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Thermodynamic Models for Chemical Processes
 Series Editor
Laurent Falk

Thermodynamic Models for

Chemical Processes

Design, Develop, Analyze and Optimize

Jean-Noël Jaubert
Romain Privat
First published 2020 in Great Britain and the United States by ISTE Press Ltd and Elsevier Ltd

Apart from any fair dealing for the purposes of research or private study, or criticism or review, as
permitted under the Copyright, Designs and Patents Act 1988, this publication may only be reproduced,
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Notices
Knowledge and best practice in this field are constantly changing. As new research and experience
broaden our understanding, changes in research methods, professional practices, or medical treatment
may become necessary.

Practitioners and researchers must always rely on their own experience and knowledge in evaluating and
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The rights of Jean-Noël Jaubert and Romain Privat to be identified as the authors of this work have been
asserted by them in accordance with the Copyright, Designs and Patents Act 1988.

British Library Cataloguing-in-Publication Data

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ISBN 978-1-78548-209-0

Printed and bound in the UK and US

 Contents

Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi

Chapter 1. Correlations for the Estimation of Thermodynamic

Properties of Pure Substances in the Liquid,
Perfect Gas or Vapor–Liquid States . . . . . . . . . . . . . . . . . . . . . . 1
1.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2. Thermodynamics of the vapor–liquid equilibrium of
a pure substance: what should be remembered . . . . . . . . . . . . . . . . . . 2
1.2.1. Phase-intensive variables and global-intensive variables . . . . . . 2
1.2.2. Conditions of two-phase equilibrium of a pure substance . . . . . . 5
1.2.3. Why should the intensive properties of the liquid and vapor
phases of a pure substance in vapor–liquid equilibrium be seen as
temperature functions? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.2.4. Critical point of a pure substance . . . . . . . . . . . . . . . . . . . . 9
1.2.5. Isotherms of a pure species in the fluid region . . . . . . . . . . . . . 9
1.2.6. Property changes on vaporization . . . . . . . . . . . . . . . . . . . . 11
1.3. Correlations for the saturated vapor pressure of pure substances . . . . 12
1.3.1. Practical expressions for the saturated vapor pressure
deduced from the Clapeyron equation . . . . . . . . . . . . . . . . . . . . . 12
1.3.2. Empirical expressions (Antoine, Wagner, Frost–Kalkwarf) . . . . . 17
1.3.3. Taking things further: constraints on the curvature of
the graphical representation of ln Psat versus 1/T . . . . . . . . . . . . . . . 17
1.3.4. Focus on the Antoine equation . . . . . . . . . . . . . . . . . . . . . . 20
1.4. Equations that can be used to correlate
the molar volumes of pure liquids . . . . . . . . . . . . . . . . . . . . . . . . . 22
1.4.1. Correlations that can be used for
molar volumes of saturated liquids . . . . . . . . . . . . . . . . . . . . . . . 22
vi Thermodynamic Models for Chemical Processes

1.4.2. Correlations that can be used for

molar volumes of subcooled liquids . . . . . . . . . . . . . . . . . . . . . . . 24
1.5. Equations that can be used to correlate
the molar volumes of saturated gases . . . . . . . . . . . . . . . . . . . . . . . 25
1.6. Equations that can be used to correlate
the enthalpies of vaporization . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
1.6.1. Use of the Clapeyron equation . . . . . . . . . . . . . . . . . . . . . . 26
1.6.2. Expression involving many adjustable parameters . . . . . . . . . . 27
1.7. Equations used to correlate the heat capacity at constant
molar pressure, molar enthalpy or molar entropy of
an incompressible liquid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
1.8. Equations that can be used to correlate the molar heat
capacity at constant pressure, molar enthalpy or
molar entropy of a perfect gas . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
1.9. Density of a pure substance . . . . . . . . . . . . . . . . . . . . . . . . . . 32
1.10. Prediction of the thermodynamic properties of pure substances . . . . 32

Chapter 2. Estimation of Thermodynamic Properties of Pure

Substances Using an Equation of State: Overview of
Available Models and Calculation Procedures . . . . . . . . . . . . . . . 35
2.1. Volumetric equation of state: a definition . . . . . . . . . . . . . . . . . . 35
2.2. General overview of the volumetric equations of state . . . . . . . . . . 35
2.3. Presentation of usual volumetric equations of state . . . . . . . . . . . . 36
2.3.1. Virial expansion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.3.2. Classic cubic equations of state. . . . . . . . . . . . . . . . . . . . . . 40
2.3.3. Introduction of volume translation in cubic
equations of state with the aim of improving
estimation of liquid densities . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
2.3.4. Equations of state relying on the statistical
associating fluid theory (SAFT) . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.3.5. Equations of state specific to particular pure substances . . . . . . . 54
2.4. Practical use of volumetric equations of state . . . . . . . . . . . . . . . . 56
2.4.1. Calculation of the state properties . . . . . . . . . . . . . . . . . . . . 56
2.4.2. Vapor–liquid equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . 56
2.5. Calculation of state properties using a
volumetric equation of state . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
2.5.1. Calculation of residual-TP properties . . . . . . . . . . . . . . . . . . 59
2.5.2. Calculation of residual-TV properties . . . . . . . . . . . . . . . . . . 61
2.5.3. Calculation of state-property changes . . . . . . . . . . . . . . . . . . 64
2.6. Vapor–liquid equilibrium calculation using a
pressure-explicit equation of state: illustration
with cubic equations of state . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
 Contents vii

