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Section 4 Thermodynamics Hendrick C. Van Ness, D.Eng . Howard P. Isermann Department of Chemical

Section 4

Thermodynamics

Hendrick C. Van Ness, D.Eng . Howard P. Isermann Department of Chemical and Bio- logical Engineering, Rensselaer Polytechnic Institute; Fellow, American Institute of Chemical Engineers; Member, American Chemical Society (Section Coeditor)

Michael M. Abbott, Ph.D.

ment of Chemical and Biological Engineering, Rensselaer Polytechnic Institute (Section Coeditor)*

Deceased; Professor Emeritus, Howard P. Isermann Depart-

INTRODUCTION

Postulate

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4-4

Postulate 2 (First Law of Thermodynamics)

4-4

. Postulate 4 (Second Law of

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4-5

4-5

Postulate

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4-5

VARIABLES, DEFINITIONS, AND RELATIONSHIPS Constant-Composition Systems

4-6

U, H, and S as Functions of T and P or T and V

 

4-6

The Ideal Gas Model

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4-7

Residual Properties.

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4-7

PROPERTY CALCULATIONS FOR GASES AND VAPORS

Evaluation of Enthalpy and Entropy in the Ideal Gas State

 

4-8

Residual Enthalpy and Entropy from PVT Correlations

4-9

Virial Equations

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4-9

Cubic Equations of State

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4-11

Pitzer’s Generalized

4-12

Liquid Phase .

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OTHER PROPERTY FORMULATIONS .

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4-13

Liquid/Vapor Phase

4-13

THERMODYNAMICS OF FLOW PROCESSES

 

Mass, Energy, and Entropy Balances for Open Systems

 

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4-14

Mass Balance for Open Systems

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4-14

. Energy Balances for Steady-State Flow Processes

General

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Energy Balance.

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4-14

4-14

Entropy Balance for Open Systems

 

4-14

Summary of Equations of Balance for Open Systems

 

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4-15

Applications to Flow Processes

 

4-15

Duct Flow of Compressible Fluids

4-15

Pipe Flow

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4-15

Nozzles

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4-15

Throttling Process.

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4-16

. Compression Processes .

Turbines

. Example 1: LNG Vaporization and Compression

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4-16

4-16

4-17

SYSTEMS OF VARIABLE COMPOSITION

 

Partial

Molar

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4-17

Gibbs-Duhem

Equation.

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4-18

Partial Molar Equation-of-State Parameters

4-18

Partial

Molar

Gibbs

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4-19

Solution Thermodynamics

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4-19

Ideal

Gas

Mixture

Model .

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4-19

Fugacity and Fugacity

4-19

Evaluation of Fugacity

4-20

Ideal Solution Model

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4-20

. Property Changes of

Excess Properties

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4-21

4-21

Fundamental Property Relations Based on the Gibbs

 

4-21

Fundamental Residual-Property

4-21

Fundamental Excess-Property Relation

4-22

Models for the Excess Gibbs

4-23

Behavior of Binary Liquid Solutions

4-26

EQUILIBRIUM

Criteria

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4-26

Phase

Rule.

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4-27

Example 2: Application of the Phase Rule

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4-27

Duhem’s Theorem

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4-27

Vapor/Liquid Equilibrium

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4-28

Gamma/Phi Approach

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4-28

Modified Raoult’s Law

Example 3: Dew and Bubble Point Calculations

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4-28

4-29

*Dr. Abbott died on May 31, 2006. This, his final contribution to the literature of chemical engineering, is deeply appreciated, as are his earlier contributions to the handbook.

4-2

THERMODYNAMICS

Data

Reduction.

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4-30

. K Values, VLE, and Flash Calculations

Solute/Solvent

Systems.

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4-31

4-31

Example 4: Flash

4-32

Equation-of-State Approach

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4-32

4-34

Extrapolation of Data with Example 5: VLE at Several Temperatures

. Liquid/Liquid and Vapor/Liquid/Liquid Equilibria

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4-34

4-35

Chemical Reaction Stoichiometry

 

4-35

Chemical Reaction Equilibria

4-35

Standard Property Changes of Reaction

4-35

. Example 6: Single-Reaction Equilibrium

Equilibrium

Constants .

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4-36

4-37

Complex Chemical Reaction Equilibria

 

4-38

THERMODYNAMIC ANALYSIS OF PROCESSES

 

Calculation of

Ideal

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4-38

. Analysis of Steady-State Steady-Flow

Lost Work

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4-39

4-39

Example 7: Lost-Work Analysis

 

4-40

THERMODYNAMICS

4-3

Nomenclature and Units

Correlation- and application-specific symbols are not shown.

 

U.S. Customary

 

U.S. Customary

Symbol

Definition

 

SI units

System units

Symbol

Definition

SI units

System units

A

Molar (or unit-mass) Helmholtz energy

J/mol [J/kg]

Btu/lb mol

P

i sat

Saturation or vapor pressure of species i

kPa

psi

[Btu/lbm]

 

A

Cross-sectional area in flow

m 2

ft 2

Q

Heat

J

Btu ft 3 /s Btu/s Btu/(lb·mol·R) Btu/(lb·mol·R) [Btu/(lbm·R)] Btu/(R·s)

â i

Dimensionless

Dimensionless

q

Volumetric flow rate

m 3 /s

 

 

Activity of species i in solution

 

Q

R

S

Rate of heat transfer

J/s

J/(mol·K)

J/(mol·K)

