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FLOW ANALYSIS FOR
HYDROCARBON
PIPELINE ENGINEERING
ALESSANDRO TERENZI
Saipem S.p.A., Fano, Italy
Alessandro Terenzi
Gulf Professional Publishing is an imprint of Elsevier
50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States
The Boulevard, Langford Lane, Kidlington, Oxford, OX5 1GB, United Kingdom
Copyright Ó 2022 Elsevier Inc. All rights reserved.
No part of this publication may be reproduced or transmitted in any form or by any

means, electronic or mechanical, including photocopying, recording, or any information
storage and retrieval system, without permission in writing from the publisher. Details
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permissions.
This book and the individual contributions contained in it are protected under copyright
by the Publisher (other than as may be noted herein).
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 using any information, methods, compounds, or experiments described
herein. In using such information or methods they should be mindful of their own safety
and the safety of others, including parties for whom they have a professional
responsibility.
To the fullest extent of the law, neither the Publisher nor the authors, contributors, or
editors, assume any liability for any injury and/or damage to persons or property as a
matter of products liability, negligence or otherwise, or from any use or operation of any
methods, products, instructions, or ideas contained in the material herein.
ISBN: 978-0-12-822466-3
For information on all Gulf Professional Publishing publications visit our

website at https://www.elsevier.com/books-and-journals
Publisher: Charlotte Cockle

Senior Acquisitions Editor: Katie Hammon
Editorial Project Manager: Jai Marie Jose
Production Project Manager: Kamesh Ramajogi
Cover Designer: Matthew Limbert
Typeset by TNQ Technologies

Contents
1. Basics of hydrocarbons thermodynamics 1

1.1 Introduction 1
1.2 Equation of state 2
1.3 Other real fluid properties 4
1.4 The principle of corresponding states 5
1.5 Equilibrium and stability of one-component fluids 10
1.6 Vaporeliquid equilibrium for one-component fluids 14
1.7 Vaporeliquid equilibrium for multicomponent fluids 21
1.8 Equation of state for multicomponent mixtures 29
1.9 Phase diagrams of reservoir fluids 32
References 38
Further reading 39
2. Steady compressible flow 41

2.1 Introduction 41
2.2 1D flow equations in conservative form 43
2.3 1D flow equations for steady adiabatic pipe flow 47
2.4 The velocity of sound 48
2.5 Isentropic flow correlations 50
2.6 Stagnation and critical properties 51
2.7 Flow in area change regions 52
2.8 The convergent nozzle 54
2.9 The convergent-divergent nozzle 57
2.10 Performance of real flow restriction devices 58
2.11 Adiabatic flow with friction in a constant area duct 60
2.12 Real gas pipeline flow properties 65
References 82
Further reading 83
3. Transient compressible flow 85

3.1 Introduction 85
3.2 Small amplitude waves in gases 86
3.3 High amplitude waves in gases 90
3.4 Discontinuities and the Riemann problem 95
3.5 Types of transient operations in pipeline systems 100
3.6 Examples of blowdown system simulations 109
v j
vi Contents
References 118
Further reading 119
4. Multiphase gaseliquid flow 121

4.1 Introduction 121
4.2 Definitions 122
4.3 Flow regimes 124
4.4 Flow pattern map 127
4.5 Basic equations and models 129
4.6 Flow regime transitions 132
4.7 Slug flow 134
4.8 Pressure drop calculations for two-phase pipelines 137
4.9 Sound velocity in two-phase fluids 141
4.10 Design of multiphase pipelines 146
References 154
Further reading 155
5. Pipeline heat transfer 157

5.2 Steady state heat transfer in cylindrical geometry 158
5.3 Steady state external heat transfer modelingdfully buried pipeline 163
5.4 Steady state external heat transfer modelingdpartially
buried or exposed pipeline 168
5.5 Transient external heat transfer modelingdfully buried pipeline 173
5.6 Insulation and heat tracing 175
References 180
6. Flow assurance issues 183

6.2 Hydrates 184
6.3 Wax deposition in pipelines 199
6.4 Asphaltene deposition in pipelines 209
References 214
Further reading 216
7. Flow properties affecting steel pipe material assessment 217

7.2 Low temperature operation 217
7.3 Ductile fracture propagation analysis 225
7.4 Post-Weld Heat TreatmentdPWHT 234
References 240
Contents vii
8. Special pipelines 243

8.2 CO2 pipelines 244
8.3 H2 pipelines 253
References 267
9. Case Studies 271

9A. Precommissioning and commissioning simulations 272
9a.1 Introduction 272
9a.2 Precommissioning and commissioning scenarios 273
9a.3 Pipeline dewatering 274
9a.4 Pipeline air drying 276
9a.5 Pipeline first filling by inert slug purging 283
9a.6 Pig stuck and dislodging 288
References 291
9B. Development of an overpressure protection system 292
9b.1 Introduction 292
9b.2 Pressure control systems and Australian standard requirements 293
9b.3 GLNG pipeline operating mode and pressure control system 294
9b.4 Determination of pressure control system setpoints by
transient hydraulic simulations 297
9b.5 Conclusions 302
References 303
9C. Solar radiationeinduced pressurization 303
9c.1 Introduction 303
9c.2 System description 304
9c.3 Thermal model and tuning 305
9c.4 Simulation results and discussion 307
References 309
9D. Multiphase flow through restrictions 309
9d.1 Introduction 309
9d.2 Multiphase flow modeling in restrictions 310
9d.3 Model matching with lab and field data 315
References 317
9E. Hydrate plug formation analysis in gas-condensate pipe 318
9e.1 Introduction 318
9e.2 Model for hydrate and ice plug formation 319
9e.3 System description 322
9e.4 Simulation results and discussion 324
References 326
viii Contents
9F. Depressurization of flashing liquids 327

9f.1 Introduction 327
9f.2 Pipeline depressurization of an HVP liquid 327
9f.3 Calculation model and sensitivities 329
9f.4 Simulation results 332
References 335
9G. Postweld heat treatment experimental verification 335
9g.1 Introduction 335
9g.2 Field measurements 336
9g.3 Measurements and comparison with calculations 337
9g.4 Conclusions 342
References 342
Index 343
CHAPTER ONE
Basics of hydrocarbons
thermodynamics
Contents
1.1 Introduction 1
1.2 Equation of state 2
1.3 Other real fluid properties 4
1.4 The principle of corresponding states 5
1.5 Equilibrium and stability of one-component fluids 10
1.6 Vaporeliquid equilibrium for one-component fluids 14
1.7 Vaporeliquid equilibrium for multicomponent fluids 21
1.8 Equation of state for multicomponent mixtures 29
1.9 Phase diagrams of reservoir fluids 32
References 38
Further reading 39
1.1 Introduction
Hydrocarbons transported by pipeline systems are usually composed
by a large number of components; at ambient temperatures, some of them
are present in the gas phase, while others are liquids. Some heavier compo-
nents may also appear as solid in some critical operating conditions (hy-
drates, waxes). Water is often present in the transported fluid mixture,
and it is usually treated as a separate phase, even if a hydrocarbon liquid
is present. The behavior of hydrocarbon mixtures depends on their com-
positions as well as the pressure and temperature conditions encountered.
The thermodynamics of mixtures is determined by the contributions of
single components; for this reason, the properties of single components
are covered first. The treatment begins with the description of the equa-
tions of state, defining the relationship between the main fluid properties;
starting with the simplest approach based on ideal gas model, more com-
plex and realistic models are introduced. Thermodynamic equilibrium
conditions are discussed by considering the relevant trends of entropy
Flow Analysis for Hydrocarbon Pipeline Engineering

© 2022 Elsevier Inc.
j
ISBN: 978-0-12-822466-3
https://doi.org/10.1016/B978-0-12-822466-3.00001-1 All rights reserved. 1
2 Flow Analysis for Hydrocarbon Pipeline Engineering
and free energies, for specific systems. Stable equilibrium occurs when it is
independent on time and its previous history, and it is able to resist to small
thermodynamic parameter fluctuations. These concepts are applied to the
analysis of vaporeliquid phase transformations, referred to both single
components and binary mixtures. The discussion is further extended to
multicomponent mixtures, as typical of hydrocarbon fluids. The descrip-
tion of their properties is developed by treating the interaction of different
components, the phase behavior including a vaporeliquid coexistence
condition occupying a finite region of the pressureetemperature diagram,
retrograde condensation phenomena, the different behaviors of reservoir
fluid as depending on their dominant components, and the interaction
with the water phase.
1.2 Equation of state

The thermodynamic properties of a fluid can be defined by using a
volumetric equation of state, providing information about the relationship
between pressure, temperature, and volume (or density).
The simpler EoS (Equation of Sate) is that relevant to the ideal gas
model, which assumes no interaction among fluid particles and neglects their
volume. It is expressed by the following:
PV ¼ RT (1.1)
where:
P ¼ fluid pressure
V ¼ fluid specific volume
R ¼ universal gas constant
T ¼ fluid absolute temperature
In term of compressibility factor Z, defined in this way,
PV
Z¼ (1.2)
RT
the ideal gas model is represented by the condition Z ¼ 1.
The compressibility factor is a parameter giving the indication of the
deviation of a real gas thermodynamic behavior from the ideal gas approx-
imation; actually, the real substances can be described by Eq. (1.1) only in a
limited range of conditions, i.e., at low pressures and moderate tempera-
tures. Hence, other equations of state have been developed on the basis
Basics of hydrocarbons thermodynamics 3
of experimental data of real fluids; the most important from a historical

point of view is the classical Van der Waals equation, given by the
following:
a
P þ 2 ðV bÞ ¼ RT (1.3)
V
In this expression, two parameters have been introduced to represent real
fluid effects, namely:
a ¼ it is a parameter relevant to the Van der Waals intermolecular forces,
which are included as an equivalent pressure term proportional to the in-
verse square of the volume
b ¼ it is a parameter representing the finite volume of molecules
Eq. (1.3) is a so-called cubic EoS, since a cubic algebraic equation must
be solved in order to obtain the volume.
The Van der Waals equation is not very accurate, but it was the first
equation capable of predicting the transition between vapor and liquid;
furthermore, it has also been the prototype for modern, more accurate
equations of state as the PengeRobinson one (Peng and Robinson,
1976), given by:
RT aðT Þ
P¼ (1.4)
V b V 2 þ 2bV b2
or the SoaveeRedlicheKwong (Soave, 1972):
RT aðT Þ
P¼ (1.5)
V b V ðV þ bÞ
The parameters of the above equations can be obtained or by fitting the
equations to PVT data for the fluid of interest or by using general relations
between them and critical point properties (see Section 1.4).
All the above expressions can be written in the following form:
Z 3 þ aZ 2 þ bZ þ g ¼ 0 (1.6)
This is again a cubic algebraic equation that must be solved to get the
compressibility factor Z, as must be for the fluid volume.
All cubic equations of state are approximate; in general, they provide a
reasonable description of thermodynamic properties of vapor and liquid
phases of hydrocarbons, and of vapor region only for many other pure fluids.
The PengeRobinson and SoaveeRedlicheKwong are, at present, among
the more popular cubic equations of state in oil and gas applications.
A different type of equation of state is the virial equation (Sandler, 1999):

PV BðT Þ CðT Þ
¼1 þ þ þ ::: (1.7)
RT V V2
where BðT Þ and CðT Þ are the temperature-dependent second and third
virial coefficients. This expression is of theoretical interest since it can be
derived from statistical mechanics with explicit formulations of the virial
coefficients in terms of particle interactions. It is a power series expansion in
specific volume about the ideal gas result. With a sufficient number of co-
efficients, the virial equation can predict the vapor phase properties with
good precision, but it is not applicable to the liquid phase. However, even in
the case of the gases, it is not recommended for pressure above 10 bar.
1.3 Other real fluid properties

One of the quantities appearing in the fundamental thermodynamic
relationships is the heat capacity. It is possible to show that, given a volu-
metric EoS, and heat capacity data as a function of temperature at a single
value of pressure P1 or volume V1, the value of the heat capacity in any other
state (represented by pressure P2 or volume V2) can be computed by the
following (Sandler, 1999):
ZP2
v2 V
CP ðP2 ; T Þ ¼ CP ðP1 ; T Þ T dP (1.8)
vT 2 P
P1
ZV2
v2 P
CV ðV2 ; T Þ ¼ CV ðV1 ; T Þ T dV (1.9)
vT 2 V
V1
where CP and CV are the constant pressure and constant volume heat ca-
pacities, respectively.
In practice, heat capacity data are usually collected for low pressure con-
ditions or large specific volumes where all fluids are ideal gases. Hence, if P1
or V1 are taken as 0 and N, respectively in Eqs. (1.8) and (1.9) above, it is
possible to write:
ZP 2
v V
CP ðP; T Þ ¼ CP* ðT Þ T dP (1.10)
vT 2 P
0
ZV
v2 P
CV ðV ; T Þ ¼ CV* ðT Þ T dV (1.11)
vT 2 V
N
where the asterisk denotes the ideal gas heat capacity. Usually, the tem-
perature dependence of the ideal gas heat capacity is given in polynomial
form as follows:
CP* ðT Þ ¼ A þ BT þ CT 2 þ DT 3 (1.12)
Other thermodynamic variables that allow to calculate the deviations of
the real fluid behavior from the ideal gas status are the “Departure
Functions.”
In particular, it is possible to show that, for what concerns the enthalpy H
and the entropy S, their changes for a real fluid are equal to that of an ideal
gas undergoing the same transformation plus the departure of the fluid from
the ideal gas behavior at the end state less the departure from the ideal gas
behavior at the initial state. These “Departure Functions” can be computed
from the equation of state, based on the following:
ZP
vV
H H IG
¼ V T dP (1.13)
vT P
0
ZP
vV R
SS IG
¼ dP (1.14)
vT P P
0
1.4 The principle of corresponding states

