium constant based upon pure liquid or solid

standard state
equilibrium constant based upon infinite dilution

standard state
Pi = y i P = partial pressure of specie i

y i = mole fraction of specie i in the vapor phase
x i = mole fraction of specie i in the liquid phase
c i = concentration of specie i (usually in the liquid
phase)
455
Relations Between Various K's

ig
K eq
L/S
K eq
ig
K eq
K eq
( )
f Po
i
=
o
i P

= oi
i P
K eq
L/S
K eq
( )
f Po
i
=
i i
K p = [Pi ]
fi
= V
i i
i
fi
= o
i f i
f io
V
i
i
f io
ig
= K eq
V
i i
ig
Note: K eq is dimensionless but KP has dimensions of pressure if 0.
456
Also:
K y = [yi ]
fi i
fi i f io
Po
ig
= V = o V = K eq V
i i P
i f i i P
i i P
i P i
Kx
=
Ky
i if i
Note: Both KP and Ky are functions of pressure through i , and Ky is directly a

function of pressure if 0.
i
K c = (c i )
i
( )
= yi c
i
f io
= K eq v
i i cP
Note: K P , K y and K c may depend upon pressure, temperature and

composition, but K eq depends only upon temperature.
457
Composition/Standard State/Reference State Matrix

Composition
Standard State
Reference State
Mole fraction
Ideal gas
Ideal gas
Mass fraction
Pure liquid or solid
Lewis-Randall
Molality
Infinite dilution
Henry's law
Molarity
Concentration
458
Reaction Equilibrium by Minimization of Gibbs Free Energy

Consider the case where m chemical species are present at fixed temperature
and pressure. The total Gibbs energy for this system is a function of the amounts
of each species present:
Gtotal = nG (n1,n2 ,n3 ,,nm )

When reactions occur, the number of atoms of each element present must be
conserved even though the atoms may be regrouped through the reactions to
form different compounds.
The mass balance for each atom provides an additional constraint for the
minimization problem:
m
A j ni aij = 0
i =1
where: Aj = number of gram atoms of element j.

ni = number of moles of substance i present.
aij = number of atoms of element j present in molecule i.
459
The total Gibbs energy for the mixture is given by:
fi m
nG = n i G i = n i G i + RT ln = ni G i + nM G
f i i =1
i =1
i =1
m
N
n
E
= ni Gi + nG + ni ln i
n
i =1
i =1
m
o
If G i = 0 for the elements in their standard state, then G i = f G i for all
compounds, and:
fi
o
nG = ni f G i + RT ln o
i =1
f i
Vapor phase:
Liquid phase:
Solid phase:
fi
f io
fi
f io
fi
f io
=
=
=
y i Vi P
(Po = 1 in most cases)
Po
L
L fi
xi i o
fi
f is
f io
xi i
(pure solids)
460
Method of Lagrange multipliers

The general objective here is to minimize a function of m variables:
g = g ( x1,x 2 ,,x m )
subject to w constraints that may be written as:
f k ( x 1,x 2 ,,x m ) = 0
k = 1,,w
The objective function (the function to be minimized) has m variables, but,

because of the w constraints, only m - w variables are independent.
The minimum in a function, h = h(y1, y2, ..., ym), where the {yi} all are
independent, occurs when:
h
=0
y i
2 h
>0
y i y j
i = 1, , m
i = 1, , m
j = 1, , m
simultaneously.
461
In the constrained problem, all m variables {xi} are not independent. One
solution is to eliminate w variables algebraically, then solve the case where the
derivatives of g with respect to the remaining m - w variables all are zero.
However, this procedure is not suited well to general applications.
An alternative method is to define a new function that is equivalent numerically to
the function of interest, but that has N independent variables.
Constraints:
fk = 0
Also:
k f k = 0, where k is an arbitrary multiplier.
k f k = 0
k =1
Define: F = g + k f k
k =1
F is numerically equal to g for all values of {xi}, therefore F is at a minimum when

g is at a minimum and vice versa.
Note:
F = F ( x1,x 2 ,,x m , 1,, w )
462
For F we have:
(m + w )
variables
m independent variables
w constraints
Now we can choose {xi} to be the independent variables. Then, the minimum
values of F and hence g, occur when:
F
x
i x
=0
for i = 1, 2, , m
j i
The values {xi} that yield the minimum for g are given by the solution to the
following set of simultaneous equations:
F
x
i x
fk = 0
=0
for i = 1, 2, , m
j i
k = 1, 2, , M
The Lagrange multipliers { k} have no physical significance.