2.6.1. Shapes of isotherms produced by cubic equations of state in

the pressure–molar volume plane: link between the form of
isotherms and the resolution of cubic equations of state . . . . . . . . . . . 66
2.6.2. Stable, metastable, unstable roots . . . . . . . . . . . . . . . . . . . . 68
2.6.3. Graphical determination of the saturated vapor pressure
by the Maxwell equal area rule. . . . . . . . . . . . . . . . . . . . . . . . . . 71
2.6.4. Plot of the stable portions of an isotherm
from an equation of state . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
2.6.5. Calculation of the vaporization properties
using an equation of state . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
2.7. Overall summary: criteria for selecting an equation of state for
modeling of the thermodynamic properties of a given pure fluid . . . . . . . 75

Chapter 3. Low-Pressure Vapor–Liquid and Liquid–Liquid

Equilibria of Binary Systems: Activity-Coefficient Models . . . . . . . 77
3.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
3.2. Classification of fluid-phase behaviors of binary
systems at low pressure and low temperature . . . . . . . . . . . . . . . . . . 78
3.2.1. Conventions for representation of isobaric and
isothermal phase diagrams of binary systems . . . . . . . . . . . . . . . . . 79
3.2.2. The four types of vapor–liquid equilibrium (VLE)
diagrams for low temperature, low pressure . . . . . . . . . . . . . . . . . . 81
3.2.3. Five types of liquid–liquid equilibrium (LLE) diagrams . . . . . . . 86
3.2.4. Fluid-phase diagrams resulting from the overlap of LLE and VLE
domains. Liquid–liquid–vapor equilibria (VLLE) . . . . . . . . . . . . . . 92
3.3. Condition of equilibrium between fluid phases of binary systems . . . 100
3.4. Vapor–liquid equilibrium relationship at low pressure . . . . . . . . . . 101
3.4.1. Estimation of the fugacity coefficient of a pure substance,
present in the expression of function Ci. . . . . . . . . . . . . . . . . . . . . 103
3.4.2. Estimation of the fugacity coefficient of a component in a
mixture, present in the expression of function Ci . . . . . . . . . . . . . . . 104
3.4.3. Estimation of the Poynting factor, present in the expression
of the function Ci . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
3.4.4. Estimation of the Ci term . . . . . . . . . . . . . . . . . . . . . . . . . 105
3.5. Activity coefficients: definition and models . . . . . . . . . . . . . . . . 106
3.5.1. Ideal solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
3.5.2. Excess Gibbs energy and activity coefficients . . . . . . . . . . . . . 108
3.5.3. Classification of activity-coefficient models . . . . . . . . . . . . . . 109
3.5.4. Purely correlative Margules models . . . . . . . . . . . . . . . . . . . 110
3.5.5. Redlich–Kister purely correlative model . . . . . . . . . . . . . . . . 112
3.5.6. The Van Laar model . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
3.5.7. The Scatchard–Hildebrand (SH) model . . . . . . . . . . . . . . . . . 115
viii Thermodynamic Models for Chemical Processes

3.5.8. The NRTL (non-random two-liquid) model with three adjustable

parameters per binary system . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
3.5.9. NRTL models with four and six adjustable
parameters per binary system . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
3.5.10. Wilson and Flory–Huggins models . . . . . . . . . . . . . . . . . . 118
3.5.11. UNIQUAC model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
3.5.12. The original UNIFAC model and its extensions . . . . . . . . . . . 124
3.5.13. Summary: an aid to selecting an activity-coefficient model . . . . 126
3.6. Calculation of the vapor–liquid equilibrium of binary
systems at low temperature and low pressure . . . . . . . . . . . . . . . . . . 128
3.6.1. Bubble-point pressure calculation . . . . . . . . . . . . . . . . . . . . 130
3.6.2. Calculation of the dew-point pressure . . . . . . . . . . . . . . . . . . 133
3.6.3. Calculation of the bubble-point temperature . . . . . . . . . . . . . . 133
3.6.4. Calculation of the dew-point temperature . . . . . . . . . . . . . . . 134
3.6.5. PT-flash calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135