The analysis presented in Sections 1.2 and 1.3 has shown that it is
possible to calculate the thermodynamic characteristics of a real substance
given only the ideal gas heat capacity and the volumetric EoS. However,
the necessary information on the EoS is not always available for all fluids.
Hence, it is possible to resort to the principle of corresponding states, which
allows to predict thermodynamic properties of fluids from generalized prop-
erty correlations based on experimental data for similar fluids.
We concentrate our attention on a volumetric EoS, which is deter-
mined by the intermolecular interactions. From the study of molecular
behavior, it has been found that molecules can be grouped into classes,
such as spherical molecules, nonspherical molecules, molecules having a

permanent dipole, and so on, and that within any one class molecular in-
teractions are similar.
It has been also found that all the members of a class obey the same volu-
metric EoS, i.e., the volumetric data of each member are fitted by simply
changing the parameters of the EoS. The fact that several different molecular
species may be described by a volumetric EoS of the same form suggests that
it might be possible to construct generalized correlations for both the EoS
and density-dependent contribution to enthalpy, entropy, and other ther-
modynamic variables. The first historical generalized correlation arose
from the study of the Van der Waals EoS. Fig. 1.1 shows the isotherms of
this equation in a P versus V diagram, for five values of temperature
including the critical temperature TC, which is defined as the maximum
temperature at which a liquid phase can exist. To be noted that this defini-
tion holds for a single component fluid only.
It can be observed in this figure that the isotherms with temperature
below the critical one exhibit a non-monotone behavior, with a local min-
imum followed by a local maximum over part of the specific volumed
pressure range. Such trend is associated with a liquidevapor transition.
While this behavior is absent for T > TC, in such a way that the liquid phase
cannot exist in this range, in the critical temperature curve, the two ex-
tremes coincide, and this point (called critical point) is an inflection point,
T1
T2
TC
T3
T4
P
V
Figure 1.1 Isotherms of the Van der Waals EOS in a plane (P,V).
where the first and second derivative of P with respect to V vanishes simul-
taneously. This is expressed analytically by the following requirements:
2
vP v P
¼ 0 and ¼ 0 at PC and VC (1.15)
vV TC vV 2 TC
By replacing Eq. (1.3) in the relations (1.15), the following expressions of
the Van der Waals parameters a and b are obtained:
VC 9VC RTC
b¼a¼ (1.16)
3 8
Using (1.16) in the Van der Waals Eq. (1.3), it is possible to get the pres-
sure PC and the compressibility factor ZC at the critical point:
a P C VC 3
PC ¼ 2
ZC ¼ ¼ (1.17)
27b RTC 8
By using the above expressions and by defining the dimensionless vari-
ables called reduced temperature Tr, reduced pressure Pr and reduced vol-
ume Vr
P T V
Pr ¼ ; Tr ¼ ; Vr ¼ (1.18)
PC TC VC
the following form of the Van der Waals equation of state is obtained:

3
Pr þ 2 ð3Vr 1Þ ¼ 8Tr (1.19)
Vr
From (1.19) it is concluded that all the fluids obeying the Van der Waals
equation of state have the same numerical value of reduced volume for given
values of Pr and Tr. Two fluids having the same values of reduced pressure
and temperature are said to be in corresponding states.
The principle of the corresponding states has been historically repre-
sented by drawing the compressibility factor Z as function of reduced pres-
sure and temperature, as shown in Fig. 1.2, where the compressibility data
for several fluids have been reported.
Fig. 1.2 demonstrates that the idea of the corresponding states is reason-
able, since the general trend of the data confirms the similarity represented
by (1.19). However, it can be observed that compressibility factors for inor-
ganic fluids are almost always below those for hydrocarbons. Furthermore, if
(1.19) were universally valid, all fluids would have the same value of the crit-
ical compressibility ZC ¼ 0.375, as shown by (1.17), while for most fluids,
the critical compressibility is in the range 0.23e0.31.
Figure 1.2 Compressibility factor for several fluids as a function of reduced pressure
and temperature. From Su and Chang (1946).
These deviations have led to the development of more complicated cor-

responding states principles. The simplest generalization is based on the
adoption of a family of different relations Z ¼ Z(Pr,Tr), with different values
of ZC, i.e., the critical compressibility factor is used as an additional param-
eter of the compressibility law:
Z ¼ ZðTr ; Pr ; ZC Þ (1.20)
In fact, other quantities have been considered as additional correspond-
ing states parameters, since the critical compressibility factor ZC is not
known with enough accuracy for many substances.
Pitzer (1995) has proposed the so-called acentric factor u as third correl-
ative parameter, which is defined in this way:
u ¼ 1:0 Log10 ðP vap ðTr ¼ 0:7Þ = PC Þ (1.21)
Here P vap ðT
r ¼ 0:7Þ is the vapor pressure of the fluid at Tr ¼ 0:7.
Even these extensions of the corresponding state concept have been
found not suitable to represent the thermodynamic behavior of some kinds
of molecules, in particular that having dipoles or quadrupoles. Hence, this
application remains limited to some classes of molecules only, as in case of
most hydrocarbons.
The modern version of the corresponding states idea is the use of gener-
alized EoS.
The Van der Waals equation is the first example of application of this
approach. In fact, the expressions (1.16), rewritten in terms of the critical
pressure and temperature in this way,
27R2 TC2 RTC
a¼ b¼ (1.22)
64PC 8PC
demonstrate that the thermodynamic properties of a class of fluids with
parameters a and b that have not been derived from a set of experimental data
can be described by knowing the fluid critical properties only. As it was said
before, the Van der Waals equation is not accurate enough, and other more
sophisticated equations are used.
In particular, we consider here the PengeRobinson equation already pre-
sented in Section 1.1, by showing that its generalized form is given by the
following:
RT aðT Þ
P¼ 2 (1.23)
V b V þ 2bV b2
with:
R2 TC2
aðT Þ ¼ 0:45724 aðT Þ (1.24)
PC
RTC
b ¼ 0:0778 (1.25)
PC
rffiffiffiffiffiffiffi 2
T
aðT Þ ¼ 1 þ c 1 (1.26)
TC
c ¼ 0:37464 þ 1:54226u 0:27u2 (1.27)

The above relationships were obtained by Peng and Robinson in order
to improve the predictions of the boiling point pressure versus temperature,
and the function aðT Þ was chosen by fitting the vapor pressure values for
many fluids. With respect to the Van der Waals scheme, the generalized
PengeRobinson approach uses one parameter more other than PC and
TC, namely the acentric factor u.
This equation can be used to calculate not only the compressibility fac-
tor, but also the departure functions for the other thermodynamic
properties.
Another very popular cubic equation of state used in the oil and gas in-
dustry is the SRK (SoaveeRedlicheKwong):
RT aðT Þ
P¼ (1.28)
V b V ðV þ bÞ
with:
R2 TC2
aðT Þ ¼ 0:42748 aðT Þ (1.29)
PC
RTC
b ¼ 0:08664 (1.30)
PC
rffiffiffiffiffiffiffi 2
T
aðT Þ ¼ 1 þ c 1 (1.31)
TC
c ¼ 0:37464 þ 1:54226u 0:27u2 (1.32)

The current industrial practice is based on the application of the corre-
sponding states concept, by assuming that different fluids are described by
the same generalized equations of state, and that their thermodynamic
behavior in an extended pressure and temperature range is described by
knowing the generalized parameters only. Such kind of equations can
give a very accurate thermodynamic picture of many substances, in partic-
ular hydrocarbons.
1.5 Equilibrium and stability of one-component fluids

The equilibrium state of a closed thermodynamic system can be
derived by using the energy and entropy balances derived from the first
and second principles of thermodynamics:
dU dV
¼ Q_ P (1.33)
dt dt
dS Q_
¼ þ S_ irr (1.34)
dt T
where:
U ¼ specific internal energy
Q_ ¼ heat transfer rate
S_ irr ¼ rate of internal generation of entropy by irreversible processes 0
In (1.33) only work due to deformation of the system boundaries is
considered.
For an adiabatic (Q_ ¼ 0) and constant volume system, the system of en-
ergy and entropy balances equations becomes
dU
¼0 (1.35)
dt
dS _
¼ Sirr 0 (1.36)
dt
Since the entropy function can only increase during the approach to
equilibrium due to (1.36), the entropy must be a maximum at equilibrium.
Hence, the equilibrium criterion for a closed and isolated system is as
follows:
S ¼ maximum (1.37)
This principle can be illustrated by referring to the simple system shown
in Fig. 1.3.
The system is composed by two subsystems containing different amounts
of the same molecular species of particles of a single-component fluid (N
represents the number of moles). They are connected by a channel of infin-
itesimal volume equipped by an ideal valve opening instantaneously. The
system is assumed adiabatic and constant volume, exchanging neither mass
neither energy with the external environment. However, the two subsys-
tems can exchange heat and mass across the communication channel
when the valve is open. For the global system, the total number of moles
N1, S1, U1, V1 N2, S2, U2, V2
Figure 1.3 Isolated nonequilibrium system.

N, the total internal energy U, the total volume, and the total entropy are
given by the addition of the two subsystems contributions:
N ¼ N1 þ N2 (1.38)
U ¼ U1 þ U 2 (1.39)
V ¼ V 1 þ V2 (1.40)
S ¼ S1 þ S2 (1.41)
By using the fundamental thermodynamic relationships, the entropy
change of each i-th subsystem after communication and mixing of particles
can be expressed as a function of changes in the number of moles, volumes,
and internal energy by the following:

vSi vSi vSi 1 Pi Gi
dSi ¼ dUi þ dVi þ dNi ¼ dUi þ dVi dNi
vUi vVi vNi Ti Ti Ti
(1.42)
where Gi is the i-th subsystem molar Gibbs energy.
The entropy change dS of the overall system can be easily obtained by
summing the two subsystems contributions, by considering that the total
quantities given by (1.38), (1.39), and (1.40) are constant:

1 1 P1 P2 G1 G2
dS ¼ dU1 þ dV1 dN1 (1.43)
T1 T2 T1 T2 T1 T2
Since the entropy must be a maximum at equilibrium, the (1.25) expres-
sion must vanish for system variations, thus obtaining the following:
1 1
¼ 0 T1 ¼ T2 (1.44)
T1 T2
P1 P2
¼ 0 P1 ¼ P2 (1.45)
T1 T2
G1 G2
¼ 0 G1 ¼ G 2 (1.46)
T1 T2
Hence, the equilibrium condition for an adiabatic isolated system states
that all its subsystems must have the same temperature, the same pressure,
and the same molar Gibbs energy.
The above discussion is based on the condition dS ¼ 0, which is neces-
sary but not sufficient for S to reach a maximum value. The further
condition d 2 S 0 assures that a maximum entropy value, giving a true

equilibrium state, has been identified. On the contrary, a minimum of the
entropy corresponds to an unstable state. Therefore, the sign of d2 S deter-
mines the stability of the thermodynamic state found from dS ¼ 0.
It is possible to determine the equilibrium and stability for other kinds of
systems also.
For instance, for a closed system kept at constant temperature and vol-
ume, the energy and entropy balance equations become
dU
¼ Q_ (1.47)
dT
dS Q_
¼ þ S_ irr (1.48)
dt T
By combining the above equations, the following relationship, written in
term of the molar Helmholtz free energy F, is obtained:
dðU TSÞ dF
¼ ¼ T S_ irr 0 (1.49)
dt dt
Since the molar Helmholtz free energy F can only decrease during the
approach to equilibrium due to (1.49), it must be a minimum at equilibrium.
Hence, the equilibrium criterion for a closed system kept at constant
temperature and volume is the following:
F ¼ minimum (1.50)
For a closed system kept at constant temperature and pressure, the energy
and entropy balance equations become the following:
dU dðPV Þ
¼ Q_ (1.51)
dt dt
dS Q_
¼ þ S_ irr (1.52)
dt T
By combining the above equations, the following relationship, written in
term of the molar Gibbs free energy G, is obtained:
dU dðPV Þ dðTSÞ dG
þ ¼ ¼ T S_ irr 0 (1.53)
dt dt dt dt
which leads to the following equilibrium criterion:
G ¼ minimum (1.54)
Table 1.1 Equilibrium and stability conditions for selected systems.

