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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

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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

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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

5.1 Introduction 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

6.1 Introduction 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

7.1 Introduction 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

8.1 Introduction 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.
4 Flow Analysis for Hydrocarbon Pipeline Engineering

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
Basics of hydrocarbons thermodynamics 5

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,
6 Flow Analysis for Hydrocarbon Pipeline Engineering

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).
Basics of hydrocarbons thermodynamics 7

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.
8 Flow Analysis for Hydrocarbon Pipeline Engineering

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.
Basics of hydrocarbons thermodynamics 9

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.
10 Flow Analysis for Hydrocarbon Pipeline Engineering

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
Basics of hydrocarbons thermodynamics 11

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.

12 Flow Analysis for Hydrocarbon Pipeline Engineering

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
Basics of hydrocarbons thermodynamics 13

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)
14 Flow Analysis for Hydrocarbon Pipeline Engineering

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
Basics of hydrocarbons thermodynamics 15

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)
16 Flow Analysis for Hydrocarbon Pipeline Engineering

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
Basics of hydrocarbons thermodynamics 17

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.
18 Flow Analysis for Hydrocarbon Pipeline Engineering

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)
Basics of hydrocarbons thermodynamics 19

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
20 Flow Analysis for Hydrocarbon Pipeline Engineering

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 .
Basics of hydrocarbons thermodynamics 21

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
22 Flow Analysis for Hydrocarbon Pipeline Engineering

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.
Basics of hydrocarbons thermodynamics 23

(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
24 Flow Analysis for Hydrocarbon Pipeline Engineering

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
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Smell and taste, perversion of,

250

Spinal irritation,

251

Temperature and pulse,

252

Urinary secretion, state of,

253

Vaginismus,

246

Vomiting,

254
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Treatment,

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Baths, use of, in,

282

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Bromides, use of,

276

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285

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Climatic,
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282

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Education, necessity of proper,

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Electricity, use of,

281-286

Emetics in controlling seizures,

285

Exercise and gymnastics, use in,

275

280
 Gold and sodium chloride, use of,

279

Gynæcological, question of,

286

287

Harsh measures, questionable value of,

276

Hydrotherapy in,

281

282

in children,

275
 Iron and zinc salts, use in,

278

Massage and Swedish movements,

280

Metallo-therapy,

284

Mind- and faith-cures, value of,

277

278

Mitchell's rest-cure,

279

Moral,

276
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278

Nitrite of amyl,

285

of contractures,

286

of paralyses,

286

of paroxysms,

285

Opium, use of,

278

Oöphorectomy, question of,

287
 Prophylactic and hygienic,

274

Sea-bathing in,

283

Hysteria as a cause of disseminated sclerosis,

884

of vertigo,

425

distinguished from brain tumors,

1055

Hysterical headache,

402
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148

YSTERO-EPILEPSY

288

Definition and synonyms,

288

Diagnosis,

307

from true epilepsy,

308

from simulation,
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Duration and course,

307

Etiology,

291

Age, influence of,

291

Emotional,

293

Painful menstruation,

293

Sex, race, and climate,

291
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289

Pathology,

291

Prognosis,

310

Symptoms,

293

Anæsthesia,

298

Contracture,

297

Digestive,

297
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301

Hystero-epileptogenic zones, significance of,

298

of contortions and great movements,

301

of delirium,

301

of emotional attitudes,

301

of epileptoid period,

300

of irregular types,
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of regular types,

293

of paroxysms,

293

304

306

Ovarian hyperæsthesia,

298

pressure, effect of,

299

Permanent,

307
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297

Treatment,

310

Compression of nerve-trunks,

310

Electricity, use of,

311-313

Metallic salts, use of,

313

Metallo-therapy,

313

Nitrite of amyl and nitro-glycerin,

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Oöphorectomy, question of,

312

Potassium bromide, use of,

313

Torsion of abdominal walls to arrest paroxysms,

311

Varieties,

290

I.

Ice, use of, in acute simple meningitis,

720
 in cerebral meningeal hemorrhage,

715

in neuritis,

1194

in tubercular meningitis,

736

Idiocy, intellectual and moral,

138

Ill-health, influence on causation of insanity,

116

117
Illusions in nervous diseases,

20

Imbecility, intellectual and moral,

138

in inflammation of the brain,

791

Imitation, influence on causation of catalepsy,

319

of hysteria,

222-229

Impotence in tumors of spinal cord,

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Impulsive insanity,

146

Inco-ordination in nervous diseases,

47-50

Inebriety, trance state in,

346

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PINAL

P
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1113

Anatomical lesions,

1131

Atrophy of anterior spinal horns, characters, etc.,

1133

1138

1139

nerve-roots and anterior columns of the cord,

1138

1139

Autopsies, tables of,

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1139

Microscopic lesions,

1137

Theories interpreting the lesions of the cord,

1140-1444

regarding origin, premature,

1132

Complication with progressive muscular atrophy,

1149

Course of,

1148

Definitions,
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Deformities of atrophic paralysis,

1127

Criticism of theory of muscular antagonism,

1128

Dislocations in,

1130

Mechanism of,

1128

1131

Muscular contraction in,

1127

Relation of weight and muscular forces,