Chapter 4. Estimation of the Thermodynamic Properties of Mixtures

from an Equation of State: An Overview of Models and Calculation
Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
4.1. The phase-equilibrium condition and the ϕ-ϕ approach. . . . . . . . . . 137
4.2. General presentation of the usual volumetric equations of
state applicable to mixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
4.3. Virial expansions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
4.4. Cubic equations of state . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
4.4.1. Generalities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
4.4.2. Classic mixing rules (known as “Van der Waals” mixing rules) . . 141
4.4.3. Advanced mixing rules by combining an equation of
state with an activity-coefficient model . . . . . . . . . . . . . . . . . . . . . 147
4.4.4. Short summary of the mixing rules for
cubic equations of state . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
4.5. Equations of state based on the “statistical associating fluid theory”
(SAFT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
4.6. Specific equations of state for particular mixtures . . . . . . . . . . . . . 161
4.7. Practical use of the equations of state for mixtures . . . . . . . . . . . . 161
4.7.1. What can be calculated from an
equation of state for mixtures? . . . . . . . . . . . . . . . . . . . . . . . . . . 161
4.7.2. Calculation of mixing properties using a
pressure-explicit equation of state . . . . . . . . . . . . . . . . . . . . . . . . 162
4.7.3. Calculation principle of vapor–liquid equilibrium
using the ϕ-ϕ approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
 Contents ix

Chapter 5. General Summary: Decision Tree to Select a

Thermodynamic Model in Order to Simulate or
Design a Chemical Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
5.1. Selection of thermodynamic models for
representation of pure substances . . . . . . . . . . . . . . . . . . . . . . . . . 169
5.2. Selection of thermodynamic models for
representation of mixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
This page intentionally left blank
 Preface

This book is not a course book but a vademecum aimed primarily at users
of process simulation software. It provides, in a condensed form, the
methods governing the choice of a thermodynamic model for a targeted
application and reminds the reader of the essential concepts on which these
methods are based. At the time of publication (2020), this book was up to
date with the main models of practical interest for the engineer and the
researcher.

Finally, because we are convinced that, in order to use these models

properly, it is important to understand – at the very least – how to carry out
the calculations of the properties of interest that result from them, we will
also refer to the major points.

Happy reading!

Jean-Noël JAUBERT
Romain PRIVAT
May 2020
 1

Correlations for the Estimation of

Thermodynamic Properties of Pure
Substances in the Liquid, Perfect
Gas or Vapor–Liquid States

1.1. Introduction

A correlation is a mathematical expression, usually simple, of a

physico-chemical property y as a function of one or several variables x.
In this chapter, dedicated to pure substances, two types of properties are
considered:
– properties depending on the temperature: for example, the heat
capacity at constant pressure of a liquid pure substance (assumed to be
incompressible), the saturated vapor pressure of a pure substance, the density
of a liquid pure substance (assumed to be incompressible), etc. In these
cases, the variable of the correlations is x = T;
– constant properties (which do not depend on the temperature): for
example, the normal boiling point, the critical pressure, the acentric factor, etc.

We will look at which principal correlations can be used for the

pure-substance thermodynamic properties that depend on the temperature T .
This chapter will end with a brief presentation of the methods that allow us
to predict the constant properties and those depending on T using only
knowledge of the chemical structure of pure substances. The variables x
of correlations then become structural information (as well as T in the case
of properties that depend on the temperature).
2 Thermodynamic Models for Chemical Processes

The T-dependent properties that are taken into consideration in this

chapter are:
– the characteristic properties of the vapor–liquid equilibrium of a pure
substance: saturated vapor pressure P sat (T ) , molar enthalpies of a boiling
liquid hLsat (T ) and of saturated vapor hGsat (T ) , molar enthalpy of
vaporization Δvap H (T ) = hGsat (T ) − hLsat (T ) , molar heat capacity at constant
pressure of the boiling liquid cPsat, L (T ) , densities of the boiling liquid ρ Lsat (T )
or of the saturated gas ρGsat (T ) ;

– properties of a pure perfect gas: molar enthalpy h • (T ) , molar heat

capacity at constant pressure cP• (T ) ;

– properties of a subcooled liquid1: molar enthalpy hLpure (T ) , molar heat

capacity at constant pressure cPpure
, L (T ) , volumetric mass ρ L
pure
(T ) . Here, we
assume that pure subcooled liquids are incompressible; in other words, their
properties are not affected by the pressure.

NOTE.– Properties of a non-perfect gaseous pure substance cannot be

described by the correlations presented in this chapter. Suitable methods
(mainly based on equations of state) are presented in the following chapters.