Equilibrium Stability
Kind of system Constraints condition condition
Isolated, adiabatic U ¼ constant, S ¼ maximum, d2 S 0

system with V ¼ constant dS ¼ 0
constant volume
Isothermal, closed T ¼ constant, F ¼ minimum, d2 F 0
system with V ¼ constant dF ¼ 0
constant volume
Isothermal, isobaric T ¼ constant, G ¼ minimum, d2 G 0
closed system P ¼ constant dG ¼ 0
Actually for all the systems considered here, the application of the equi-
librium criteria determines that they are at uniform temperature, pressure,
and molar Gibbs free energy.
The equilibrium and stability conditions for the system under consider-
ation, written for a single-component fluid, are summarized in Table 1.1. It
is possible to show that they are also valid for multicomponent fluids.
From the stability criteria listed in Table 1.1, three fundamental thermo-
dynamic inequalities can be derived for systems considered in a stable equi-
librium state:

vP vU
CV > 0; < 0; > 0 (1.55)
vV T vT
1.6 Vaporeliquid equilibrium for one-component

fluids
Now we are going to analyze the equilibrium of two phases (vapor
and liquid) on the basis of the discussion exposed in Section 1.5. In
Fig. 1.4, some isothermal curves in a plane (P,V) are shown, as given by a
typical cubic EoS. These curves are represented for increasing temperature
(T1 < T2 < T3 < T4 < T5). We can observe that the isotherms labeled by
T1 and T2 do not have a monotone trend, but they present a minimum fol-
lowed by a maximum in a certain region of the (P,V) diagram. Therefore,
while for the high-temperature isotherms the stability condition ðvV
vP Þ <
T
0 is fulfilled everywhere, this is not true for the low-temperature isotherms.
Actually, the regions of the diagram where the stability violation occurs are
not physically realizable and cannot be observed in practice. Thus, in this
T1
T2
T3
T4
T5
P
V
Figure 1.4 Isotherms on a plane (P,V) predicted by a cubic equation of state.
particular thermodynamic region, the cubic equations of state fail to predict

the real behavior of the fluid, and their trend must be replaced by another
physical description. The isotherm at temperature T3 has a single point for
which the first and second derivatives of pressure which respect to volume
vanish simultaneously: this is called critical point and T3 is the critical tem-
perature (usually identified as TC).
A low-temperature isotherm is represented alone in Fig. 1.5; it is shown
that the intersection of a horizontal line at constant pressure with the curve
gives three possible values for the volume of the fluid, V 0 , V 00 , and V 000 . One
of these, V 00 , is on the part of the isotherm that is unphysical for the above
mentioned stability reasons. The other two values have a physical meaning
instead, and they represent the volumes of the liquid and vapor phase,
respectively, at the specified pressure and temperature.
The true thermodynamic behavior in the region between V 0 and V 000 is
shown in Fig. 1.6, where a phase change occurs along the considered
isotherm isobar represented by the horizontal section which boundary vol-
umes are the single-phase liquid and vapor volumes labeled as V L and V V .
This is the vaporeliquid coexistence region. The two-phase mixture spe-
cific volume V M varies in this region since, although the specific volumes
of the single phases are fixed, the vapor fraction a in the mixture varies
from 0 to 1, thus giving the following:
V M ¼ aV V þ ð1 aÞV L (1.56)
Isotherm T1 < T3
Isobaric Line
P
V' V'' V'''

V
Figure 1.5 Low-temperature isotherm in a plane (P,V) predicted by a cubic EoS.
Isotherm T1 < T3
P
V L
V V
V
Figure 1.6 Real low-temperature isotherm in a plane (P,V) including the vaporeliquid
phase transition.
Thus, the isotherm section predicted by a cubic EoS in the two-phase

region of a single-component fluid must be replaced by the isobaric hori-
zontal line shown in Fig. 1.6.
The question that remains is the value of pressure corresponding to the
vaporeliquid coexistence region. The criterion to be applied in order to
find this pressure is the equality of the two phases Gibbs free energies, as
derived from Section 1.5. From fundamental thermodynamic relationships,

the free Gibbs energy variation DG along an isotherm is given by the
following integral:
ZP 00
DG ¼ VdP (1.57)
P0
Thus, by using the equation of state which provides the relationship
among V and P, the value of the phase change pressure P f is obtained
by the following:
ZP 00 ZP 00 ZP a
GV GL ¼ 0 ¼ VdP þ VdP þ VdP (1.58)
Pa P0 P 00
where P 0 and P 00 are the minimum and maximum pressure values in the phase
transition region. Graphically, this corresponds to the equality between the
regions A and B of Fig. 1.5, comprised between the horizontal transition line
and the isotherm curve given by the cubic EoS. Fig. 1.4 must be replaced by
Fig. 1.7, showing the true thermodynamic behavior associated to the phase
transition, in which the two-phase mixture region is included inside a dome-
shaped envelope curve crossing the low-temperature isotherms. For
T1
T2
TC
T4
T5
Liquid-Vapour Coexistence Region

P
V
Figure 1.7 Real isotherms in a plane (P,V) including the vaporeliquid coexistence
region.
Liquid-Vapour Transition Curve
Critical Point
(TC , PC )
P
T
Figure 1.8 Liquidevapor transition curve in a plane (P,T).
temperatures above the critical temperature, no phase transition can occur,

and the fluid is said to be in the supercritical condition or dense phase gas.
A typical phase transition curve in a (P,T) diagram has the form shown in
Fig. 1.8, ending with the critical point identified by the couple (TC, PC).
Again, for temperatures above the critical temperature, no phase transition
can occur (supercritical fluid). For temperatures T < TC and pressures
P > PC, the fluid is in the liquid phase, but its thermodynamic properties,
close to the critical conditions, are very similar to that of the supercritical
gas in such a way they are practically indistinguishable.
The equation P ¼ PðT Þ of the phase transition curve can be derived by
applying the equality of the Gibbs free energies relevant to the two phases:
G V ðT ; PÞ ¼ G L ðT ; PÞ (1.59)
From (1.59), it descends that for small changes of pressure and temper-
ature the changes of the Gibbs free energies are small and equal:
dGV ¼ dGL (1.60)
From fundamental thermodynamic relationships, the differentials of
(1.60) can be expressed in terms of the other thermodynamic quantities in
this way:
V V dP S V dT ¼ V L dP SL dT (1.61)
And, by indicating with DV ; DS the changes in specific volume and entropy

when passing from one phase to the other, from (1.61), we obtain the
following:
vP DS DH
¼ ¼ (1.62)
vT DV T DV
where DH is the phase transition enthalpy variation, also called latent heat of
vaporization (or condensation). The (1.62) is known as Clapeyron equation.
The pressure at which the liquid and vapor phases are in equilibrium is
termed vapor or saturation pressure, here indicated as P vap . From (1.62),
its trend as function of temperature P vap ¼ f ðT Þ can be obtained. At
temperatures for which the vapor pressure is not very high, it results that
V V >> V L and DV zV V . Furthermore, if the vapor can be treated as
ideal, we have DV ¼ V V ¼ RT P , thus giving the following:
dP vap P vap DH vap
¼ (1.63)
dT RT 2
that can be written also as follows:
dðln P vap Þ DH vap
¼ (1.64)
dT RT 2
where DH vap ¼ H V H L is just the latent heat of vaporization.
The integration of (1.64) gives the wanted vapor pressure temperature
function; if it is assumed that the temperature dependence of DH vap is negli-
gible, we get the following:
DH vap
ln P vap ¼ þC (1.65)
RT
where C is an integration constant.
A common correlation used to reproduce the vapor pressure as temper-
ature function is the Antoine equation, which is very similar to (1.65) and it
is expressed in this way:
D
ln P vap ¼ þC (1.66)
T þE
where D and E are correlating parameters.
The discussion reported so far has been concerned with the analysis of
stable equilibrium states of a single-component fluid. However, metastable
states as the superheated liquid and the subcooled vapor can occur in
Isotherm T1 < T3
Superheated Liquid
Subcooled Vapour
P
VV VL
V
Figure 1.9 Metastable states along an isotherm in a plane (P,V).
experiments. In fact, by suitable experimental procedures in which the ther-

modynamic transformation along an isotherm is realized very slowly, by
avoiding as much as possible the onset of bubble nucleation in case of liquid
and of droplet nucleation in case of vapor, the one-phase isotherm sections
can be prolonged outside the stability region as shown in Fig. 1.9. The liquid
belonging to the extended left isotherm portion is said superheated liquid
and the vapor belonging to the extended right isotherm portion is said sub-
cooled vapor. Both these states are metastable since they exist as one-phase
fluids in a region where the two-phase transition should have had occurred,
and if slightly perturbed, the fluid experiences a sudden transition toward the
stable condition.
Actually, in the study of liquidevapor equilibria, it is common practice
to utilize the so-called fugacity in the equilibrium equation, instead of the
Gibbs free energy.
The fugacity f is defined in this way:
0 1
ZP
GðT ; PÞ G IG ðT ; PÞ 1 RT
f ¼ P exp ¼ P exp@ V dP A
RT RT P
0
(1.67)
Another quantity correlated to the fugacity is the fugacity coefficient
f ¼ Pf .
GIG ðT ; PÞ in (1.67) represents the Gibbs free energy of the fluid treated
as an ideal gas.
The fugacity has in fact the units of pressure, and it becomes equal to the
pressure at pressure low enough that the fluid approaches the ideal gas state.
The reason for introducing this parameter in the phase equilibrium
calculations is that it is directly related to the EoS by the expression
(1.67), and it possible to show that the Gibbs free energy equality crite-
rion shown in (1.59) is equivalent to the equality of fugacities or fugacity
coefficients:
f V ðT ; PÞ ¼ f L ðT ; PÞ (1.68)
fV ðT ; PÞ ¼ fL ðT ; PÞ (1.69)
For low pressure liquids, it can be found that the fugacity is equal to its
vapor pressure at the same temperature, that is:
f L ðT ; PÞ ¼ P vap ðT Þ (1.70)
1.7 Vaporeliquid equilibrium for multicomponent

fluids
The phase equilibrium in multicomponent mixtures can be studied by
making reference to the equality of fugacities as shown in Section 1.6 and
considering that now the situation is influenced by the fluid composition,
i.e., by the relative amount of a component with respect to the others.
Thus, Eq. (1.68) should be rewritten in this way, for the i-th component
of a mixture:
fiV ðT ; P; yÞ ¼ fiL ðT ; P; xÞ (1.71)
where y; x are the vapor and liquid molar compositions, respectively.
The fugacity of a component in a liquid or vapor phase of a mixture is
expressed by the following:
IM
!
G i ðT ; PÞ Gi ðT ; PÞ
fi ðT ; P; xÞ ¼ xi P exp
L
(1.72)
RT
IM
!
G i ðT ; PÞ Gi ðT ; PÞ
fi ðT ; P; yÞ ¼ yi P exp
V
(1.73)
RT
The differences of the above fugacity definitions with respect to the

single-component one reported by (1.67) are the following:
• There is a dependence of the fugacity from the component molar frac-
tion xi or yi , according to the phase which is considered
• The quantity appearing inside the exponential argument is not the Gibbs
free energy but its derivative with respect to the number of moles Ni of
the i-th component, called also chemical potential G i ¼ vN vG
i
• The ideal term for the chemical potential is referred to an ideal mixture,
i.e., a mixture in which the interactions between the molecules are
negligible
However, while usually for a vapor the expression (1.73) can be used
directly, with reference to a specific EoS, in some cases, this is not possible
for a liquid, because it can happen that a suitable EoS is not available. In this
case, the fugacity of the component in the liquid phase fiL ðT ; P; xÞ can be
correlated to the fugacity of the component considered alone fiL ðT ; PÞ,
through the so-called activity coefficient gi :
fiL ðT ; P; xÞ ¼ xi gi ðT ; P; xÞfiL ðT ; PÞ (1.74)
Hence, there are two different methods to study the liquidevapor equi-
librium of a multicomponent mixture:
(i) Method 4 4: the fugacities of both phases are defined by using an EoS
(ii) Method g 4: the fugacity of the vapor phase is calculated by an EoS,
while the fugacity of the liquid phase is calculated by an activity
coefficient
It must be observed that the method (a) is more accurate, since it can give
a congruent description over a wide range of pressure and temperature, in
particular, close to the critical region. The main disadvantage of method
(b) is that it is based on a different modeling of the two phases, which
may come in conflict when the properties of the two phases should be iden-
tical, i.e., in the critical region.
As a first example of application of the equilibrium calculation method,
we consider a binary mixture at low pressure. In this simple case, the
following simplifications can be made for the definition of the fugacities:
(1) The fugacity of the i-th component in the vapor phase fiV ðT ; P; yÞ can
be expressed by the LewiseRandall rule (Sandler, 1999), valid just at
low pressure, in this way:
fiV ðT ; P; yÞ ¼ yi P ¼ Pi (1.75)
that is, it is equal to the component partial pressure Pi in the vapor mixture.
(2) The fugacity of the i-th component in the liquid phase fi L ðT ; P; xÞ can
be expressed by the activity coefficient model:
vap
fi L ðT ; P; xÞ ¼ xi gi ðT ; P; xÞPi ðT Þ (1.76)
vap
that is, it is proportional to the component vapor pressure Pi ðT Þ
at the
specified temperature. A further simplification can be made if the liquid
phase is assumed to behave as an ideal liquid mixture (gi ðT ; P; xÞ ¼ 1):
vap
fiL ðT ; P; xÞ ¼ xi Pi ðT Þ (1.77)
The application of the equilibrium condition (1.56) becomes the
following:
vap
yi P ¼ Pi ¼ xi Pi ðT Þ (1.78)
By summing (1.63) over all components we obtain the following:
X vap
P¼ xi Pi ðT Þ (1.79)
i
Eq. (1.79), called Raoult’s law, shows that the total pressure of an ideal
mixture P is given by the sum of the products of liquid phase mole fractions
by vapor pressure of each component.
Fig. 1.10 shows Eq. (1.79) in graphical form, with reference to a binary
mixture whose lighter component liquid mole fraction is x1 and its vapor
vap
pressure is P1 , while the same parameters relevant to the heavier compo-
vap
nent are called x2 and P2 , respectively. The most important conclusion
drawn from this diagram is that the equilibrium pressure is a linear function
of the liquid phase mole fraction.
Once the equilibrium total pressure has been obtained for a certain liquid
molar composition, the vapor equilibrium composition can be calculated by
(1.78); for instance, the lighter component vapor molar fraction is the
following:
vap
x1 P1
y1 ¼ (1.80)
P
The complete vaporeliquid equilibrium diagram can be built by vary-
ing the liquid molar composition and determining the corresponding va-
por molar composition by (1.80). Fig. 1.11 presents the equilibrium
pressure as function of the composition of both phases at fixed
0.9
T=fixed
0.8
0.7
P
0.6
P (bar)
x1P1vap
0.5
0.4
0.3
x2P2vap
0.2
0.1
0
0 0.2 0.4 0.6 0.8 1
Lighter Component Mole Fraction in the Liquid Phase
Figure 1.10 Equilibrium pressure and species liquid phase fugacities versus liquid mole
fraction for a low pressure ideal binary mixture at fixed temperature.
1
T=fixed
0.9 Liquid
0.8
0.7 Tie Line

