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Liquid-Vapor Phase-Change
Phenomena
Liquid-Vapor Phase-Change
Phenomena
An Introduction to the Thermophysics of

Vaporization and Condensation Processes
in Heat Transfer Equipment
Third Edition
Van P. Carey
CRC Press
Taylor & Francis Group
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Boca Raton, FL 33487-2742
© 2020 by Taylor & Francis Group, LLC

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Dedication
To Judith, Elizabeth and Sean.

Contents
Preface...............................................................................................................................................xi
Nomenclature.................................................................................................................................. xiii
Author Biography.............................................................................................................................xix
Introductory Remarks......................................................................................................................xxi
Part I T
hermodynamic and Mechanical Aspects of
Interfacial Phenomena and Phase Transitions
Chapter 1 The Liquid-Vapor Interfacial Region: A Nanoscale Perspective..................................3

1.1 A Molecular Perspective on Liquid-Vapor Transitions...................................... 3
1.2 The Interfacial Region - Molecular Theories of Capillarity............................ 11
1.3 Nanoscale Features of the Interfacial Region.................................................. 17
1.4 Molecular Dynamics Simulation Studies of Interfacial Region
Thermophysics.................................................................................................. 21
1.5 Small System Effects........................................................................................26
References...................................................................................................................34
Problems...................................................................................................................... 36
Chapter 2 The Liquid-Vapor Interface: A Macroscopic Treatment............................................. 39

2.1 Thermodynamic Analysis of Interfacial Tension Effects................................. 39
2.2 Determination of Interface Shapes at Equilibrium.......................................... 45
2.3 Temperature and Surfactant Effects on Interfacial Tension............................. 51
2.4 Surface Tension in Mixtures............................................................................ 54
2.5 Near Critical Point Behavior............................................................................ 56
2.6 Effects of Interfacial Tension Gradients........................................................... 57
References...................................................................................................................64
Problems...................................................................................................................... 65
Chapter 3 Wetting Phenomena and Contact Angles.................................................................... 69

3.1 Equilibrium Contact Angles on Smooth Surfaces........................................... 69
3.2 Wettability, Cohesion, and Adhesion............................................................... 72
3.3 The Effect of Liquid Surface Tension on Contact Angle................................. 76
3.4 Adsorption and Spread Thin Films.................................................................. 79
3.5 Contact Angle Hysteresis................................................................................. 85
3.6 Other Metrics for Wettability...........................................................................90
3.7 A Nanoscale View of Wettability.....................................................................94
3.8 Wetting of Microstructured and Nanostructured Surfaces..............................96
References................................................................................................................. 103
Problems.................................................................................................................... 105
vii
viii Contents
Chapter 4 Transport Effects and Dynamic Behavior at Interfaces............................................ 109

4.1 Transport Boundary Conditions..................................................................... 109
4.2 Kelvin-Helmholtz and Rayleigh-Taylor Instabilities...................................... 113
4.3 Interface Stability of Liquid Jets.................................................................... 121
4.4 Waves on Liquid Films................................................................................... 127
4.5 Interfacial Resistance in Vaporization and Condensation Processes............. 134
4.6 Maximum Flux Limitations........................................................................... 142
4.7 Non-Equilibrium and Heat Flux Effects on Interface
Boundary Conditions...................................................................................... 146
References................................................................................................................. 149
Problems.................................................................................................................... 151
Chapter 5 Phase Stability and Homogeneous Nucleation.......................................................... 153

5.1 Metastable States and Phase Stability............................................................ 153
5.2 Thermodynamic Aspects of Homogeneous Nucleation
in Superheated Liquid.................................................................................... 164
5.3 The Kinetic Limit of Superheat...................................................................... 171
5.4 Comparison of Theoretical and Measured Superheat Limits........................ 176
5.5 Thermodynamic Aspects of Homogeneous Nucleation
in Supercooled Vapor..................................................................................... 180
5.6 The Kinetic Limit of Supersaturation............................................................ 184
5.7 Wall Interaction Effects on Homogeneous Nucleation.................................. 189
5.8 Nanobubbles................................................................................................... 192
References................................................................................................................. 197
Problems.................................................................................................................... 198
Part II Boiling and Condensation Near Immersed Bodies
Chapter 6 Heterogeneous Nucleation and Bubble Growth in Liquids....................................... 203