1.2. Thermodynamics of the vapor–liquid equilibrium of a pure

substance: what should be remembered

1.2.1. Phase-intensive variables and global-intensive variables

The intensive state of a two-phase system can be described by two sets of

variables:
– phase-intensive variables, which are the intensive variables specific
to one of the two phases of the system, for example, the temperature of
the liquid phase, the pressure of the gas phase, the density of the liquid, the
molar heat capacity of the gas phase at constant pressure, etc.;

1 The term “subcooled” refers to a liquid that has been brought to a temperature below
its boiling point. Consequently, the pure substance is not boiling (is not at vapor–liquid
equilibrium).
 Correlations for the Estimation of Thermodynamic Properties of Pure Substances 3

– global-intensive variables that are not specific to a given phase but

which instead characterize the two-phase system as a whole (i.e. the whole
system). As an example, we cite the molar proportion of the gas
phase (defined as the quantity of matter present in the gas phase divided by
the global quantity of matter in the system, i.e. the sum of the quantities of
matter in the liquid and gas phases), the global density (defined as the global
mass of the system, i.e. mliquid + mgas , divided by the global volume,
i.e. Vliquid + Vgas ), etc.

NOTE.– As explained in the following, at the vapor–liquid equilibrium, the

two phases have the same temperature (TL = TG ), the same pressure
( PL = PG ) and each component has the same chemical potential in each
phase ( μi , L = μi ,G ). Thus, the temperature, pressure and chemical potential
of a component i are both phase-intensive and global-intensive variables.

Since the extensive properties are additive, the global extensive

properties of a two-phase system are obtained by adding the extensive
properties of the two phases:

Qtwo-phase = Qliquid phase + Qgas phase

   
system
   Extensive property Extensive property
Global extensive of the liquid phase of the gas phase
property

 n (quantity of matter in mol)

 3 [1.1]
V (volume in m )

with : Q =  H (enthalpy in J)
 −1
C P (heat capacity in J ⋅ K )
...

Consequently, the relationship between the molar properties of the phases

Qliquid phase
that derive from extensive properties ( qliquid phase = , qgas phase =
nliquid phase
Qtwo-phase
Qgas phase system
) and global molar properties ( qtwo-phase = ) is:
ngas phase system ntwo-phase
system
4 Thermodynamic Models for Chemical Processes

nliquid phase ngas phase

qtwo-phase = qliquid phase + qgas phase [1.2]
system ntwo-phase ntwo-phase
system system

with q = {v, h, cP ...} . Equation [1.2] introduces the molar proportions of the
phases:

Molar proportion of gas: τ = ngas phase / ntwo-phase

 system
 [1.3]
 Molar proportion of liquid: 1 − τ = nliquid phase / ntwo-phase
 system

Figure 1.1 represents a two-phase system that illustrates, on the one hand,
the notion of extensive (also known as total) and intensive properties that are
specific to one of the phases, and, on the other hand, the notion of properties
that are characteristic of the two-phase system (known as global).

Figure 1.1. Definition of total, total molar, global and global molar properties
 Correlations for the Estimation of Thermodynamic Properties of Pure Substances 5

1.2.2. Conditions of two-phase equilibrium of a pure substance

For two-phase equilibrium to be observed, three conditions must be met:

– thermal equilibrium condition: there is no heat transfer between
the phases in equilibrium, and consequently, these necessarily have the same
temperature:
TI = TII [1.4]

– mechanical condition of equilibrium: there is no work transfer of

the pressure forces between the phases in equilibrium, and consequently,
these are necessarily at the same pressure:
PI = PII [1.5]

– diffusive equilibrium condition: there is no transfer of matter between

the phases in equilibrium, and consequently, the chemical potential of the
pure substance g (molar Gibbs energy) is the same in both phases:

g I = g II [1.6]

1.2.3. Why should the intensive properties of the liquid and

vapor phases of a pure substance in vapor–liquid equilibrium be
seen as temperature functions?

The answer to this question is provided by the Gibbs phase rule described
below. This theorem concerns the variance of a thermodynamic system, the
definition of which is also provided.

According to the previous paragraph, the intensive variables of a phase α

are the temperature Tα , the pressure Pα and the total molar properties yα
( y ∈ {v, h, g , s ...}).

DEFINITION.– The variance is defined as the number of independent

INTENSIVE variables of PHASES that need to be set (specified) in order to
characterize the INTENSIVE variables of ALL PHASES.
6 Thermodynamic Models for Chemical Processes

The Gibbs phase rule is a theorem asserting that the variance of a

thermodynamic system that contains one or several phases in equilibrium,
with no other characteristics, is given by the expression:

υ = variance of the system


υ = c + 2 −ϕ with: c = number of components [1.7]
ϕ = number of phases in equilibrium


Consequently, the variance of a two-phase system ( ϕ = 2 ) that contains a

pure substance ( c = 1 ) is υ = 1. This means that by specifying a single
intensive variable of one out of the two phases, and the value of all the
others is then set.