P (bar)
x y
0.6
0.5 Vapour
0.4
0.3
0 0.2 0.4 0.6 0.8 1
Lighter Component Mole Fraction
Figure 1.11 Equilibrium pressure versus lighter component mole fraction for a low
pressure ideal binary mixture at fixed temperature.
temperature. The compositions of the two coexisting phases at a fixed

pressure are obtained by the intersection of a horizontal line with the vapor
and liquid curves. The section of this line connecting the equilibrium
composition in the two phases is called tie line. The diagrams presented so
far are referred to constant temperature systems, but pressure can also be
fixed and equivalent phase diagrams can be derived. The region above
the liquid equilibrium pressure line is occupied by a liquid phase mixture,
while the region below the vapor equilibrium pressure line is occupied by
a vapor phase mixture; the two coexisting phases are present between the
two lines. The liquid equilibrium pressure line is also called bubble-point
curve, while the vapor equilibrium pressure line is called dew-point curve,
since the first one corresponds to the condition of formation of the first
vapor bubbles when the fluid is coming from the liquid region and it is
depressurized, and the second one corresponds to the condition of forma-
tion of the first liquid droplets when the fluid is coming from the vapor
region and it is compressed.
The main indication drawn from this kind of diagrams is the important
difference with the phase transition phenomenon of single-component
fluids: in fact, while for a fixed temperature, a single boiling (and condensa-
tion) pressure exists for a one-component substance, for a binary mixture, a
complete phase transition curve depending on composition exists.
The process of composition variation during a thermodynamic transfor-
mation as an isotherm expansion can be visualized in Fig. 1.6, where the
same binary mixture represented in Figs. 1.10 and 1.11 has been analyzed.
The starting point of the expansion is in the liquid phase, and the relevant
lighter component molar fraction in the mixture is about 0.45. When the
fluid is depressurized by keeping the temperature constant (vertical line of
Fig. 1.12), it crosses the bubble-point curve and the first bubbles of vapor
begin to form. The tie-line of this point indicates that in the liquid phase,
which is predominant at this point in the system, the molar composition
is the initial one, while in the vapor phase, the amount of the lighter compo-
nent is much higher than in the liquid, since it is more volatile and prone to
evaporate faster than the other heavier components (the relevant molar frac-
tion in the vapor phase is about 0.75). When the fluid is further expanded,
the tie-line indicates that the lighter component molar fraction decreases in
both phases: in the liquid phase, because it is more volatile and tends to evap-
orate early leaving the liquid richer in the heavier component, and in the
vapor phase because, while at the beginning the vapor bubbles were
composed mainly by this light element, during the expansion, the heavier
fluid begins to evaporate also, enriching the vapor phase. When the mixture
crosses the dew-point line, all the fluid has been converted into vapor, hav-
ing the initial molar composition as obvious. The same evaporation trend
1
Starting Point of Depressurization
T=fixed
0.9
Liquid
0.8
0.7 x'
P (bar)
y'
x''
0.6 y''
x'''
y'''
0.5
Vapour
0.4
Final Point of Depressurization
0.3
0 0.2 0.4 0.6 0.8 1
Figure 1.12 Isothermal expansion of a low pressure ideal binary mixture in the phase
equilibrium diagram as function of lighter component mole fraction.
could be followed also in the corresponding equilibrium diagram drawn as a

function of the heavier component mole fraction, taking into account that
the curves would have an opposite slope.
Until now we have considered the case of ideal mixtures for which the
Raoult’s law was valid, giving a linear trend of the equilibrium pressure
versus the liquid molar composition.
In practice, few liquid mixtures are ideal, and the real trends are often
expressed as nonlinear equilibrium curves. As an example of this situation,
Fig. 1.13 shows the phase diagram of a mixture in which both the transition
curves present a maximum, coincident for a given composition. Such kinds
of mixtures are called azeotropic mixtures or azeotropes, and their occur-
rence can be annoying for distillation processes. In fact, such procedures
are based on the separation of components of a mixture by variation of a
certain physical parameter, as temperature, for instance, which allows phase
segregation; the efficiency of the distillation is proportional to the distance of
the transition curves in the phase diagram; that is, the distillation is as better as
the two curves are far each from the other. When an azeotrope occurs, this is
detrimental since in the curves contact point the composition of both phases
is exactly equal and no separation between the components can be made by
segregating the phases.
1.6
T=fixed
Liquid
1.4
1.2
P (bar)
Vapour
1
0.8
0.6
0.4
0 0.2 0.4 0.6 0.8 1
Figure 1.13 Equilibrium pressure versus lighter component mole fraction for an azeo-
tropic binary mixture at fixed temperature.
The previous discussion has been focused on the study of low pressure
vaporeliquid equilibrium, involving the use of activity coefficients to
describe the behavior of the liquid phase. Now we are going to examine
high pressure phase equilibria for mixtures in which both phases fugacities
are calculated by an equation of state (method 4 4).
One example of the situation of interest is represented in Fig. 1.14,
where the equilibrium curves are shown for three different values of temper-
ature, T1 < T2 < T3, for a certain binary mixture.
The lowest isotherm curves, drawn for T ¼ T1, are below the critical
temperature of both components; hence, in this case vapor and liquid exist
for all compositions. This condition is similar to the low pressure diagram of
Fig. 1.11.
The other two equilibrium curves are relevant to temperatures above the
critical temperature of the lighter component; hence, this component
cannot exist as a liquid at these temperatures, nor can mixtures very rich
in it. Therefore, both these equilibrium curves end at lighter component
mole fractions <1, and at higher mole fractions, only vapor is present.
The ending points of these higher temperature curves, at which the relevant
bubble and dew point curves intersect, are two critical points for the binary
mixture. Thus, there is not a single critical point for a mixture, but a range of
critical conditions as function of pressure, temperature, and composition.
50
T=T3 T=T2
45
40
Liquid Liquid
Vapour
35
Vapour
30
P (bar)
25
20
15 T=T1
10 Liquid
Vapour
5
0
0 0.2 0.4 0.6 0.8 1
Figure 1.14 Equilibrium pressure versus lighter component mole fraction for a binary
mixture at three values of temperaturedHigh pressure range.
In Fig. 1.15, the bubble and dew point curves of a binary mixture are
plotted as a function of temperature, for various fixed compositions. The
leftmost curve represents the vapor pressure of the lighter component,
whose mole fraction is indicated as x1. Obviously for a one-component fluid
the bubble and dew point curves would coincide with the unique vapor
pressure curve. The rightmost curve is the vapor pressure of the heavier
component, while intermediate curves are the bubble and dew point curves
for several fixed compositions of the mixture. The red curve connecting all
the critical points relevant to each composition is called Critical Locus. Actu-
ally, the phase diagram constructed so far can be thought as the envelope of
the equilibrium curves relevant to all the possible mixture compositions. As
already stated with reference to Figs. 1.11 and 1.12, it can be observed that
the boiling or condensation process of a multicomponent mixture does not
occur along an isotherm isobar transformation, but a finite region of the
phase diagram is involved.
65
Critical Locus
60 x1=0.7 x1=0.5 x1=0.3

x1=0.9
x1=0.1
55 x1=1
P (bar)
x1=0
50
45
40
280 290 300 310 320 330 340 350 360 370
T (K)
Figure 1.15 Equilibrium pressure versus temperature for a binary mixture at various
values of molar composition.
When multicomponent mixtures (with more than two components) are

considered, the shape of the phase diagram is similar to that of Fig. 1.15, but
with an envelope curve limiting the vaporeliquid coexistence region much
more influenced by the contributions of the different molecules. Thus, it is
not possible to single out the limiting vapor pressure curves of the lighter and
heavier components, since the form of the envelope curve is rounded and
dome shaped.
In the next Section 1.8, the application of cubic EoS for multicompo-
nent mixtures will be presented, while in Section 1.9, the discussion about
thermodynamic equilibrium will be extended to typical hydrocarbon multi-
component mixtures treated in oil and gas applications.
1.8 Equation of state for multicomponent mixtures

In order to describe the thermodynamics of multicomponent mixtures
by applying the equations of state as per Sections 1.2 and 1.4, it is necessary
to introduce the composition as an additional variable. This is done by
adopting appropriate mixing rules for the calculation of the parameters
appearing in the reference equations, thus allowing to find them as averaged
from those of pure components.
When considering the parameters a and b for the PengeRobinson and

SRK equations of state (23) and (28), to N-component mixtures, the
following classical mixing rules can be applied:
X
N X
N
a¼ zi zj aij (1.81)
i¼1 j¼1
X
N
b¼ zi bi (1.82)
i¼1
where zi and zj are the mole fractions of component i and j, respectively. The
term bi is the b-parameter of component i found from Eq. (1.25) or (30). The
term aij is determined from:
pffiffiffiffiffiffiffiffi
aij ¼ ai aj 1 kij with kij ¼ kji (1.83)
The calculation of aij requires the use of a binary interaction parameter
kij , which is usually determined by minimizing the difference between the
calculated and experimental data on the binary mixtures. There are several
publications in the literature where the values of kij for the PengeRobinson
and SRK equations can be found (see, for instance, Vidal, 2003). Values of
interaction parameters for some typical components in hydrocarbon mix-
tures are shown in Table 1.2. In the case of a mixture containing large quan-
tities of nitrogen or carbon dioxide, it is necessary to use specific correlations
Table 1.2 Binary interaction parameters for hydrocarbon components using

PengeRobinson EoS.
N2 CO2 C1 C2 C3 iC4 nC4 iC5 nC5 C6
N2 0.02 0.03 0.044 0.078 0.1 0.087 0.092 0.1 0.164

CO2 0.02 0.09 0.13 0.12 0.13 0.135 0.121 0.125 0.077
C1 0.03 0.09 0.003 0.016 0.026 0.019 0.006 0.026 0.055
C2 0.044 0.13 0.003 0.001 0.007 0.01 0.008 0.042
C3 0.078 0.12 0.016 0.001 0.007 0.003 0.011 0.027 0.023
iC4 0.1 0.13 0.026 0.007 0.007
nC4 0.087 0.135 0.019 0.01 0.003 0.017
iC5 0.092 0.121 0.006 0.011 0.06
nC5 0.1 0.125 0.026 0.008 0.027 0.017 0.06 0.018
C6 0.164 0.077 0.055 0.042 0.023 0.018
Obtained from data in Knapp, H., Doring, R., Oellrich, L., Plocker, U., Prausnitz, J. M., 1982. Vapor-
liquid equilibria for mixtures of low-boiling substances. DECHEMA, Chemistry Data Series, Vol. VI,
Frankfurt/Main. Blanks indicate no data are available from which the kij could be evaluated. In such
case, estimates from mixtures of similar compounds could be used.
Table 1.3 Binary interaction parameters for

waterehydrocarbon pairs using Penge
Robinson or SRK EoS.
Hydrocarbon
component Water
N2 0.08
CO2 0.15
H2S 0.03
C1 0.45
C2 0.45
C3 0.53
iC4 0.52
nC4 0.52
iC5 0.5
nC5 0.5
C6 0.5
for the binary interaction parameters. The works of Moysan et al. (1986) and
Nishiumi et al. (1988) report such specific correlations for the cases of carbon
dioxide and nitrogen, respectively.
When considering systems containing water, gaseous acids (H2S or
CO2), or alcohols/glycols (which usually are added in order to avoid the for-
mation of hydrates), in addition to hydrocarbon, the classical mixing rules do
not provide an accurate description of the behavior of the mixture.
The simplest way to describe the thermodynamic behavior of hydrocar-
bon mixtures and aqueous components would be to use the SRK or Penge
Robinson EoS as presented in previous chapters. Table 1.3 shows typical bi-
nary interaction coefficients kij for water and hydrocarbon component pairs,
that have been determined to give a fairly good match of the water solubility
in a hydrocarbon phase. This modeling is at the expense of the scarce pre-
diction of solubility of hydrocarbons in water, which will be simulated to be
almost zero. Evaluations essentially neglecting the solubility of hydrocarbons
in water can be satisfactory for many practical purposes, but accurate solubi-
lity simulation results are important for some applications. Actually, it is
found that a good prediction of water solubility in hydrocarbon mixtures
can be obtained by using the Mathias and Copeman (1983), correlation
for the aðT Þ function in SRK EoS Eq. (1.31), expressed by the following:
pffiffiffiffiffi pffiffiffiffiffi pffiffiffiffiffi
aðT Þ ¼ 1 þ C1 ð1 Tr Þ þ C2 ð1 Tr Þ2 þ C3 ð1 Tr Þ3 2 for Tr < 1
pffiffiffiffiffi
aðT Þ ¼ ½1 þ C1 ð1 Tr Þ2 for Tr 1
(1.84)
The Huron and Vidal model can be used to accurately predict the hydro-
carbon solubility in water instead (Huron and Vidal, 1979).
1.9 Phase diagrams of reservoir fluids