463
Application to Single Phase Reactions

Total Gibbs energy:
Gtotal = nG (n1,n2 ,,nm )
Constraints (atom balances):

m
A j ni aij = 0
i =1
where:
(j
= 1, 2, , w )
m = number of chemical species present

w = number of different atoms present.
Then, the Lagrangian function to be minimized is:

m
F = nG j A j nk akj
j =1
k =1
w
So:
F
n
i n
j i
w
w
w
fi
(nG )
=
+ j aij = G i + j aij = G i + RT ln + j aij
fi
j =1
j =1
ni n j i j =1
464
If all the fugacities are based upon the elements in their standard states, the
simultaneous equations become:
w
fi
F
o
= f G i + RT ln o + j aij
ni
fi
j =1
Reaction equilibrium occurs when
f G oi
+ RT ln
fi
f io
+ j aij = 0
j =1
(i = 1, 2, , m)
( j = 1, 2,,w )
A j ni aij = 0
i =1
{ni} are the variables to be solved.

Perfect gas standard states
f io = Pio
Liquid or solid standard states
f io = f iL or f is
465
Fugacity Expressions:
Gas phase
fiV = y i Vi P
Liquid phase
fLi = x i if i
Solid phase
fsi = x i isf is
Useful Reference:
J. H. Dluzniewski & S. B. Adler, "calculation of complex reaction and/or phase
equilibrium problems," Industrial & Chemical Engineering Symposium
Series, 25, Institution of Chemical Engineers, London, 1972, Pages 4:21 - 4:26.
466
Reaction Equilbrium Using Reaction Coordinate

Each reaction provides one equation with one unknown (the reaction coordinate)
for each independent chemical reaction present.
Single Reaction
For the case of a single reaction, the mole fraction is related to the reaction
coordinate through stoichiometry by
xi =
n oi + i
n oi + i
i
Then, the mole fraction product becomes
o
n i + i
Kx =
o
i n i + i
i
i
467
Gas Phase (Fugacity Coefficient)

Use the fugacity coefficient notation
o
n
i + i
Ky =
o
i n i + i
i
i
o i
r G o
fi
=
exp
RT
P
i
This gives one equation, with the single unknown . The equation is implicit
because the i are dependent upon {yi}.
Liquid Phase (Activity Coefficient)
Use the activity coefficient notation
o
n
i + i
Kx =
o
i n i + i
i
i
o i
r G o
fi
= exp
RT
f
i
i i
This gives one equation, with the single unknown . The equation is implicit
because the i are dependent upon {xi}.

468
Multiple Independent Reactions

For multiple reactions, each reaction introduces an equation with a corresponding
unknown, usually resulting in a set of coupled simultaneous equations in the
various reaction coordinates.
The stoichiometry gives
xi =
n oi + ik k
k
n oi + k ik
i
k
i
where the subscript i denotes the individual chemical species (m total) and the
subscript k denotes the independent chemical reactions (r total).
The product based upon mole fractions becomes
i
o
n i + ik k
k
k
Kx =
i
o
n
+
i
k ik
i
k
i
(i = 1,2,,m )
(k = 1,2,,r )
469
Using the fugacity coefficient notation or the activity coefficient notation (see
single reaction section) then provides a system of simultaneous equations in the
reaction coordinate variables, i .
Heat Effects Associated with Reactions
The amount of energy that must be transferred as heat to compensate for
reaction effects is an important design parameter. This can be done conveniently
when the free elements in their standard states as used as the zero reference
point for all enthalpy calculations.
The amount of energy that is transferred as heat during a constant pressure
process (assuming that no shaft work is involved) is
total
total
Q = Hfinal
Hinitial
The enthalpy of any mixture may be expressed as