For example, let us suppose that the pressure PG of the gas phase of a
pure substance in vapor–liquid equilibrium is specified. Because of
the Gibbs phase rule, this then necessarily sets the pressure of the other
phase in equilibrium (this is obvious as the condition of equilibrium between
phases imposes PL = PG ), the temperature common to the two phases
TL = TG (common according to the phase-equilibrium condition), the molar
volumes vLsat and vGsat of the phases, the molar enthalpies hLsat and hGsat of the
phases, etc.

A two-phase equilibrium is therefore monovariant. This feature

induces an immediate graphical consequence: in the plane projections of
phase diagrams for pure substances with two intensive phase variables as
X and Y coordinates (e.g. pressure–molar volume, pressure–temperature,
molar enthalpy–molar entropy planes), two-phase equilibria are represented
by curves (the curves are the graphical representations of single-variable
functions).

Similarly, the Gibbs phase rule, which predicts that the variance of a pure
single-phase substance ( ϕ = 1 ) is equal to 2 and that the variance for a
pure three-phase substance is zero, the associated graphical representations
in the plane projections of the phase diagrams will be surface regions and
single points respectively. These remarks are summarized in Figure 1.2
(the definition of the critical point, which is represented in this figure, will be
provided at a later stage).
 Correlations for the Estimation of Thermodynamic Properties of Pure Substances 7

Melting curve
P
Single-phase liquid
ν=2

Single-phase solid
LSE
ν=2
ν=1
Critical point
ν=0
LVE
ν=1
Vaporization
Sublimation curve
curve Triple point
(LSVE)
Single-phase
ν=0
SVE vapor
ν=1 ν=2 T

Figure 1.2. Projection of the phase diagram for a pure substance in the
pressure–temperature plane. Illustration of the relationship between the variance of a
system and the nature of its representation on the plane. VLE = vapor–liquid
equilibrium, LSE = liquid–solid equilibrium, SVE = solid–vapor equilibrium, LSVE =
liquid–solid–vapor equilibrium

Let us now return to the example of a vapor–liquid pure substance for which
we specified the pressure of the gas phase. We will illustrate on a graph the
monovariant nature of this two-phase equilibrium. Figure 1.3 is a representation
in the (P, ν) and (P, T) plane projections of the phase diagram of a given pure
substance. The specification of the pressure PG of the gas phase in vapor–liquid
equilibrium is shown by a horizontal dot-dash straight line.

Figure 1.3. Illustration of the Gibbs phase rule in the case of a pure substance in
vapor–liquid equilibrium for which the pressure of the gas phase is specified. Left:
phase diagram of a pure substance in the plane (P, v). Right: phase diagram in the
plane (P, T). “L”: single-phase liquid domain, “V”: single-phase vapor domain, “L+V”:
two-phase vapor–liquid domain; “C”: critical point
8 Thermodynamic Models for Chemical Processes

The ( P, v ) plane shows that by specifying PG , the following properties

are then defined: (i) a unique molar volume for the liquid phase ( vLsat )
defined by the intersection point of the bubble point curve (representing the
vapor–liquid equilibrium pressure versus vLsat ) and the horizontal straight
line P = PG , (ii) a unique molar volume for the gas phase ( vG ) found at the
intersection of the dew point curve (representing the vapor–liquid
equilibrium pressure versus vGsat ) and the horizontal straight line P = PG . The
( P, T ) plane, on the other hand, shows that this specification induces also a
unique vapor–liquid equilibrium temperature TL = TG (at the intersection of
P = PG and the vaporization curve).

NOTE.– The temperature of a pure substance in vapor–liquid equilibrium is

known as the boiling point temperature. When the pressure is specified, it
is noted Tbp ( P ). The normal boiling point temperature, denoted as Tbp° , is
the boiling point temperature under normal pressure P° = 1 atm , in other
words 101,325 Pa.

Choice of the variable for correlations of phase-intensive properties

for pure substances in vapor–liquid equilibrium: the previous paragraph
insists on the need to set an intensive variable of a phase in order to
characterize a vapor–liquid pure substance. In practice, often the temperature
is chosen as the correlation variable. In doing so, the intensive properties of
the phases are written: PL (T ) = PG (T ) [pressures], hGsat (T ), hLsat (T ) [molar
enthalpies], vLsat (T ), vGsat (T ) [molar volumes], g Lsat (T ) = g Gsat (T ) [molar
Gibbs energies], etc.

NOTE.– The pressure of a pure substance in vapor–liquid equilibrium is

known as the saturated vapor pressure. When the temperature is specified,
it is written P sat (T ). The molar volumes of the liquid and gas phases in
vapor–liquid equilibrium are known as molar volumes of the saturated
liquid and saturated gas phases, denoted respectively as vLsat (T ) and
vGsat (T ).