This section describes the different types of petroleum reservoir fluids
which are commonly encountered by exploration. A proper classification of
a reservoir is important since the fluid type is a deciding factor in the produc-
tion scheme. The properties of interest also differ between different types of
reservoirs.
Fig. 1.16 shows a typical pressureetemperature phase diagram of a hy-
drocarbon multicomponent system with a specific overall composition. In
the phase diagram, the two-phase region is enclosed by a continuous bound-
ary called the phase envelope. This phase envelope consists of a bubble point
branch and a dew point branch, with the two branches connected at the crit-
ical point where the coexisting liquid and vapor become identical in terms of
intensive properties. As said in Section 1.7, in contrast to a single component
system, the critical point of a multicomponent system is generally not the
maximum temperature and the maximum pressure of the two-phase region.
Figure 1.16 Typical pressureetemperature phase diagram for a hydrocarbon multi-

component system.
The maximum temperature point and the maximum pressure point are
called the cricondentherm and the cricondenbar, respectively.
In the two-phase region, a set of quality lines (dashed lines) can be drawn
to indicate constant percentage liquid volume. The bubble point and the
dew point branches correspond to the two special quality lines with 100%
and 0% liquid, respectively. All of the quality lines converge to the critical
point.
The single-phase region can be further divided into a liquid region and a
gas region, where the former refers to the region above the bubble point
curve with temperatures lower than the critical temperature and the latter
refers to the remaining part of the diagram.
The following general characteristics of a multicomponent mixture
phase diagram can be identified:
• The two-phase region tends to shrink when there is a dominant
component, while it tends to spread when the molar distribution is
more split to different components
• If a constant temperature expansion is carried out, crossing the two-phase
envelope, the molar composition of the phases progressively changes; at
the beginning, the vapor phase is richer in the lighter component, then
the heavier components prevail when pressure decreases; the liquid phase
progressively loose its lighter components and diminishes as relative
amount in the mixture
• When the composition is richer in heavy components, the phase enve-
lope tends to move toward higher temperatures.
A special phenomenon called retrograde condensation can be observed
for mixtures due to the existence of two dew point pressures at temperatures
higher than the critical temperature but lower than the cricondentherm. As
shown in Fig. 1.16, both a low pressure dew point D1 and a high pressure
dew point D2 exist at temperature T1; for a depletion process
A/D2 /B/C/D1 at constant temperature T1, an infinitesimal amount
of liquid will form when the system reaches D2, and a further decrease in
pressure will increase the liquid volume fraction until it reaches its maximum
at B. The increase of the condensed liquid (usually called the liquid dropout)
with decreasing pressure is contrary to the common intuition and named
retrograde condensation. It should be noted that B is only the maximum
in the liquid volume fraction rather than the absolute amount of the liquid
dropout. The absolute liquid dropout can still increase after B, but the in-
crease is not enough to counteract the expansion effect so that the liquid vol-
ume fraction decreases. After C, further decrease in pressure will reduce the
absolute liquid dropout due to the revaporization. The decrease continues

until an infinitesimal amount of liquid is left at D1.
Petroleum reservoirs are described or classified based on the composition
of the petroleum fluid and the temperature and pressure prevailing in the
reservoir. However, the dimensions of a petroleum reservoir are large and
the composition of the petroleum fluid varies depending on the location
in the reservoir due to the influence of gravity, the geothermal gradient,
and the geologic history of the reservoir.
When a petroleum reservoir is discovered, it is common practice to clas-
sify the reservoir into one of the following types: natural gas, gas condensate,
volatile oil, or black oil, based on the location of initial reservoir conditions
with respect to the phase envelope of the reservoir fluid. Black oil definition
will, here, also cover heavy oil and extra heavy oil. The classification has a
direct impact on the economical and technical evaluation, and thereby on
the production strategy. For example, some aspects of the fluid properties,
such as volumetric properties, are important for the estimation of the petro-
leum reserves. Others are of importance for the flow assurance. Potential
production problems have to be addressed as early as possible.
Table 1.4 shows the typical molar composition of petroleum reservoir
fluids and the corresponding calculated phase envelopes are shown in
Fig. 1.17.
For natural gas, the initial reservoir temperature is higher than the cricon-
dentherm of the reservoir fluid and the reservoir conditions never fall inside
the two-phase region during a depletion procedure. Natural gas is further
Table 1.4 Typical molar composition of petroleum reservoir fluids.

Mol %
Component Dry gas Rich gas Gas condensate Volatile oil Black oil
N2 1.0 0.3 0.5 0.5 0.7

CO2 0.3 1.1 3.3 2.2 2.0
C1 92.0 68.0 73.0 60.7 33.0
C2 3.2 15.0 7.7 8.0 6.6
C3 2.0 10.0 4.1 4.7 7.0
iC4 0.4 1.3 1.0 0.9 2.4
nC4 0.4 2.5 1.3 2.0 2.8
iC5 0.3 0.5 0.5 0.7 1.8
nC5 0.3 0.5 0.6 0.8 1.7
C6 0.1 0.4 0.9 4.0 2.9
C7þ 0.0 0.3 7.1 15.5 39.1
450
400
350
300
Pressure (bara)
250
200
150
100
50
0
-100 0 100 200 300 400 500
Temperature (°C)
Figure 1.17 Phase envelopes for different types of reservoir fluids. The dashed line in-
dicates the depletion line for an isothermal reservoir. Fluids with critical points to the
right of the depletion line belong to oil reservoirs, while the rest belongs to gas
reservoirs.
subdivided into rich (or wet) gas and dry gas, where compared with a dry
gas, a rich gas contains a larger fraction of C2eC6 components, and its phase
envelope is larger and reaches higher temperatures (see Fig. 1.17). The
typical gas/oil ratio of a rich gas is 60,000e100,000 scf/stb
(11,000e18,000 Sm3/m3) and its stock tank oil is usually water-white
with a specific gravity higher than 60 degrees API.
The initial temperature of a gas condensate reservoir lies between the
critical temperature and the cricondentherm of the reservoir fluid. In such
a case, the fluid exists as a gas at initial conditions, but during pressure deple-
tion, liquid will drop out due to retrograde condensation below the high
pressure dew point. A typical gas condensate has a gas/oil ratio in the range
8000e70,000 scf/stb (1400e12,000 Sm3/m3). The stock tank oil is usually
slightly colored and its API gravity is usually greater than 50 degrees.
In the case of both volatile oil and black oil, the initial reservoir temper-
ature is below the critical temperature of the reservoir fluid. The fluid there-
fore exists as a liquid at initial conditions; however, on pressure depletion,
the bubble point will eventually be reached.
Volatile oil differs from black oil quantitatively only in terms of having a
relatively larger fraction of light and intermediate hydrocarbon components.
As a result, its critical temperature is much closer to the reservoir tempera-