H
total
(T ,P ) = nm H (T ,P ) + ni Hi (T ,P )
i =1
Express the pure material enthalpies relative to their standard states as
Hi (T ,P ) = Hi (T ,P ) Hio (T ,P ) + Hio (T ,P ) Hio T o ,P o + Hio T o ,P o
)
470
When the enthalpies are expressed relative to the free elements in their standard
states
Hio
(T
,P
0
=
o
fHi
for free elements

for compounds
The middle term comes from
Hio
(T ,P )
Hio
(T
,P
)=
o
C p,i
dT
To
P
where
Po
Hio
= 0
dP
T
0
Po
Hio
P dP
ideal gas standard states

liquid or solid standard states
The first term on the right is
H i (T ,P )
H oi
H R (T ,P )
(T ,P ) =
0
ideal gas
liquid or solid
471
Summarize results
H
where
total
(T ,P ) = nm H (T ,P ) + ni Hi (T ,P )
i =1
ig
o
dT + H R (T ,P ) ideal gas
f Hi + C p,i
To
H i (T ,P ) =
T
H o + C /s dT
liquid or solid
p,i
f i
To
472
IONIC SOLUTIONS
Molality
To describe the behavior of ionic solutions, compositions often are expressed
using molalities.
Definition:
Notation:
Molality is the number of moles of solute per kilogram of solvent.
ni = number of moles of solute (i)

no = number of moles of solvent.
M o = molar mass of solvent
mi = molality of solute (i)
Then:
mi
1000ni
noM o
xi =
ni
no + nk
k
mi ni (1000 )
=
xi
noM o
no + nk
k
ni
1000 no + nk
1000
k
=
=
noM o
x oM o
473
mi
1000
As nk 0 (a very dilute solution),
xi
Mo
and
mi
1000x i
Mo
Volume Concentration
Definition:
ci
ni
V
total mass = V = noM o + nk M k

k
Then
V=
noM o + nk M
k
Substitution into the definition of concentration produces

ci =
ni
x i
noM o + nk M
Mo
(dilute solution)
474
Treatment of Solution Thermodynamics

The properties of the various species in the solution usually are described as
follows
Solute:
G i = G i
fi
+ RT ln
fi
Solvent:
Go = Go
fo
+ RT ln
fo
Solute:
fi = i m i f i
Solvent:
fo = o x i fo
Solute:
f i
Solvent:
fo = fugacity of pure liquid solvent
lim
mi 0
fi
m
i
475
Then
Solvent: Go = Gibbs energy of pure solvent as a liquid at the same
temperature and pressure as the solution
Solute:
G i = Gibbs energy of the solute in a hypothetical ideal solution of

unit molality at the same temperature and pressure as the
solution
Alternate form based upon volume concentrations
Solute: fi = i c i fi
Solute:
f i
lim
ci 0
fi
c
i
Solute: Go = Gibbs energy of the solute in a hypothetical ideal solution of

unit concentration at the same temperature and pressure as
the solution
476
Summary of Conventions for Activities

Form of fugacity
Convention
Mixture
Solutes
Solvents
LR/LR
x i i f i
f i = f iL
f i = f iL
HL1/LR
x i i f i
HL2/LR
HL3/LR
x o ofo
mi i f i
x o ofo
c i i f i
f i
f i
fi
x = i
i
f i = f iL
lim
mi 0
fi
m
i
f o = foL
lim
ci 0
fi
c
i
f o = foL
lim
x i 0
f i
477
Free Energy of Formation in Solution

Consider a vapor in equilibrium with a liquid solution:
Vapor:
GvI
where:
= Gio
fi
P
+ RT ln o = Gio + RT ln y i i o
P
fi
P o is the standard state pressure (at which Gio is specified), and

usually is at unit pressure.
Liquid Solution:
GLI
where:
= Gi
fi
mi
+ RT ln = Gi + RT ln i o
mi
fi
m oi is the standard state molality (at which Gi is specified), and usually

is at unit molality.
478
Then, application of the equilibrium condition produces
Gio
mi
P
+ RT ln y i i o = Gi + RT ln i o
P
mi
Gi
Gio
or
y P m o
= RT ln i i oi
i m i P
The difference between the standard states must be independent of solution

composition because the standard states are fixed states.
Use a dilute solution and a pure vapor to evaluate the numerical value of the
difference between the standard states.
479
Electrolytes
Notation:
where:
M + A = +Mz + + Az
M = positive ion
A = negative ion
z + = charge of positive ion

z = charge of negative ion
+ = number of positive ions in electrolyte balance

= number of negative ions in electrolyte balance
Example
+
H2SO 4 2H + SO 4
+ = 2
= 1
z+ = 1
z = 2
480
Charge Balance
z = +z + + z = 0
if original molecule is neutral
Notation:
no = number of moles of solvent

mu =
number of moles of undissociated electrolyte ( M + A )
m+ =
number of moles of positive ions ( Mz + )
m =
number of moles of negative ions ( Az )
Dissociation Stoichiometry
m + = + (m mu )
m = (m mu )
481
Classes of Electrolytes
A weak electrolyte has a small degree of dissociation:
mu >> m+ ,m
A strong electrolyte has almost complete dissociation:
mu << m,mu 0
The Gibbs energy relative to the infinite dilution standard state is related to the
Gibbs energy relative to ideal gas standard state by
Gi
Gio
y P m o
= RT ln i i oi
i m i P
For a pure vapor, y i = 1