The definitions of the boiling point temperature (at a specified pressure)

and of the saturated vapor pressure (at a specified pressure) are summarized
in Figure 1.4.
 Correlations for the Estimation of Thermodynamic Properties of Pure Substances 9

LSE
P

Critical
point
P sat (T )

LVE
P specified
Triple point

SVE
T
Tbp (P) T specified

Figure 1.4. Illustration of the definitions of the saturated vapor pressure and of the
boiling point temperature in the pressure–temperature plane of a pure substance.
VLE = vapor–liquid equilibrium, LSE = liquid–solid equilibrium, SVE = solid–vapor
equilibrium

1.2.4. Critical point of a pure substance

The critical point of a pure substance can be defined in three ways:

– in the (P, T) plane, it is the end point of the vaporization curve of a pure
substance (see Figure 1.2);
– in the (P, ν) plane, this is the common maximum for the bubble point
and dew point curves (see Figure 1.3);
– on the critical isotherm in the (P, ν) plane, it is a point of inflection with
a horizontal tangent. This definition of the critical point is illustrated in the
following section.

1.2.5. Isotherms of a pure species in the fluid region

In the (P, ν) plane, an isotherm for a pure substance is a curve made up of

all the (molar volume, pressure) couples associated with the same
temperature.

Subcritical isotherms (subcritical means that the temperature is below

the critical point temperature) are made up of three sections:
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The Project Gutenberg eBook of Memories of the
Civil War
 This ebook is for the use of anyone anywhere in the United
States and most other parts of the world at no cost and with
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eBook.

Title: Memories of the Civil War

Author: Henry B. James

Release date: August 10, 2022 [eBook #68723]

Language: English

Original publication: United States: Franklin E. James, 1898

Credits: David E. Brown and the Online Distributed Proofreading

Team at https://www.pgdp.net (This file was produced
from images generously made available by The
Internet Archive)

*** START OF THE PROJECT GUTENBERG EBOOK MEMORIES

OF THE CIVIL WAR ***
Fraternally Yours,
Henry B. James.
 MEMORIES OF
THE CIVIL WAR.
BY
Henry B. James.
Co. B, 32nd Mass. Volunteers.

“To you my comrades whether far or near,

I send this message, let our past revive;
Come, sound reveille to our hearts once more.”

NEW BEDFORD, MASS.

FRANKLIN E. JAMES.
1898
 To my Boys,
Who delighted in their childhood
to hear their father tell stories of
the war, and at whose desire these
memories have been recalled, this
book is
—DEDICATED.—
 CONTENTS.
CHAP. PAGE.
I ENLISTMENT 1
II TO THE SEAT OF WAR 6
III ON THE MARCH 10
IV ANTIETAM 14
V UNDER ARREST 17
VI IN CAMP 21
VII FREDERICKSBURG 25
VIII CHANCELLORSVILLE 29
IX BRANDY STATION & ALDIE 33
X GETTYSBURG 38
XI MINE RUN 44
XII A LETTER FROM THE FRONT 48
XIII RE-ENLISTED 52
XIV AT HOME AGAIN 55
XV IN THE WILDERNESS 59
XVI LAUREL HILL 63
XVII WILDERNESS CAMPAIGN 69
XVIII LEAVES FROM MY DIARY 73
XIX COLD HARBOR 79
XX NORFOLK RAILROAD 85
XXI EXTRACTS FROM MY DIARY 88
XXII PETERSBURG 92
XXIII PEEBLE’S FARM 97
XXIV WELDON RAILROAD 101
XXV HATCHER’S RUN 106
XXVI ON FURLOUGH 112
XXVII WOUNDED 117
XXVIII CLOSING SCENES 123
XXIX MUSTERED OUT 128
 PREFACE
I have written this account of my experience in the service of my
country from memory, aided by old diaries, letters, etc., and have
endeavored to be as accurate as possible, in regard to dates and
events of historical importance, but if mistakes occur, it cannot be
wondered at, after such a lapse of time. Some of my diaries were
lost upon the battlefield, and of those that remain, many of the
entries were in pencil and are almost effaced.
I had no intention when I began writing of making a long story, but as
I went on, memory brought back many a stirring scene, many a
weary march, many a tender thought of comrades who shared them
all with me, and so I have written them down as they came to me.
My thanks are due my wife for so carefully editing, and my son for
printing my attempt to keep in a permanent form, my recollections of
the War of the Rebellion.
 Chapter I.
ENLISTMENT.
To Arms! To Arms! Our country calls for aid,
Of faithful sons an offering must be made.
From every hamlet in the loyal North,
Her sturdy yeomen in their strength go forth;
Mechanics, merchants, all professions too,
Give up the arts of peace, another to pursue.