ture. During the depletion, volatile oils show a larger shrinkage factor due to
the large amount of gas released. The typical gas/oil ratio for a volatile oil is
2000e3500 scf/stb (360e620 Sm3/m3). Its stock tank oil is usually greenish
to orange in color with an API gravity between 45 and 55 degrees.
The gas/oil ratio for a black oil is usually below 700 scf/stb (120 Sm3/m3)
and the stock tank oil color can range from brown to black with an API
gravity between 15 degrees and 40 degrees. Black oils with a gas/oil ratio
less than 200 scf/stb (36 Sm3/m3) and an API gravity less than 15 degrees
are sometimes known as low shrinkage oils. When API gravity is less than
20 degrees, the oil is usually classified as heavy oil. Heavy oil and natural
bitumen are oils set apart by their high viscosity and high density (low
API gravity). These attributes reflect the invariable presence of up to 50
weight percent asphaltenes, very high molecular weight hydrocarbon mol-
ecules incorporating many heteroatoms in their lattices. Almost all heavy oil
and natural bitumen are alteration products of conventional oil. According
to some classification (Meyer et al., 2007), heavy oils have a viscosity greater
than 100 cP.
A reservoir fluid with its critical temperature very close to the reservoir
temperature is called a near critical fluid. Such a near critical fluid can be
either a gas condensate or a volatile oil, and it is characterized by a dramatic
change in the liquid volume fraction just below the saturation pressure. For
the near critical gas condensate, a small pressure drop below the dew point
will give rise to a large amount of liquid dropout.
Water is always associated with petroleum hydrocarbons in their produc-
tion. Not only is water found almost invariably in reservoirs in appreciable
quantities as connate, interstitial, or formation water, but it is also deliber-
ately injected to improve oil recovery. Water interacts with hydrocarbon
fluids in terms of flow, expansion, and sometimes dissolution and release
of soluble gases. Furthermore, solid precipitation including scaling and hy-
drate formation due to temperature and pressure change may cause consid-
erable damage during the production process.
Formation water contains dissolved salts (primarily sodium chloride)
and dissolved gases (primarily methane and ethane). It bears little relation-
ship to sea water although both are generally called brine or salt water. The
formation water has much higher salinity, ranging from 200 to
300,000 ppm (around saturation), compared with around 35,000 ppm of
sea water.
According to Sorensen et al. (2002), the SRK equation of state with Hu-
ron and Vidal mixing rule can be used for systems of hydrocarbon and salt
water. The salts are treated as “ordinary” components with hypothetical crit-
ical properties. In the water phase, each salt molecule is assumed to split into
as many “molecules” as the number of ions formed when the salt dissociates
in aqueous solution. NaCl will, for example, split into a Naþ ion and a CI
ion and be treated as two hypothetical molecules (one Naþ and one CI).
Salts have the effects of decreasing both the water freezing point and gas
solubility.
The solubility of hydrocarbons in water is very low, while that of
methane in water is no more than 1 mol% at common reservoir conditions.
From methane to propane, the solubility decreases by a factor of two to
three on going from one hydrocarbon gas to the next heavier one, and
the solubility of heavier liquid hydrocarbons is much smaller. Furthermore,
the solubility of hydrocarbons increases with pressure, with this effect being
more prominent for lighter hydrocarbons and at low pressures. On the
other hand, at constant pressure, the solubility of hydrocarbons has a tem-
perature minimum, before which it decreases with temperature and after
which it increases. Within common reservoir temperature and pressure
ranges, an increase in hydrocarbon solubility with temperature is usually
observed.
The equilibrium water content in hydrocarbons is generally larger than
the corresponding hydrocarbon solubility in water, especially at low pressure
and high temperature. Therefore, in the case of liquid hydrocarbons, the
water content can be orders of magnitude higher. However, since the water
content decreases with pressure and increases dramatically with temperature,
the water content in light hydrocarbon gases can be lower at low tempera-
ture and high pressure.
The chart by McKetta and Wehe (1958) provides a good estimation of
the water content in hydrocarbon gases as a function of temperature and
pressure. By that chart, the saturated water content of gases can be deter-
mined, i.e., the point at which a liquid water phase will precipitate. For
this reason, it is commonly called the water dew point chart.
As an example, Fig. 1.18 shows the calculated phase envelope diagram
for the natural gas composition called Rich Gas in Table 1.4, containing
0.05 mol % of water. The equilibrium curves have been calculated by using
the PengeRobinson EoS and Huron and Vidal method for hydrocarbone
water. The dashed line in this diagram is the WDP (Water Dew Point)
curve. On the right of this curve, water is in form of water vapor within
120
Critical Point
100 Gas Phase
Two-phase
liquid hydrocarbon
80 and liquid water
Pressure (bara)
WDP Curve
60 Hydrocarbon
Three-phase
gas-liquid
hydrocarbon
two-phase
gas-liquid and
40 liquid water
20
0
-100 -80 -60 -40 -20 0 20 40 60
Temperature (°C)
Figure 1.18 Phase envelope for wet natural gas. The dashed line indicates the WDP
(Water Dew Point) curve.
the hydrocarbon gas phase. On the left, liquid water is formed and consti-
tutes a distinct and separate phase in the mixture; inside the hydrocarbon
phase envelope, a three-phase fluid is present. When low temperatures
and high pressure are considered, water and hydrocarbon can form a new
solid phase called hydrate (see Section 6).
References
Huron, M.J., Vidal, J., 1979. New mixing rules in simple equations of state for representing
vapour-liquid equilibria of strongly non-ideal mixtures. Fluid Phase Equil. 3 (4),
255e271.
Knapp, H., Doring, R., Oellrich, L., Plocker, U., Prausnitz, J.M., 1982. Vapor-liquid equi-
libria for mixtures of low-boiling substances. In: DECHEMA, Chemistry Data Series,
Vol. VI. Frankfurt/Main.
Mathias, P.M., Copeman, T.W., 1983. Extension of the Peng-Robinson equation of state to
complex mixtures: evaluations of the various forms of the local composition concept.
Fluid Phase Equilib 13, 91e108.
McKetta, J.J., Wehe, A.H., 1958. Use this chart for water content of natural gases. Petroleum
Refiner 37 (8), 153.
Meyer, R.F., Attanasi, E.D., Freeman, P.A., 2007. Heavy Oil and Natural Bitumen Re-
sources in Geological Basins of the World. Open File-Report 2007e1084. U.S. Depart-
ment of the Interior, U.S. Geological Survey.
Moysan, J.M., Paradowski, H., Vidal, J., 1986. Prediction of phase behaviour of gas-
containing systems with cubic equations of state. Chem. Eng. Sci. 41 (8), 2069e2074.
Nishiumi, H., Tsutomu, A., Katsuhiko, T., 1988. Generalization of the binary interaction
parameter of the Peng-Robinson equation of state by component family. Fluid Phase
Equil. 42, 43e62.
Peng, D., Robinson, D.B., 1976. A new two-constant equation of state. Ind. Eng. Chem.
Fundam. 15 (1), 59e64.
Pitzer, K.S., 1995. Thermodynamics, third ed. McGraw-Hill, New York, NY.
Sandler, S.I., 1999. Chemical and Engineering Thermodynamics, third ed. John Wiley &
Sons, New York, NY.
Soave, G., 1972. Equilibrium constants from a modified Redlich-Kwong equation of state.
Chem. Eng. Sci. 27, 1197e1203.
Sorensen, H., Pedersen, K.S., Christensen, P.L., 2002. Modeling of gas solubility in brine.
Org. Chem. 33, 635e642.
Su, G.J., Chang, C.H., 1946. A generalized van der Waals equation of state for real gases. Ind.
Eng. Chem. 38, 803.
Vidal, J., 2003. Thermodynamics: Applications in Chemical Engineering and the Petroleum
Industry. Editions Technip.
Further reading
Reid, R.C., Prausnitz, J.M., Sherwood, T.K., 1977. The Properties of Gases and Liquids,
third ed. McGraw-Hill Book Co., New York, NY.
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for a few days ago he departed to Christ.” Hearing this, Finten and
Columb and all who were there present fell on their faces on the
ground and wept bitterly. Finten then asked, “Whom did he leave as
his successor?” “Baithene, his disciple,” they replied. And we all
cried out, “It is meet and right.” Columb said to Finten, “What wilt
thou do now, Finten?” He answered, “With God’s permission, I will
sail over to Baithene, that wise and holy man; and if he receive me, I
will take him as my abbot.”’[295] Baithene enjoyed the abbacy,
however, for two years only, and died in the year 599, on the same
day of the year as Saint Columba, on which day his festival was
likewise held.[296]
A.D. 599-605. His successor was Laisren, son of Feradhach,
Laisren, son of who was also a descendant of Conall Gulban,
Feradhach. and had been superior of Durrow during
Columba’s life. It was in his time that the discussion commenced
between the Roman and the Irish Church regarding the proper time
for keeping Easter. The mission of Columbanus to Gaul in the year
590, and that of Augustine to Britain in 597, had now brought the
Roman Church in contact with the British and Irish Churches, and
this—the most salient point of difference between them—became at
once the subject of a contest for the enforcement of uniformity on the
one part, and the maintenance of their ancient customs, to which the
Celtic mind clings with peculiar tenacity, on the other. Augustine, on
his death in 604, was succeeded by one of his companions, named
Laurentius; and this prelate, Bede tells us, ‘did not only attend to the
charge of the new church that was gathered from the English people,
but also regarded with pastoral solicitude the old natives of Britain,
and likewise the people of the Scots who inhabit the island of Ireland
adjacent to Britain. For observing that the practice and sentiments of
the Scots in their own country, and also those of the Britons in Britain
itself, were contrary to church order in many things, particularly
because they used not to celebrate the solemnity of Easter at the
proper time, but supposed, as we have shown above, that the day to
be observed in commemoration of the Lord’s resurrection was
included in the week from the fourteenth to the twentieth day of the
moon, he, in conjunction with his fellow-bishops, wrote them a letter
of exhortation, beseeching and entreating them to keep the bond of
peace and Catholic observances with that church of Christ which is
extended all over the world. The beginning of his letter is here given:
“To our lords and most dear brethren the bishops or abbots
throughout all Scotia (or Ireland), Laurentius, Mellitus and Justus,
bishops, the servants of the servants of God. When the Apostolic
See, according to her practice in all the world, stationed us in these
western parts to preach to the pagan nations here, and so it came to
pass that we entered into this island which is called Britain, before
we were acquainted with it, supposing that they walked in the ways
of the universal church, we felt a very high respect for the Britons as
well as the Scots, from our regard to their sanctity of character; but
when we came to know the Britons, we supposed the Scots must be
superior to them. However, we have learned from Bishop Daganus
coming into this island and Abbot Columbanus coming into Gaul,
that the Scots differ not at all from the Britons in their habits. For
Bishop Daganus, when he came to us, would not take meat with us,
no, not so much as in the same lodging where we were eating.”’[297]
This letter does not appear to have had any effect; but it shows the
spirit in which the two churches came into contact with each other.
A.D. 605-623. Laisren died in the following year.[298] His
Fergna Brit, son of successor was Fergna Brit, or the Briton. From
Failbhe. what he derived this epithet it is impossible to
say, for certain it is that he also was of the tribe of the patron saint
and a descendant of Conall Gulban. He had apparently been a pupil
in the monastery of Iona during Columba’s life, and Adamnan
mentions him as Virgnous—the Latin form of Fergna—‘a youth of
good disposition, and afterwards made by God superior of this
church in which I, though unworthy, now serve.’[299] In his time we
again hear of two of the three great island monasteries which are
specially mentioned in the Irish Annals. In 611 Tighernac records the
death of Neman, bishop of Lismore; and in 617 of Donnan of Egg
having been burnt on the fifteenth day before the kalends of May, or
17th April, with his martyr clerics.[300] The tale of their martyrdom is
thus told in the gloss upon the Martyrology of Angus the Culdee
already quoted. It says, ‘Donnan then went with his muintir, or
monastic family, to the Gallgaedalu, or Western Isles, and they took
up their abode there, in a place where the sheep of the queen of the
country were kept. This was told to the queen. Let them all be killed,
said she. That would not be a religious act, said her people. But they
were murderously assailed. At this time the cleric was at mass. Let
us have respite till mass is ended, said Donnan. Thou shalt have it,
said they. And when it was over, they were slain every one of them,’
The Calendar of Marian Gorman has the following commemoration:
‘Donnan the great with his monks. Fifty-two were his congregation.
There came pirates of the sea to the island in which they were, and
slew them all. Eig is the name of that island.’[301] The island of Egg is
the most easterly of a group of islands lying between the promontory
of Ardnamurchan and the island of Skye. It faces a wild and rugged
district on the mainland, extending from Ardnamurchan to Glenelg,
still known by the name of the Garbhcriochan, or rough bounds. The
Christian religion appears to have as yet hardly penetrated the
western districts north of Ardnamurchan, as is indicated by the
dedications of their churches. The island of Egg was probably at this
time connected with this district as a pasture island reserved for their
flocks of sheep; and, while the people would seem to have been
favourable to the little Christian colony established in the island by
Donnan, the rule had passed into the hands of a queen who was still
pagan and employed pirates to destroy them, who burnt the wooden
church in which they were celebrating the eucharist, and the whole
community accordingly perished. We have also at this time a slight
trace of the Columban Church in the eastern districts of the northern
Picts in the Irish Annals, which record in 616 the death of Tolorggain
or Talarican, who is associated in the Scotch Calendars with the
Church of Fordyce on the south shore of the Moray Firth, and who
gives his name to the great district of Cilltalargyn, or Kiltarlity, in the
district of the Aird, extending from the river Ness to the bounds of
Ross-shire.[302]
The only other event which took place while Fergna Brit was abbot
was one which was destined to lead to a great extension of the
Columban Church. In the year 617 there arrived at Iona some young
and noble Angles of Bernicia. They were the sons of Aidilfrid, king of
Bernicia, who, while still pagan, as were his people, had been slain
by Aeduin, king of Deira. Bede tells us that his sons, with many of
the youth of the nobility, took refuge among the Scots or Picts, where
they lived in banishment during the whole of Aeduin’s reign, ‘and,’
says Bede, ‘were there catechised according to the doctrine of the
Scots, and regenerated by the grace of baptism.’[303] Many of them
were no doubt sent to the monastery of Iona to receive this
catechetical instruction, and among them was certainly Osuald, the
second son of Aidilfrid, who was at that time about thirteen years old,
and who, we are expressly told, with his followers had, ‘when in
banishment, received the sacraments of baptism among the seniors
of the Scots,’ by whom those of the monastery of Iona are meant. He
appears to have remained there during the rest of Fergna’s tenure of
the abbacy, and the first ten years of that of his successor.
A.D. 623-652. Fergna died in the year 623,[304] and was
Segine, son of succeeded by Segine, son of Fiachna and
Fiachna. nephew of Laisren the third abbot, who of course
also belonged to the tribe of the patron saint, the race of Conall
Gulban. The presidency of Segine over the family of Iona was chiefly
remarkable for two great events in two opposite directions. One was
the extension of the Columban Church into the Anglic kingdom of
Northumbria; the other, that a large section of the Irish Church
conformed to Rome: and both events appear to have taken place at
the same time.
A.D. 634. At the time that the sons of Aidilfrid fled from
Extension of the face of King Aeduin, the latter and his people
Columban Church were still pagans; but the king having married the
to Northumbria.
daughter of the Christian king of Kent, in the
eleventh year of his reign he was converted to Christianity by the
preaching of Paulinus, who had been ordained bishop by Archbishop
Justus of Canterbury, and accompanied the queen to York. Aeduin
was baptized at York on Easter Sunday in the year 627, ‘in the
church of Saint Peter the apostle, which he himself had there built of
timber whilst he was being catechised and instructed in order to
receive baptism. In that city also he appointed the see for the
bishopric of his instructor and bishop, Paulinus.’[305] The people of
the two provinces of Bernicia and Deira followed their king, and
ostensibly embraced Christianity. As soon as the news reached
Rome that the nation of the Northumbrians with their king had been,
by the preaching of Paulinus, converted to the faith of Christ,
Honorius I., who was at that time Pope, sent the ‘pallium’ to Paulinus,
and at the same time wrote letters of exhortation to King Aeduin,
exhorting him with fatherly charity that his people should persist in
and profess the faith of truth which they had received.[306] When this
letter reached York, King Aeduin had been slain, the heathen Penda
of Mercia and the apostate Caedwalla of Wales were in possession
of the country, the infant Christian Church was trampled under foot,
and Paulinus, with his ‘pallium,’ had fled back to Kent. After a year, in
which the land had been given up to paganism, Osuald, who was
now thirty years old, and to whom the right to the Anglic throne had
opened by the death of his brother Ainfrid, invaded Northumbria, and
won his kingdom by the battle of the Heavenly Field, at Denisburn,
near Hexham. His first object was to restore the Christian Church
which had been swept away; and for this purpose he naturally turned
to the church where he himself had been trained in the Christian
faith. As Bede tells us, ‘He sent to the seniors of the Scots, among
whom himself and his fellow-soldiers, when in banishment, had
received the sacrament of baptism, desiring they would send him a
bishop, by whose instructions and ministry the Anglic nation which
he governed might be taught the advantages of faith in the Lord and
receive its sacraments. Nor were they slow in granting his request,
but sent him Bishop Aidan, a man of singular meekness, piety and
moderation.’[307] Bede further tells us that ‘it is reported that when
King Osuald had asked a bishop of the province of the Scots to
minister the word of faith to him and his nation, there was first sent
another man of more austere disposition, who, after preaching for
some time to the nation of the Angles and meeting with no success,
and being disregarded by the Anglic people, returned home, and in
an assembly of the seniors reported that he had not been able to do
any good in instructing that nation he had been sent to preach to,
because they were untameable men, and of a stubborn and
barbarous disposition. They, as is testified, in a great council
seriously debated what was to be done, being desirous of the good
of the nation in the matter which it demanded, and grieving that they
had not received the preacher sent to them. Then said Aidan, who
was also present in the council, to the priest then spoken of, “I am of
opinion, brother, that you were more severe to your unlearned
hearers than you ought to have been, and did not at first,
conformably to the apostolic discipline, give them the milk of more
gentle doctrine, till, being by degrees nourished with the Word of
God, they should be capable of greater perfection, and be able to
practise God’s sublimer precepts.” Having heard these words, all
who sat with him, turning on him their eyes, began diligently to weigh
what he had said, and presently concluded that he deserved to be
made a bishop, and ought to be sent to instruct the unbelievers and
unlearned, since he was found to be endowed with the grace of a
singular discretion, which is the mother of other virtues; and
accordingly, being ordained, they sent him to preach.’[308] Bede adds
that ‘most of those that had come to preach were monks, and that
Bishop Aidan was himself a monk of the island called Hii, whose
monastery for a long time held the pre-eminence over almost all
those of the northern Scots, and all those of the Picts;’ and again,
‘that from the aforesaid island, and from this college of monks, was
Aidan sent to instruct the province of the Angles in Christ, having
received the episcopal grade. At this time Segine, abbot and priest,
presided over that monastery.’ There can therefore be little doubt
that the great council was held in Iona under the presidency of Abbot
Segine; and it would almost appear that he himself had gone
personally to Northumbria on the failure of the first mission, as
Adamnan refers to a conversation which he says Abbot Failbe
solemnly declared that he himself heard between King Osuald and
Abbot Segine after the battle of the Heavenly Field had been fought.
[309]
As the first missionary sent had been a priest, and the result of
Aidan’s interposition was that all declared him worthy of the
episcopate, there can be little doubt that, as we have already had
occasion to show, the distinction of the orders and the superiority of
the episcopal grade were fully recognised. By the custom of the
Scottish Church, only one bishop was necessary for the
consecration of another bishop. That there were bishops in the
Columban Church we know, for Bede tells us that ‘all the province,
and even the bishops, were subject to the abbot of Iona;’ and, as we
have seen, two of the monasteries subject to Iona—Lismore and
Cinngaradh, or Kingarth—had episcopal heads. There may have
been an especial reason why it should be better that Aidan should
have episcopal orders, which did not exist in the case of the
Columban monasteries; for, as the head of a remote church, he
might have to ordain priests from among his Anglic converts; while
the Columban Church had Ireland at its back as a great storehouse
of clerics, both bishops and priests. When, therefore, it is said that
he received the episcopal grade, no doubt a bishop had been called
in to consecrate him. But though he was thus enabled to exercise
episcopal functions, in other respects the organisation of the church
thus introduced into Northumbria, both with respect to jurisdiction
and to its monastic character, was the same as that of the Columban
Church at home; for, instead of fixing his episcopal seat at York, he
followed the custom of the monastic church by selecting a small
island near the Northumbrian coast, bearing the Celtic name of Inis
Metcaud,[310] but known to the Angles as Lindisfarne, as the site of
his monastery, which he was to rule as episcopal abbot. Bede tells
us that, ‘on the arrival of the bishop, the king appointed him his
episcopal see in the isle of Lindisfarne, as he himself desired; which
place, as the tide flows and ebbs, twice a day is enclosed by the
waves of the sea like an island, and again, twice in the day, when the
shore is left dry, becomes contiguous to the land,’—a very apt
description of the island, which is now called Holy Island; and Bede
adds, in his Life of Cudberct, ‘And let no man marvel that in this
same island of Lindisfarne, which is of very small extent, there
should be, as we mentioned above, the seat of a bishop, and, at the
same time, as we now state, the residence of an abbot and monks.
For so it is, in truth. For one and the same habitation of the servants
of God contains both at the same time. Yea, all whom it contains are
monks; for Aidan, who was the first bishop of this place, was a monk,
and was always wont to lead a monastic life, with all his people.
Hence, after him, all the bishops of that place until this day exercise
the episcopal functions in such sort, that, while the abbot, who is
chosen by the bishop with the consent of the brethren, governs the
monastery, all the priests, deacons, chanters, readers and the other
ecclesiastical orders, with the bishop himself, observe in all things
the monastic rule.’[311] This Northumbrian church was therefore an
exact counterpart of the monastic church of which Iona was the
head; and Bede bears a noble testimony to its efficiency as a
missionary church. He says, ‘From that time many from the region of
the Scots came daily into Britain, and with great devotion preached
the word of faith to those provinces of the Angles over which King
Osuald reigned; and those among them that had received priests’
orders administered to the believers the grace of baptism. Churches
were built in several places; the people joyfully flocked together to
hear the Word; possessions and lands were given of the king’s
bounty to build monasteries; the younger Angles were by their
Scottish masters instructed; and greater care and attention were
bestowed upon the rules and observances of regular discipline.’[312]
A.D.634. The same year which brought to Segine this
Church of the important request from King Osuald of
southern Scots of Northumbria brought him likewise a letter of not
Ireland conforms
less importance, but one of a very different tenor,
to Rome.
from the head of one of the dependent
monasteries in Ireland. This letter[313] was written by Cummian, one
of the most learned of the Irish ecclesiastics, and believed to have
been abbot of the monastery of Durrow in King’s County, founded by
Columba shortly before he passed over from Ireland to Iona; and it is
still extant. It is addressed to the abbot ‘Segine, successor of Saint
Columba, and other holy men, and to Beccan the anchorite, his dear
brother according to the flesh and in the spirit, with his wise
companions.’ In this letter he tells him that, when the Roman mode
of computation was first introduced into Ireland, he did not adopt it;
but, retiring in private for a year, he entered into the sanctuary of
God, that is, the holy Scripture, and examined it as well as he was
able; after that, works on history; lastly, whatever cycles he could
meet with. He then gives a very learned summary of the result of his
investigations which led him to adopt the Roman system as correct.
When the year had expired, he says, he applied to the successors of
our ancient fathers, of Bishop Ailbe, of Kieran of Clonmacnois, of