In the limit of infinite dilution, i = 1
If the vapor is treated as an ideal gas, i = 1
482
Then
Gi
Gio
= RT ln
lim
mi 0
P m o
oi
m i P
Using the above results, the free energy of formation in solution is defined as
f Gi
(solution) =
f Gio
+ RT ln
lim
mi 0
f m o
i oi
i m i P
where: f G oi = Gibbs energy of formation of species i as a perfect gas at the

standard state pressure
f G i = Gibbs energy of formation of species i in a hypothetical ideal

solution of unit molality
This type of approach often is used for solutions of electrolytes in water, e.g.
salts, inorganic acids, etc.
483
Gibbs Energy of Electrolyte Solution

General form:
dGtotal = S total dT +V total dP + i dn i

i
Using the notation defined for electrolyte solutions changes this equation to
dGtot = S tot dT +V tot dP + u dmu + +dm + + dm + o dno
The differential stoichiometry relations are

dm + = + (dm dmu )
dm = (dm dmu )
Then
dGtot = S tot dT +V tot dP + [ u + + m ]dmu + [ + + + ]dm + o dno

In the usual restriction to constant temperature and pressure, the first two terms
on the right hand side become zero, so that
dGtot = [ u + + ]dmu + [ + + + ]dm + o dno

484
In a closed system, no ,m are constant, leading to
dGtot = [ u + + ]dmu
The only independent variable remaining is mu , therefore equilibrium occurs
when
Gtotal
mu
=0
T ,P,m,n
o
= u + +
that may be put in the form
i Gi = 0
i
where i = 1 for undissociated electrolyte. Note that this form is exactly the same
as that for chemical equilibrium.
485
For the form:
G i = G i
i mi
+ RT ln o
mi
i G i = 0 Gu = +G+ + G
i
which become, upon substitution

Gu = +G+ + G + RT ln ++ m++ m
Nomenclature
= + +
= ++
mean ionic activity coefficient
m = m++ m mean ionic molality

Then
Gu = +G+ + G + RT ln[ m ]
486
Equilibrium Involving Ionic Solutions

Vapor/Liquid Equilibrium
Vapor-liquid equilibrium for electrolyte solutions most often is of interest for
determining experimentally the activity coefficient of the solvent in the solution,
although some solutes (e.g., HCl) are sufficiently volatile that ion activity
coefficients may be determined in this way.
For the solvent,
P
o =
x oo Po
foL = x o ofoL x o oo Po
fov = y oov P P
487
Solid/Liquid Phase Equilibrium

Solvent
The activity coefficient of the solvent also can be determined by measuring the
freezing point depression. For aqueous solutions, if the solid formed is pure ice
(usually the case for ice, the solvent fugacity is
foL = x o ofoL
1
o =
xo
fos = fos = foL
Note that as freezing occurs, solvent is removed from the solution resulting in an
increasing solute concentration. Therefore, the above relation must be applied to
the conditions when the amount of ice goes to zero.
488
Solute
Assume the solid to be pure electrolyte
Gus = Gus = GuL = +G+ + G + RT ln[ m ]

where m = m++ m = solubility product (SP)
General case:
SP = constant
Dilute solution:
and
m++ m S.P.
(lnSP ) Hu hus
Temperature dependence:
=
T
RT 2
where Hu is the partial molar enthalpy at infinite dilution.
489
Equilibrium Constants for Ionic Solutions

Dissociation reaction:
M + A = +Mz + + Az
Equilibrium condition:
Gu = +G+ + G
Also:
Gu = Gu + RT ln (mu u )
G+ = G+ + RT ln (m + + )
G = G + RT ln (m )
Substitution and algebraic manipulations produce
+G+
+ G
Gu
(m )
= RT ln
mu
= RT lnK e
where
Ke
m )
(
=
mu u
m++ m
=
= true dissociation constant
mu u
490
Also
K e = K e (T ,P ) because the states denoted by are at infinite dilution at the

same temperature and pressure as the solution.
Then
r G = RT lnK e = + f G+ + f G f Gu
Apparent Dissociation Constant