[J/(kg·K)]

a

i

Partial parameter, cubic equation of state

Universal gas constant

Molar (or unit-mass) entropy

B

2d virial coefficient,

cm 3 /mol

 

cm 3 /mol

 

density expansion

 

S

G

Rate of entropy generation, Eq. (4-151)

J/(K·s)

B i

Partial molar second

virial coefficient

cm 3 /mol

 

cm 3 /mol

   

ˆ

 

T

Absolute temperature

K

R R Btu/(lb·mol) [Btu/lbm] ft/s ft 3 /(lb·mol) [ft 3 /lbm] Btu Btu Btu/s

B

Reduced second virial coefficient

3d virial coefficient, density

T

c

Critical temperature

K

C

cm 6 /mol

2

cm 6 /mol

2

U

Molar (or unit-mass) internal energy

J/mol [J/kg]

ˆ

expansion

Reduced third virial coefficient

4th virial coefficient, density expansion

 

u

Fluid velocity

m/s

C

D

cm 9 /mol

3

cm 9 /mol

3

V

Molar (or unit-mass) volume

m 3 /mol [m 3 /kg]

 

W

Work

J

J

B

2d virial coefficient, pressure expansion

3d virial coefficient, pressure expansion

kPa

1

kPa

1

W s

Shaft work for flow process

C

kPa

2

kPa

2

W

s

Shaft power for flow process

J/s

x

x

i

Mole fraction in general

Mole fraction of species i in liquid phase

 

D

4th virial coefficient, pressure expansion Interaction 2d virial coefficient Interaction 3d virial

coefficient Heat capacity at constant pressure Heat capacity at constant volume

Fugacity of pure species i

kPa

3

kPa

3

i

B ij

cm 3 /mol

 

cm 3 /mol

 

y

i

Mole fraction of species i in vapor phase

C

ijk

cm 6 /mol

2

cm 6 /mol

2

Z

Compressibility factor

Dimensionless

Dimensionless

z

Elevation above a datum level

m

ft

C

P

J/(mol·K)

Btu/(lb·mol·R)

 

Superscripts

C

J/(mol·K)

Btu/(lb·mol·R)

E

Denotes excess thermodynamic property

 

V

id

Denotes value for an ideal solution

f i

kPa

psi

ig

Denotes value for an ideal gas

ˆ

f

i

G

g

g

Fugacity of species i in solution

Molar (or unit-mass) Gibbs energy

Acceleration of gravity

G E /RT

kPa

J/mol [J/kg]

m/s 2

Dimensionless

psi

Btu/(lb·mol)

[Btu/lbm]

ft/s 2

Dimensionless

l

lv

R

t

v

Denotes liquid phase

Denotes phase transition, liquid to vapor

Denotes residual thermodynamic property

Denotes total value of property

Denotes vapor phase

Denotes value at infinite dilution

 

H

Molar (or unit-mass) enthalpy

J/mol [J/kg]

Btu/(lb·mol)

 

[Btu/lbm]

 

Subscripts

K i

Dimensionless

Dimensionless

 
 

K j

Equilibrium K value, y i /x i Equilibrium constant for chemical reaction j Henry’s constant for solute species 1

Dimensionless

Dimensionless

c

Denotes value for the critical state

 

cv

Denotes the control volume

k 1

kPa

psi

fs

Denotes flowing streams

 

n

Denotes the normal boiling point

M

Molar or unit-mass solution property (A, G, H, S, U, V)

r

Denotes a reduced value

rev

Denotes a reversible process

M

Mach number

Dimensionless

Dimensionless

 

Greek Letters

 

M i

Molar or unit-mass pure-species property

 
 

α, β

As superscripts, identify phases

(A

i , G i , H i , S i , U i , V i )

β

Volume expansivity Reaction coordinate for reaction j Defined by Eq. (4-196)

K 1

°R 1

M

i

Partial property of species i in solution

ε j

mol

lb·mol

 

(A

i , G i , H i , S i , U i , V

i

)

 

Γ i (T)

J/mol

Btu/(lb·mol)

M

R

Residual thermodynamic property

 

γ

Heat capacity ratio C P /C V Activity coefficient of species i in solution

Dimensionless

Dimensionless

M

E

,

Excess thermodynamic property

(A

R , G R , H

R

,

S

R

U R , V R )

 

γ i

Dimensionless

Dimensionless

(A

E , G

E

, H

E

,

S

E

,

U E , V E )

κ

Isothermal compressibility Chemical potential of species i Stoichiometric number of species i in reaction j

Molar density

kPa 1

psi 1

M i E

Partial molar excess thermodynamic property Property change of mixing

 

µ i ν i , j

J/mol

Btu/(lb·mol)

Dimensionless

Dimensionless

M

 

(

A, G, H, S, U, V)

 

ρ

mol/m 3

lb·mol/ft 3

M° j

Standard property change of reaction j (G j °, H j °, C °)

P

j

 

σ

As subscript, denotes a heat reservoir

m

Mass

kg

lbm

Φ

i

Defined by Eq. (4-304) Fugacity coefficient of

pure species i

Fugacity coefficient of species i in solution

Dimensionless

Dimensionless

Mass flow rate

 

kg/s

 

lbm/s

   

m

 

φ i

Dimensionless Dimensionless

n

Number of moles

 

n

Molar flow rate Number of moles of species i

 

ˆ

φ i

Dimensionless

Dimensionless

n i

   

P

Absolute pressure

kPa

psi

ω

Acentric factor

Dimensionless

Dimensionless

G