Edwin Emery.

I have often been asked to narrate my experience in the War of the

Rebellion, and have as often refused, but now after the lapse of thirty
three years since the close of that fearful struggle between brother
men, I feel that perhaps it would be well, for the satisfaction of those
who so earnestly desire it, to “Fight my battles over again.”
Mine was not an exceptional experience, only that of many a boy of
’61, but it may partly answer the question so often asked: “What did
the privates do?”
I have often wondered how it happened that I, born of quaker stock
on my mother’s side (she was descended from the Kemptons, who
were among the first settlers of our quaker city of New Bedford,)
should have had such a natural leaning towards scenes of adventure
and conflict. It may well have been that I inherited it from the paternal
side of the house, for my father’s father, John James, was taken
prisoner on board his ship during the War of 1812, and thrown into
an English prison, and I have often, during my childhood, listened to
his tales of warfare and bloodshed, and longed to be a man that I
might fight and avenge the wrongs inflicted on my devoted country in
its earlier days; and how I wished, as I read of the War of the
Revolution, that I might have lived in those stirring days, and done
my part in creating the American Nation.
Certainly it did not seem possible that occasion would ever arise
when I should be one of the defenders of that great nation.
The attack on Fort Sumter, the shot that so stirred the loyal hearts of
the men of the North, awakened in me an ardent desire to enlist and
help avenge the insult to our country’s flag, but my father was so
opposed to the idea that I reluctantly yielded to his authority until a
few months later, during a visit to my brother in Woburn, Mass., I
enlisted November 2nd 1861, just past my twentieth birthday, in Co.
B, 1st Battalion, afterwards the 32nd Mass. Infantry. The company
was raised by George L. Prescott, of Concord, Mass.
We were mustered into the United States service on November 27th,
and on December 3rd were sent to Fort Warren, Boston harbor, to
guard prisoners of war, among them being the confederate generals
Buckner and Tilghman, Commodore Barron, Colonel Pegram, the
confederate commissioners Mason and Slidell, the mayor and chief
of police of Baltimore, and many others.
I remember an incident that may be of interest to which I was an
eye-witness: General Buckner was walking on the parapet, under
guard, when a foreign man of war was being saluted in accordance
with military usage; a large 32 lb. gun was belching forth half minute
salutes; as he drew near it, wrapped in deep thought, not seeming to
notice what was taking place the order came to fire just as he was
abreast of the gun; he realized his danger and jumped forward just in
time, for the next instant the gun was discharged, and the prisoner
must have felt that it was indeed a narrow escape.
Many other interesting incidents connected with these celebrated
prisoners occur to me, but they would make my story too long.
We were drilled in the art of war during all that winter, and under the
strictest military discipline, the commander of the fort being that
brave old martinet of the regular army, Colonel Justin E. Dimmock.
My brother George also enlisted in the same company as myself and
was with me at Fort Warren, but the hardships and exposures of that
long cold winter and an attack of typhoid fever undermined his health
to such an extent that he was discharged a short time before we left
Fort Warren for the seat of war in the following May.
The hard and laborious life of the army seemed to agree with me,
and from the day of my enlistment until the time I was wounded,
more than three years later, my health was perfect, which was
something to be thankful for, in the army.
I did not regret leaving my brother behind me for I felt that one son
was enough for my father to spare for his country’s service; besides
my brother had a wife and child, while I was young, with no mother
to mourn for me, should I fall, and I felt that I could be spared better
than those who had home ties, and that I could face hardships and
dangers better than those who had families depending upon them. In
short it seemed my duty and pleasure to go to the war.
 Chapter II.
TO THE SEAT OF WAR.
They turned from home, from wife and child,
And all that life held sweet,
Into the hell of battle, calm
They walked with steady feet,
Resolved for wounds and pain and death;
In sacrifice complete.

Unknown.