Brendan, of Nessan and of Lugidus, that they might tell him what
they thought of the excommunication directed against them from the
Apostolic See; and they having assembled together, some in person,
others by representatives, at Magh Lene, or the plain of Lene, in
which the monastery of Durrow was situated, came to the resolution
that they ought to adopt without scruple the more worthy and
approved practice recommended to them by the successors of the
apostles of the Lord. They accordingly enjoined him to celebrate
Easter in the following year with the universal church. Not long after,
however, there arose up a certain whited wall, pretending that he
was for upholding the traditions of his elders, which caused disunion
and partly rendered void what had been agreed to. Upon this it was
determined by ‘our seniors’ that if questions of a more weighty
character should arise, they ought to be referred, according to the
decree of the synod, to the head of cities. They therefore sent some
that they knew to be wise and humble, as children to a mother, and
having a prosperous journey by the will of God, and some of them
having come to the city of Rome, they returned in the third year, and
they saw everything accord with what they had heard, or rather they
obtained a much clearer view of the matter, as seeing instead of
hearing; and, being in one lodging with a Greek and a Hebrew, a
Scythian and an Egyptian, they all celebrated their Easter together in
St. Peter’s Church, while they differed from them by a whole month.
And they solemnly assured him of this, saying, This Easter is
celebrated to our knowledge all the world over. ‘These statements,’
adds Cummian, ‘I have made, not with a view to attack you, but to
defend myself.’ Such is the substance of Cummian’s letter;[314] and
as the times for celebrating Easter according to the Roman and to
the Irish computation would be separated by the interval of a month
in the year 631,[315] the synod must have been held about 630, the
return of the deputies taken place in 633, and the letter have been
written in the following year. According to Bede, Pope Honorius in
this year ‘wrote to the nation of the Scots, whom he had found to err
in the observance of Easter, earnestly exhorting them not to esteem
their small number, placed in the utmost borders of the earth, wiser
than all the ancient and modern churches of Christ throughout the
world, and not to celebrate a different Easter, contrary to the Paschal
calculation and the synodical decrees of all the bishops upon
earth;’[316] and the result was that, as Bede tells us, ‘the Scots which
dwelt in the southern districts of Ireland, by the admonition of the
bishop of the Apostolic See, learned to observe Easter according to
the canonical custom;’ while the northern province of the Scots and
the whole nation of the Picts adhered to the old custom of the
country.[317]
The distinction here drawn by Bede between the Scots inhabiting
the southern districts and the northern province of the Scots
obviously refers to the old traditional division of Ireland into two
parts, termed severally Leth Mogha and Leth Cuinn, which were
divided from each other by a ridge extending from the mouth of the
Liffey to Galway, and termed Eisgir Riada.[318] The southern districts
were Munster and Leinster south of the Liffey. The northern division
contained the rest of Leinster, Ulster and Connaught. Durrow, though
a Columban monastery, was situated in the southern division, and
probably now broke off from the jurisdiction of Iona and, along with
the rest of the Irish Church in the southern division of Ireland,
conformed to Rome.
We meet with a passing notice of the monastery of Lismore in the
following year, when Tighernac records the death of its abbot
Eochaidh; and in the same year Abbot Segine appears to have
founded a church in Rechrann, or the island of Rathlin off the north
coast of Ireland.[319]
Some years after a letter appears to have been sent from the Irish
Church to Pope Severinus, who succeeded Honorius in 640, but
died within the year, which called forth a reply from his successor
John, while Pope-elect, by the person who had taken the letter,
which Bede tells us was ‘full of great authority and erudition for
correcting the same error,’ and at the same time admonished them
to be careful to crush the Pelagian heresy, which, he had been
informed, was reviving amongst them. Bede gives us the opening of
this epistle thus:—‘To our most beloved and most holy Tomianus,
Columbanus, Cromanus, Dinanus, and Baithanus, bishops; to
Cromanus, Ernianus, Laistranus, Scellanus, and Segenus, priests; to
Saranus and the rest of the Scottish doctors or abbots, greeting from
Hilarius, the arch-priest and keeper of the place of the holy Apostolic
See; from John, the deacon and elect in the name of God; from John
the chief secretary and keeper of the place of the holy Apostolic See,
and from John the servant of God and councillor of the same
Apostolic See.’[320] These Scottish doctors or abbots, with Tomianus,
who was bishop of Armagh, at their head, all belonged to the
northern province, and this appeal had no effect in altering their
relation towards the Church of Rome. But it is instructive to observe
that Segenus or Segine, abbot of Iona, is placed among the clergy of
the Irish Church, of which his monastery, with its dependent
monasteries in Scotland, was ranked as forming a part. Ten years
afterwards news came of the death of Aidan, after a sixteen years’
episcopate over the church of Northumbria; and Finan, ‘who had,’
says Bede, ‘been sent from Hii, the island and monastery of the
Scots,’ succeeded him.[321]
A.D. 652-657. Segine’s own death followed a year after. His
Suibhne, son of successor was Suibhne, of whom we know
Cuirtri. nothing except that his father’s name was Cuirtri,
but it is unlikely that at this early stage any one who did not belong to
the tribe of the patron saint could be elected an abbot, and the only
notice we have of him is his death after having been five years in the
abbacy.[322]
A.D. 657-669. He was succeeded in the abbacy by Cummene
Cummene Ailbhe, Ailbhe, the nephew of his predecessor Segene,
son of Ernan. whose tenure of office was signalised by equally
important events. His first year is coincident with the extension of the
dominion of Osuiu, the Northumbrian king, over the Britons of
Strathclyde, the southern Picts and the Scots of Dalriada; but,
though the latter ceased for a time to possess an independent king,
the rule of Northumbria could not have affected the church to which
her own church was affiliated. Accordingly, when Finan, the
successor of Aidan, died, we find that Colman was also ‘sent out of
Scotia,’ and succeeded him as bishop.[323] Tighernac records, in the
same year, the death of Bishop Finan and of Daniel, bishop of
Cinngaradh or Kingarth, in Bute; and in the following year, a visit of
Abbot Cummene to Ireland;[324] and, as Bede says of Finan that he
was ordained and sent by the Scots, while, in the case of Colman,
he uses the expression that he was sent out of Scotia, or Ireland,
this rather confirms our suspicion that the bishops called in to
consecrate these Northumbrian missionaries were the bishops of
Kingarth, and that the death of Bishop Daniel in the same year
rendered an appeal to Ireland necessary.
A.D. 664. While, however, Segine’s tenure of the abbacy
Termination of saw the extension of the Columban Church into
Columban Church Northumbria, that of his nephew Cummene was
in Northumbria.
doomed to see its extinction after it had for thirty
years been the church of the country. The cause was the
controversy regarding the proper time for celebrating Easter. It had
been raised, during the episcopate of Finan, by some ecclesiastics
who came from Kent or France; and among them, says Bede, ‘was a
most zealous defender of the true Easter, whose name was Ronan,
a Scot indeed by nation, but instructed in ecclesiastical truth either in
the parts of France or of Italy, who, by disputing with Finan,
corrected many, or at least induced them to make a more strict
inquiry after the truth; yet he could not amend Finan, but on the
contrary made him the more inveterate by reproof, and an open
opposer of the truth, he being of a hot and violent temper.’[325] The
royal family, too, were divided. The queen, Eanfled, being from Kent
and having a Kentish priest, Romanus, with her, followed the
Catholic mode, so that one year the king and queen both celebrated
their Easter at different times. Under Colman the controversy
became more bitter, and the king Osuiu and his son Alchfrid were
now opposed to each other, the latter having been instructed in
Christianity by Wilfrid, a most learned man, who had been originally
trained in the Scottish monastery of Lindisfarne, but had gone from
thence to Rome to learn the ecclesiastical doctrine, and spent much
time at Lyons with Dalfin, archbishop of Gaul, from whom he had
received the coronal tonsure. Agilberct, bishop of the West Saxons,
a friend to Alchfrid and to Abbot Wilfrid, having come to Northumbria,
suggested that a synod should be held to settle the controversy
regarding Easter, the tonsure and other ecclesiastical affairs. This
was agreed to; and it was accordingly held, in the year 664, at the
monastery of Streanashalch, near Whitby, where the abbess Hilda, a
woman devoted to God, then presided. The king Osuiu and his son
Alchfrid were both present. On the Catholic side was Bishop
Agilberct, with the priests Agatho and Wilfrid, James and Romanus.
On the Scottish side was Bishop Colman with his clerics from Scotia,
or Ireland, the abbess Hilda and her followers, and Bishop Cedd of
Essex, who had been ordained by the Scots, and acted as
interpreter for both parties. The king called upon Colman and Wilfrid
to conduct the discussion. It is given at length by Bede, but it is
unnecessary to say more than that the usual arguments were used.
Colman pleaded that the Easter he kept he received from his elders;
and all his forefathers, men beloved of God, are known to have
celebrated it after the same manner. Wilfrid opposed the custom of
the universal church and the authority of Rome. Colman asks, ‘Is it to
be believed that our most reverend father Columba, and his
successors, men beloved by God, who kept Easter after the same
manner, thought or acted contrary to the divine writings? whereas
there were many among them whose sanctity is testified by heavenly
signs and the working of miracles which they performed, whose life,
customs and discipline I never cease to follow, nor question their
sanctity.’ Wilfrid replied, ‘Concerning your father Columba and his
followers, whose sanctity you say you imitate and whose rule and
precepts you observe, which have been confirmed by signs from
heaven, I might answer that when many, on the day of judgment,
shall say to our Lord that in his name they prophesied and cast out
devils and wrought many wonders, our Lord will reply that He never
knew them. But far be it from me that I should say so of your father,
because it is more just to believe what is good than what is evil of
persons whom one does not know. If that Columba of yours—and I
may say ours also, if he were Christ’s—was a holy man and powerful
in miracles, yet should he be preferred before the most blessed
prince of the apostles, to whom our Lord had given the keys of the
kingdom of heaven?’ And as Colman admitted that these words were
spoken to Peter, and could not show that any such power was given
to Columba, the king decided to obey the decrees of Rome, and all
present gave their assent and, renouncing the more imperfect
institution, hastened to conform themselves to that which they found
to be better.[326] Bede then tells us ‘that Colman, perceiving that his
doctrine was rejected and his sect despised, took with him such as
were willing to follow him and would not comply with the Catholic
Easter and the coronal tonsure—for there was much controversy
about that also—and went back into Scotia, or Ireland, to consult
with his people what was to be done in this case.’ And he adds that
Colman carried home with him part of the bones of the most
reverend father Aidan, and left part of them in the church where he
had presided, ordering them to be interred in its sacristy.[327]
The character which this most candid historian gives of the church
of the Scots in Northumbria so much reflects that of the parent
church of Iona, that it may be well to insert it. He says of Bishop
Colman, ‘How great was his parsimony, how great his continence,
the place which they governed shows for himself and his
predecessors, for there were very few houses besides the church
found at their departure, indeed no more than were barely sufficient
for their daily residence. They had also no money but cattle; for, if
they received any money from rich persons, they immediately gave it
to the poor, there being no need to gather money or provide houses
for the entertainment of the great men of the world? for such never
resorted to the church except to pray and hear the Word of God. For
this reason the religious habit was at that time in great veneration, so
that, wheresoever any cleric or monk happened to come, he was
joyfully received by all persons, as God’s servant; and, if they
chanced to meet him as he was upon the way they ran to him and,
bowing, were glad to be signed with his hand or blessed with his
mouth. Great attention was also paid to their exhortations; and on
Sundays the people flocked eagerly to the church or the
monasteries, not to feed their bodies, but to hear the Word of God;
and, if any priest happened to come into a village the inhabitants
flocked together forthwith to hear from him the Word of Life. For the
priests and clerics went into the villages on no other account than to
preach, baptize, visit the sick and, in few words, to take care of
souls; and they were so free from the curse of worldly avarice, that
none of them received lands and possessions for building
monasteries, unless they were compelled to do so by the temporal
authorities.’[328]
Though Bede tells us in general terms that Colman returned to
Ireland, he did not actually do so till after four years; for he mentions
afterwards that Colman ‘repaired first to the isle of Hii, or Iona,
whence he had been sent to preach the word of God to the Anglic
nation. Afterwards he retired to a certain small island which is to the
west of Ireland, and at some distance from its coast, called, in the
language of the Scots, Inisboufinde,’ and Tighernac places this event
in the year 668.[329] As he had taken the relics of Aidan with him, it
was probably during this interval that he founded the church of Fearn
in Angus, dedicated to Aidan, and the church of Tarbet, in Easter
Ross, with which his own name is connected; and if he reported to
Abbot Cummene, as no doubt he would, the discussion he had held
with Wilfrid, and the appeal which he had made in vain to the
authority of Columba as a man whose sanctity was testified by
heavenly signs and the working of miracles, it probably led to
Cummene’s writing the Life of their great saint, which Adamnan calls
‘the book which he wrote on the virtues of St. Columba,’[330] in
vindication of the assertion. This Life is still extant, and the whole of
it has been embodied in Adamnan’s more elaborate production.
Tighernac records the death of Cummene in the year 669, and along
with it those of two saints who belonged to the church among the
southern Picts—Itharnan or Ethernanus, of Madderdyn, now
Madderty in Strathearn, and Corindu, or Caran, of Fetteresso in the
Mearns.[331]
A.D. 669-679. His successor was Failbhe, son of Pipan, also
Failbhe, son of a descendant of Conall Gulban, and the first year
Pipan. of his tenure of the abbacy also saw Wilfrid in
possession of the diocese of York. According to Bede, he at this time
administered the bishopric of York and of all the Northumbrians, and
likewise of the Picts as far as the dominions of king Osuiu extended.
[332]
His diocese therefore comprehended the territories of the
southern Picts, the Britons of Strathclyde and the Scots of Dalriada,
over all of which King Osuiu had extended his rule. Wilfrid retained
this extensive diocese during the entire period of Failbhe’s abbacy;
and, so far as he could make his power felt, his influence would no
doubt be exercised against the Columban Church; for, as Eddi tells
us, ‘under Bishop Wilfrid the churches were multiplied both in the
south among the Saxons and in the north among the Britons, Scots
and Picts, Wilfrid having ordained everywhere presbyters and
deacons, and governed new churches.’[333] But the territories of the
northern Picts were beyond his reach; and Failbhe’s tenure of the
abbacy is chiefly remarkable for the extension of the Columban
Church to those rugged and almost inaccessible districts which lay
on the western seaboard between Ardnamurchan on the south and
Loch Broom on the north.
A.D. 673. The principal agent in effecting this was
Foundation of Maelrubha, who was of the race of the northern
church of Hy Neill, but belonged to a different sept from that
Applecross by
which had the right of furnishing abbots to the
Maelrubha.
monastery of Iona. He was connected through his
mother with Comgall of Bangor, and became a member of that
monastery which, as situated among the Picts of Ireland, well fitted
him to be a missionary to those of the same race in Scotland. He
came over to Britain in the year 671, and two years afterwards he
founded the church of Aporcrosan, now Applecross,[334] from which
as a centre he evangelised the whole of the western districts lying
between Loch Carron and Loch Broom, as well as the south and
west parts of the island of Skye, and planted churches in Easter
Ross and elsewhere. The dedications to him show that his
missionary work was very extensive. In the same year Failbhe went
to Ireland, where he appears to have remained three years,[335] and
was probably engaged in arrangements for extending the missionary
work; for it is probably at this period that we must place the arrival of
Comgan with his sister Kentigerna and her son Fillan in the district of
Lochalsh, where they planted churches, as well as in the districts
south of it as far as Loch Sunart.[336] At this time too the church in
Egg appears to have been restored.[337] In the year 678 Wilfrid was
ejected from his extensive bishopric, but Failbhe only survived this
event one year, when his death is recorded; and at the same time we
have a trace of the church in the eastern territories of the northern
Picts, in the death of Neachtan Neir, who can be identified with the
great saint of Deeside in Aberdeenshire, called by the people there,
Nathalan, or Nachlan.[338]
A.D. 679-704. We are now brought in our narrative to the very
Adamnan, son of important period when Adamnan, the biographer
Ronan. of Columba, ruled over his monastery as ninth
abbot. He was also a descendant of Conall Gulban, and belonged to
the tribe of the patron saint. He was born in 624, just twenty-seven
years after the death of Saint Columba. During the first six years of
his abbacy, the rule of the Angles, under King Ecgfrid, still extended
as far as it did during the reign of his father Osuiu. After the ejection
of Wilfrid from the diocese in this its fullest extent, it was divided
between Bosa and Eata, the latter being appointed bishop of the
northern part; and three years afterwards it was still further divided,
Trumuin being appointed bishop over the province of the Picts which
was subject to the Angles. The defeat and death of King Ecgfrid,
however, at the battle of Dunnichen in the year 685 terminated this
rule of the Angles, and with it the interference of the Anglic bishops
with the Columban Church. The Scots of Dalriada recovered their
independence. The southern Picts were relieved from the more
direct yoke of the Angles, and Trumuin fled from his diocese.
A.D. 686. The new king Aldfrid had been long in exile in
His first mission to Ireland, where he was known by the name of
Northumbria. Flann Finn, and Adamnan was on terms of
friendly acquaintance with him. His first proceeding was to go on a
mission to him to ask the release of the Irish captives whom Berct,
King Ecgfrid’s general, had carried away from the plain of Breg; and
the Irish Life of Adamnan gives us the route he took. It says ‘The
North Saxons went to him and plundered Magh Bregh as far as
Bealach-duin; they carried off with them a great prey of men and
women. The men of Erin besought of Adamnan to go in quest of the
captives to Saxonland. Adamnan went to demand the prisoners, and
put in at Tracht-Romra. The strand is long, and the flood rapid; so
rapid that if the best steed in Saxonland ridden by the best horseman
were to start from the edge of the tide when the tide begins to flow,
he could only bring his rider ashore by swimming, so extensive is the
strand, and so impetuous is the tide.’ Adamnan appears therefore to
have gone in his curach and entered the Solway Firth, which is
evidently the place meant, and landed on the southern shore. He
succeeded in his undertaking, and brought sixty of the captives back
to their homes.[339]
Adamnan repairs His next step was to repair the monastery,
the monastery of which had probably fallen into disrepair during
Iona. Failbhe’s time; and for this purpose he sent
twelve vessels to Lorn for oak trees to furnish the necessary timber.
[340]
In this monastery he received Arculfus, a bishop of Gaul, who
had gone to Jerusalem to visit the holy places, and returning home
was driven by a violent storm on the west coast of Britain and made
his way to Iona and passed the winter there. During the dreary winter
months, Adamnan committed to writing all the information he could
obtain from him as to the holy places; and this work is still extant.[341]
A.D. 688. In 688 Adamnan proceeded on a second
His second mission to King Aldfrid, with what object is not
mission to known; but it appears to have been connected
Northumbria.
with the affairs of Dalriada. This second visit to
Northumbria had very important consequences both for himself and
for his church; for Bede tells us that ‘Adamnan, priest and abbot of
the monks that were in the isle of Hii, was sent ambassador by his
nation to Aldfrid, king of the Angles, where, having made some stay,
he observed the canonical rites of the church, and was earnestly
admonished by many who were more learned than himself not to
presume to live contrary to the universal custom of the church in
relation to either the observance of Easter or any other decrees
whatsoever, considering the small number of his followers, seated at
so distant a corner of the world. In consequence of this he changed
his mind, and readily preferred those things which he had seen and
heard in the churches of the Angles to the customs which he and his
people had hitherto followed. For he was a good and a wise man,
and remarkably learned in the knowledge of the Scriptures;’[342] and
Abbot Ceolfrid of Jarrow, in his letter to King Naiton of the Picts, who
calls him ‘Adamnan, the abbot and renowned priest of the
Columbans,’ says that he visited his monastery, and narrates at
length the conversation he had with him, to which he attributes
Adamnan’s conversion.[343] ‘Returning home,’ continues Bede, ‘he
endeavoured to bring his own people that were in Hii, or that were
subject to that monastery, into the way of truth, which he himself had
learned and embraced with all his heart; but in this he could not
prevail.’ We have thus the anomalous state of matters that the abbot
of the monastery had conformed to Rome, but that his monks and
those of the dependent monasteries refused to go along with him. In
the year after his return to Iona, the death of Iolan, bishop of
Cinngaradh, or Kingarth in Bute, is recorded; and in 692, which the
annalist marks as the fourteenth after the decease of his
predecessor Failbhe, he went to Ireland, but for what especial
purpose which might render the reference to Failbhe appropriate, we
do not learn; and the following year we find him again in Iona, when
the body of Brude mac Bile, king of the Picts, who died in 693, is
brought for interment.[344]
A.D. 692. Four years after, in the year 697, he goes again
Synod of Tara. The to Ireland, and on this occasion he was
northern Scots, accompanied by Brude, son of Derile, king of the
with the exception
Picts. His object was to obtain the sanction of the
of the Columban
monasteries, Irish people to a law exempting women from the
conform to Rome. burden laid upon all, of what was called Fecht
and Sluagad, or the duty attending hostings and
expeditions. For this purpose a synod was held at Tara, which was
attended by thirty-nine ecclesiastics presided over by the abbot of
Armagh, and by forty-seven chiefs of tribes, at the head of whom
was the monarch of Ireland. The law exempting women from this
burdensome duty was termed ‘Lex innocentium;’ and the enactments
of the synod were called Cain Adhamhnain or ‘Lex Adamnani,’
because among its results was the privilege of levying contributions
under certain conditions.[345] In the list of those present occurs the
name of Brude mac Derili ri Cruithentuaithe, or King of Pictland. It is
to the occasion of this visit to Ireland that must be referred the
statement of Bede that ‘he then sailed over into Ireland to preach to
those people, and, by modest exhortation declaring the true time of
Easter, he reduced many of them, and almost all that were not under
the dominion of those of Hii, from their ancient error to the Catholic
unity, and taught them to keep the proper time of Easter. Returning
to his island after having celebrated Easter in Ireland canonically, he
most earnestly inculcated the observance of Easter in his monastery,
yet without being able to prevail; and it so happened that he
departed this life before the next year came round. For the divine
goodness so ordained it that, as he was a great lover of peace and
unity, he should be taken away to everlasting life before he would be
obliged, on the return of the time of Easter, to have still more serious
discord with those that would not follow him in the truth.’[346] It would
therefore appear that Adamnan did not return to Iona till the year of
his death, which took place on the 23d of September in the year 704,
and in the seventy-seventh year of his age.[347]
At what period of Adamnan’s abbacy he wrote his life of the patron
saint and founder of the monastery cannot be fixed with any
accuracy, but it was after his visit to Aldfrid in 688; and, as he states
that he did so at the urgent request of his brethren, and alludes
incidentally to the discord which arose among the churches of
Ireland on account of the difference with regard to the Easter feast, it
was probably compiled before the same discord had arisen between
the brethren of Iona and himself as their abbot.[348] Neither can the
precise period be fixed when he founded those churches in the
eastern districts which are dedicated to him; but no doubt, after the
termination of the Anglic rule over the southern Picts and Scots of
Dalriada, he would be desirous to strengthen the Columban Church;
and his relations with the kings of the Picts who reigned after the