The apparent dissociation constant is a convenient quantity because it does
not require knowledge of the activity coefficient.
m++ m m
Ka =
=
mA
mA
z+
for the dissociation reaction: M + A = +M
+ Az
491
Example 1
H2CO3 H + + HCO3
HCO3 H + + CO3=
Simplify notation for ease in use of subscripts
H2CO3 A
H+ B
HCO3 C
CO2= D
Reaction 1: A B + C
Reaction 2: C B + D
Reaction 3: A 2B + D
Equilibrium for reaction 1:
2
B C mB mC BC
mB mC
K1 =
=
Am A
Am A
Equilibrium for Reaction 2:
3
B D mB mD B2 D mB mD BD
mB mD
K2 =
=
=
2
C mC
B C mC
BC
mC
2
3
= B C , BD
= B2 D
where BC
Equilibrium for Reaction 3:

Note:
3
B2 D mB2 mD BD
mB2 mD
K3 =
=
A mA
A mA
K 3 = K 1K 2
492
Example 2:
+++
2Fe
A
++
+ Sn 2Fe
B
C
++
++++
+ Sn
D
Equilibrium constant
3
C2 D mC2 mD CD
mC2 mD
Ke = 2
= 3 2
2
A B mAmB AB mAmB
Temperature Dependence of Ke
lnK e +H + + H H
=
T
RT 2
Free Energies of Ions in Solution

The free energies of formation of individual ions cannot be calculated on an
absolute scale, instead they must be considered in neutral pairs.
493
Example:
1
H2 ( g ) + O2 ( g ) H2O ( )
2
f GHo O( )
H2O ( ) H+ + OH (aqueous )
f G +
H , OH
(aq )
f GHo+ , OH = f GHo O( ) + f G +
Free energy of ions in solution:
H , OH- (aq )
Example:
H2 ( g ) +
1
O2 ( g ) H2O ( )
2
o
f GH
O( )
2
3
1
H2 ( g ) + N2 ( g ) NH3 (aq )
2
2
f GNH
3 (aq )
NH3 (aq ) + H2O ( ) NH+4 + OH-
f G
NH+4 , OH- (aq )
Free energy of ions in solution:
o
f GNH
=
G
+
f
, OH (aq )
4
NH+4 ,
f GNH
f GHo O( )
aq
(
)
3
2
OH (aq )
-
494
Hydrogen Ion Convention
To allow tabulation of f G , adopt the convention that:
f GHo+ = 0
for H at unit molality at all temperatures
Also
f HHo+ = 0 = f SHo+
Galvanic Cells
G =
work done at constant T,P in a reversible reaction
-zFE
number of Faradays passing through the cell
Faraday's constant = 96,500 coulombs/mole eq.
electromotive force (volts)
where
495
Also
G = i G i
where:
G i = +G+ + G + RT ln[ m ]
i G i = zFE
Examples:
Platinum electrode:
1
H H+ + e2
Mercury electrode:
1
Hg2Cl2 + e- Hg ( ) + Cl2
Total reaction:
1
1
H2 + Hg2Cl2 HCl + Hg ( )
2
2
Then
1
1
FE = GHCl + GHg G H 2 G Hg 2Cl2
2
2
GHCl = G + + G - + 2RT ln ( m )
H
Cl
(The previous equation assumes that HCl is a strong electrolyte, i.e., that
essentially all HCl is dissociated.)
496
Because the vapor and liquid are in equilibrium, the partial molar Gibbs energy
for hydrogen in the solution is
GH2 = GHo2 + RT lnfH2 GHo2 + RT lnPH2
(at low pressures )
Because neither mercury nor mercurous chloride dissolve in water to a significant

extent
L
GHg = GHg
S
GHg2Cl2 = GHg
2Cl2
Then
1 s
1 o
FE = G + + G - + GHg
GHg
GH2 RT ln PH2 ln ( m )
Cl
2
2
H
Cl
2
2
or
m
FE = FE + RT ln
PH
2
o
where:
1 s
1 o
FE o = G + + G - + GHg
GHg
G
=
G
Cl
H
r
2 2
H
Cl
2
2 2
E o = emf of a solution of unit molality