On the 25th of May we left Fort Warren for the seat of war. Arriving at
Washington we went into camp Alexander. June 30th our battalion,
now composed of six companies, was ordered to join the army on
the peninsula. Embarking on the transport Hero we arrived at
Fortress Munroe July 2nd.
We continued on up the James river, landing at what was formerly
President Harrison’s plantation, on July 4th 1862. Now began our
soldier life in earnest, for fighting was then going on; mud was knee
deep and all was confusion. We were assigned to the brigade of
Gen. Charles Griffin, division of Gen. Morell, in Fitz John Porter’s
command, afterwards the Fifth Army Corps.
We were drawn up in line and given 80 rounds of ammunition. Just
then an officer rode up covered with mud, and said: “Well boys, I will
give you a chance at the rebs; keep cool and fire low!” Off he went,
and I was informed it was Gen. George B. McClellan.
We moved through a piece of woods, and were opened upon by a
battery. It was getting to be pretty warm, when the order came
“Forward to charge the battery,” but before we could move, the order
was countermanded, and we retreated; this was the end of the
Seven Days Fight.
We camped upon the banks of the river and staid there six weeks,
every day sickness and death reducing our ranks, for it was a very
unhealthy place. In fact it was the worst place that could be imagined
for a camp, marshy, wet ground, dust and mud alternating; what
wonder is it that our men sickened and died? Here on August 9th
Lieut. Nathaniel French Jr., one of the most promising officers in our
regiment died of malarial fever.
Through it all my health remained perfect, and I was always ready
for duty. Many of our regiment were here detailed to act as guards
over the quartermaster’s stores on the river bank.
Soon after our arrival at Harrison’s Landing, President Lincoln visited
and reviewed our army. Our division stood in line from four o’clock in
the afternoon until after nine in the evening, and then a party rode by
in the moonlight, one of whom was said to be the President of the
United States; as he was the only one who wore a stove-pipe hat,
we concluded that it must be a fact, that we had been duly reviewed,
and gladly broke ranks and prepared our suppers.
On the night of August 1st the enemy ran six pieces of artillery down
on the opposite side of the James river, and about midnight opened
upon our camp, and cold iron rained upon us, ending our slumbers
for that night. We had two tents for the officers, and five for the men,
and solid shot went through them all, but we escaped serious injury,
which seemed rather remarkable. We were more than eager to leave
this sickly camp and life of inaction, but here we had to stay and wait
for marching orders.
 Chapter III.
ON THE MARCH.
And we marched away to join the fray,
Where the work of death was done,
And soon we stood where the battle clouds
Hid the face of the mid-day sun.

’Mid the battle’s din our ranks grew thin,

And we dug our comrades’ graves,
By brook and rill, by vale and hill,
And laid away our braves.

Benj. Russell Jr.

Marching orders came on August 10th, and we gladly took up our

line of march, passing through Williamsburg, Yorktown and Big
Bethel to Newport News, where we boarded steamer Belvidere for
Acquia Creek, thence by rail to Stafford Courthouse, near
Fredericksburg. We were still kept on the move, and on August 27th
we marched out on the Gainesville road, and formed in line of battle;
here we had quite a sharp brush with the enemy. We were
endeavoring to head him off in his march northward, but were too
late, and had to chase him as rapidly as possible.
March 6, 1865.
I shall never forget the long and weary march of the next day, which
happened to be my twenty-first birthday. All that hot, dusty day was
spent in a forced march, and we suffered greatly for water, of which
there was none to be had in that dreary country. Along in the
afternoon I came to a puddle of water covered with green slime, in
which partly lay a dead mule, who had probably died while trying to
slake his thirst. I did not take warning by him, but brushed aside the
green scum and took a drink; it was wet and that was all that could
be said of it.
I dragged myself along until within an hour of sunset, and then I
dropped by the roadside as hundreds had done before me. Our
surgeon came along, and kindly urged me to keep on, saying we
were to camp in a piece of woods about a mile further on; but I was
too far gone to stir then. I rested an hour or so, and then limped into
camp; too weary to get anything to eat or drink, I took off my
equipments and without even unrolling my blanket, dropped upon
the ground, and with my knapsack for a pillow, slept all night the
dreamless sleep of a tired soldier.
When the boys reached camp, their first thought was to find water;
there was but one well in the vicinity, and that was found under
guard reserved for the headquarters mess. The indignant rank and
file drove off the guard and helped themselves to the water.
Some of the boys, not knowing of the well, went into the swamp and
dipped up the stagnant water there. No wonder there was a large
amount of sickness after that time. It did not make me sick, but I felt
rather lame when I awoke in the morning.
Next day, August 29th, we arrived on the old battle ground of Bull
Run, in time to take part in the second battle of Bull Run. Again we
had to fall back, and again we took up the line of march.
The next day we moved at 3 o’clock A. M. and camped at 11 P. M.,
after a march of twenty eight miles. At Chantilla we met the enemy
on September 1st, but after a short engagement again kept on,
marching through Georgetown into the state of Maryland. It was hot
weather, and many of the men fell exhausted by the way; but we
must not pause, for the enemy was still pressing northward and we
must get between him and our own loved homes.
When we reached the South Mountain battle ground, that fierce
conflict was over and they were burying the dead. I saw the body of
General Reno who was killed in that battle. We had won a victory,
but the loss was very heavy, and we had lost the gallant Reno, a
serious blow for our cause. The idol of his men, they greatly
mourned his loss.
“There was one poor fellow spoke up clear,
How he suffered before he died!
I am dying boys, but I feel no fear,
For I’ve fought by Reno’s side.”