6.1 Heterogeneous Nucleation at a Smooth Interface.......................................... 203
6.2 Nucleation from Entrapped Gas or Vapor in Cavities....................................209
6.3 Criteria for the Onset of Nucleate Boiling..................................................... 217
6.4 Bubble Growth in an Extensive Liquid Pool.................................................. 222
6.5 Bubble Growth Near Heated Surfaces........................................................... 228
6.6 Bubble Departure Diameter and the Frequency of Bubble Release............... 235
References................................................................................................................. 242
Problems.................................................................................................................... 245
Chapter 7 Pool Boiling............................................................................................................... 249

7.1 Regimes of Pool Boiling................................................................................. 249
7.2 Mechanisms and Models of Transport During Nucleate Boiling.................. 254
7.3 Correlation of Nucleate Boiling Heat Transfer Data...................................... 265
7.4 Limitations of Nucleate Boiling Processes and the Maximum
Heat Flux Transition....................................................................................... 275
7.5 Minimum Heat Flux Conditions.................................................................... 291
7.6 Film Boiling................................................................................................... 293
Contents ix
7.7 Transition Boiling........................................................................................... 316

References................................................................................................................. 322
Problems.................................................................................................................... 327
Chapter 8 Other Aspects of Boiling and Evaporation in an Extensive Ambient....................... 331

8.1 Additional Parametric Effects on Pool Boiling.............................................. 331
8.2 The Leidenfrost Phenomenon........................................................................ 341
8.3 Fluid-Wall Interactions and Disjoining Pressure Effects............................... 351
8.4 Pool Boiling Heat Transfer on Micro and Nano Structured Surfaces............ 362
8.5 Fundamentals of Pool Boiling in Binary Mixtures........................................ 367
References................................................................................................................. 381
Problems.................................................................................................................... 387
Chapter 9 External Condensation.............................................................................................. 391

9.1 Heterogeneous Nucleation in Vapors............................................................. 391
9.2 Dropwise Condensation.................................................................................. 395
9.3 Film Condensation on a Flat, Vertical Surface..............................................404
9.4 Film Condensation on Cylinders and Axisymmetric Bodies......................... 419
9.5 Effects of Vapor Motion and Interfacial Waves............................................. 423
9.6 Condensation in the Presence of a Noncondensable Gas............................... 428
9.7 Enhancement of Condensation Heat Transfer................................................ 438
References................................................................................................................. 442
Problems.................................................................................................................... 447
Part III Internal Flow Convective Boiling and Condensation
Chapter 10 Introduction to Two-Phase Flow............................................................................... 453

10.1 Two-Phase Flow Regimes.............................................................................. 453
10.2 Basic Models and Governing Equations for One-Dimensional
Two-Phase Flow............................................................................................. 463
10.3 Determination of the Two-Phase Multiplier and Void Fraction..................... 470
10.4 Analytical Models of Annular Flow.............................................................. 487
10.5 Effects of Flow Passage Size and Geometry.................................................. 498
References.................................................................................................................500
Problems.................................................................................................................... 503
Chapter 11 Internal Convective Condensation............................................................................ 507

11.1 Regimes of Convective Condensation in Conventional (Macro) Tubes......... 507
11.2 Analytical Modeling of Downflow Internal Convective Condensation......... 511
11.3 Correlation Methods for Convective Condensation Heat Transfer................ 519
11.4 Convective Condensation in Microchannels, Advanced Modeling,
and Special Topics.......................................................................................... 535
11.5 Internal Convective Condensation of Binary Mixtures................................. 542
References................................................................................................................. 549
Problems.................................................................................................................... 552
x Contents
Chapter 12 Convective Boiling in Tubes and Channels.............................................................. 555