497
Also
2 RT ln m + FE = FEo 2 RT ln
(m, E are measurable [observable] variables)

Note
lim
m0
=1
lim
m0
2RT ln (m ) + F E = F E o
Therefore, E o can be obtained by extrapolating the measurements to infinite

dilution.
Again, the electrode potentials come in pairs, so the electrode potential
associated with the hydrogen ion is defined to be zero
1
E o = 0 for
H2 H+ (aq ) + e2
Using this definition, various reactions can be used to generate tables of single
electrode potentials for various ions.
Note:
f G = zFE o
498
Activity Coefficient Models for Electrolyte Solutions

Ionic Strength
The ionic strength of the solution is
1
2
all ions
in solution
mi z i2
Debye Limit Law

Debye and Huckel derived a theoretical expression for the behavior of the ionic
activity coefficient in the infinite dilution limit:
ln = 1.174 z + z
In this treatment, the solvent is treated as a structureless background continuum

with a fixed permittivity () and dielectric strength (D), and the interactions
between electrically charged particles are used to calculate the contribution of an
individual ion to the solution.
499
Extended Debye-Huckel Theory

The Debye-Huckel result can be extended to higher concentrations in the form
ln = 1.174 z + z
1+
Pitzer Model
Pitzer combined intermolecular interactions and electrical charge interactions to
express the excess Gibbs energy in the form
GE
1
1
= w f ( ) + ik ( ) ni nk + 2 ik ni nk n
RT
w i k
w i k
where w is the mass of water present, and the 's are osmotic virial
coefficients. The second osmotic virial coefficient is treated as a function of
ionic strength, while the third osmotic virial is assumed not to be affected by ionic
strength.
500
The activity coefficient expression then is

ln
3/ 2
(
)
2
+
C
= z + z f + m + B + m 2
where:
2
f = 3A
+ ln 1+ b
1+ b b
C =
3
C
2
1
A =
2 (1000 )N A s
3
e2
D
kT
o s
3/ 2
501
For a single 1:i or j:1 electrolyte

B = 2 o +
) (
2 1
2
1
1+
0.5
I exp
2
= 2.0 (kg/mol)
1/2
= 1.2 (kg/mol)
1/2
For a single 2:2 electrolyte

B
) (
2 i
2
1
1+
0.5
exp i
i
i
2
i =1 i
2
= 2 o +
1 = 1.4 (kg/mol)
1/2
2 = 12 (kg/mol)
1/2
o , 1 and C are adjustable parameters that are determined by fitting

experimental data.
502
Meissner Model
Meissner and co-workers developed a corresponding states model for electrolyte
solutions that provides activity coefficients for single electrolytes in solution using
a reduced ionic activity coefficient
oij = ( )
1/ z + z
The corresponding states prediction is made using a single Meissner parameter
(q ) for each aqueous electrolyte.

o
ik
oik
qiko
= 1+ B (1+ 0.1 ) B DH
ik
lnDH
ik = 1.174
1+ C
o
B = 0.75 0.065qik
C = 1+ 0.055qiko exp 0.023 3
T Tref
o
o
q ik
T
=
q
T
( ) ik ( ref ) 1
z
z
+
503
Values for the Meissner parameters are given for several electrolytes in the
following table.
Meissner Parameters for Selected Electrolytes at 25 C
Electrolyte
q oik
Electrolyte
q oik
HCl
6.69
FeCl2
2.16
LiCl
5.62
CaCl2
2.40
NaCl
2.23
MgSO4
0.15
KCl
0.92
CuSO4
0.00
NH4NO3
-1.15
AlCl3
1.92
Na2SO 4
-0.19
Al2 (SO4 )3
0.36
K2SO4
-0.25
A more complete table is available in Kusik & Meissner, "Electrolyte activity

coefficients in inorganic processing," in Fundamentals of Hydrometallurgical
Processing, AIChE Symposium Series, pp. 14 - 20 (1978).
504

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Chemical Engineering 623

Applications of Thermodynamics to Chemical Engineering

CHEN 623 Lecture Notes (Date of last revision: 11/07/2014)

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Lee-Kesler (1975) ..........................................................................................................277

Experimental Problems Near Critical Point ............................................................................341

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Langmuir isotherm .............................................................................................................532

CHEN 623 Lecture Notes (Date of last revision: 11/07/2014)

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