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1. Basics of hydrocarbons thermodynamics 1

2. Steady compressible ﬂow 41

3. Transient compressible ﬂow 85

4. Multiphase gaseliquid ﬂow 121

5. Pipeline heat transfer 157

6. Flow assurance issues 183

7. Flow properties affecting steel pipe material assessment 217

8. Special pipelines 243

9. Case Studies 271

9F. Depressurization of ﬂashing liquids 327

Flow Analysis for Hydrocarbon Pipeline Engineering

1.2 Equation of state

of experimental data of real ﬂuids; the most important from a historical

A different type of equation of state is the virial equation (Sandler, 1999):

1.3 Other real ﬂuid properties

1.4 The principle of corresponding states

such as spherical molecules, nonspherical molecules, molecules having a

These deviations have led to the development of more complicated cor-

c ¼ 0:37464 þ 1:54226u 0:27u2 (1.27)

c ¼ 0:37464 þ 1:54226u 0:27u2 (1.32)

1.5 Equilibrium and stability of one-component ﬂuids

N1, S1, U1, V1 N2, S2, U2, V2

Figure 1.3 Isolated nonequilibrium system.

condition d 2 S 0 assures that a maximum entropy value, giving a true

Table 1.1 Equilibrium and stability conditions for selected systems.

Isolated, adiabatic U ¼ constant, S ¼ maximum, d2 S 0

1.6 Vaporeliquid equilibrium for one-component

particular thermodynamic region, the cubic equations of state fail to predict

V' V'' V'''

Figure 1.5 Low-temperature isotherm in a plane (P,V) predicted by a cubic EoS.

Thus, the isotherm section predicted by a cubic EoS in the two-phase

derived from Section 1.5. From fundamental thermodynamic relationships,

Liquid-Vapour Coexistence Region

Liquid-Vapour Transition Curve

temperatures above the critical temperature, no phase transition can occur,

And, by indicating with DV ; DS the changes in speciﬁc volume and entropy

Figure 1.9 Metastable states along an isotherm in a plane (P,V).

experiments. In fact, by suitable experimental procedures in which the ther-

1.7 Vaporeliquid equilibrium for multicomponent

The differences of the above fugacity deﬁnitions with respect to the

0.7 Tie Line

temperature. The compositions of the two coexisting phases at a ﬁxed

could be followed also in the corresponding equilibrium diagram drawn as a

60 x1=0.7 x1=0.5 x1=0.3

When multicomponent mixtures (with more than two components) are

1.8 Equation of state for multicomponent mixtures

When considering the parameters a and b for the PengeRobinson and

Table 1.2 Binary interaction parameters for hydrocarbon components using

N2 0.02 0.03 0.044 0.078 0.1 0.087 0.092 0.1 0.164