12.1 Regimes of Convective Boiling in Conventional (Macro) Tubes................... 555
12.2 Onset of Boiling in Internal Flows................................................................. 561
12.3 Subcooled Flow Boiling................................................................................. 567
12.4 Saturated Flow Boiling................................................................................... 575
12.5 Critical Heat Flux Conditions for Internal Flow Boiling............................... 590
12.6 Post-CHF Internal Flow Boiling....................................................................608
12.7 Internal Flow Boiling in Microchannels and Complex
Enhanced Flow Passages................................................................................ 625
12.8 Internal Flow Boiling of Binary Mixtures..................................................... 639
References................................................................................................................. 650
Problems.................................................................................................................... 661
Appendix I: Basic Elements of the Kinetic Theory of Gases.................................................... 663
Appendix II: Saturation Properties of Selected Fluids............................................................. 673
Appendix III: Analysis Details for the Molecular Theory of Capillarity................................ 681
Index............................................................................................................................................... 687
Preface
This book was inspired by the need for instructional material for a graduate-level course on heat
transfer with phase change taught in Mechanical Engineering at UC Berkeley on a yearly basis.
The initial goal in assembling this book was to provide a coherent presentation of the nonequilib-
rium thermodynamics and interfacial phenomena associated with vaporization and condensation,
as well as the heat transfer and fluid flow mechanisms in such processes. Since the initial publi-
cation of this book, this field has grown to encompass microscale and molecular-level perspec-
tives on the physics of liquid-vapor phase transformations. Applications involving vaporization
and condensation are often arising in micro- and nanoscale systems, and there is a need to educate
graduate students in engineering in a way that includes this perspective. In response to this need,
coverage of molecular-level perspectives of interfacial phenomena and phase transformations, and
the effects of reducing system size to the microscale and nanoscale level has been expanded in this
third edition.
The book focuses on the fundamental thermophysics and transport principles that underlie the
mechanisms of condensation and vaporization processes. Those who work in the field know that the
number of technical reports, papers, and books dealing with boiling and condensation processes is
enormous. Coverage of all the work in these areas is clearly impossible within the limited space of
a basic text. In the interest of conciseness, the tone of presentation in this book is illustrative rather
than exhaustive. In most cases, the basic physical mechanisms associated with a particular phase-
change phenomena are describe in detail, followed by a representative sample of the best models
applicable to the circumstances of interest. Simple idealized models are sometimes explored to gain
insight into how the mechanisms of the process interact, and to provide a more direct understanding
of trends and parametric relationships. Throughout the text, the importance of basic phenomena to
a wide variety of applications is discussed.
The sequence of chapters in this book was chosen to facilitate instruction at the advanced under-
graduate or graduate level in mechanical or chemical engineering. The chapters in Part I of the book
deal entirely with nonequilibrium thermodynamics and interfacial phenomena. As it is covered
first, this material provides a useful foundation on which the later discussion of boiling and con-
densation phenomena can build. Part II covers boiling and condensation processes on the external
surfaces of a body exposed to an extensive ambient. The material on internal flow boiling and
condensation in Part III follows that in Part II because many of the concepts that apply to external
condensation and boiling apply in a modified form to convective boiling or condensation in tubes.
The coverage of these topics focuses on the fundamental physics and methods to analyze and pre-
dict performance in applications. Although space limitations do not permit extensive discussion of
application-related topics, references are provided throughout the text that will lead an interested
reader to more detailed discussion of related special topics and applications. The progressive flow
of ideas provided by the book’s structure should make it useful to practicing engineers who wish
to gain a further understanding of the thermophysics of vaporization and condensation processes
through individual study.
The author is indebted to the numerous students at Berkeley and colleagues in the heat transfer
and thermophysics community who have provided useful comments, criticisms, and suggestions
regarding the content of this text. Changes in this third edition reflect efforts to respond to this
input. The changes also have aimed to include results of recent research into micro- and nanoscale
aspects of vaporization and condensation processes. The author is particularly grateful to Professor
John H. Lienhard IV, Professor Dennis O’Neal, and Professor Ralph Seban for their insightful com-
ments on the earliest versions of this text. More recent input from Professor John Rose, Professor
xi
xii Preface
Nenad Miljkovoc, and Professor Jungho Kim has also helped guide revisions to update this text. An
expression of gratitude is also due to the many investigators who have contributed to this area over
the past 70 years. It is only through their combined efforts that a clear overview of the physics of
these processes is possible.
Van P. Carey
Berkeley, California
Nomenclature
A surface or cross-sectional area
Af fin area
Ao tube open area
Ap prime surface area
b fin height
Bo boiling number [= q ′′ /Ghlv ]
BoL Bond number [= g(ρl − ρv ) L2 /σ (where the length scale L depends on the circumstances
of interest)]
boiling number (= q n /Ghlv )
cpl liquid specific heat
cpv vapor specific heat
Ca capillary number [= µ lV /σ ]
Co convection number {= [(1 – x)/x]0.8[ρv /ρl ]0.5}
dd bubble departure diameter
dt tube diameter
dh hydraulic diameter based on wetted perimeter
(dP/dz)fr frictional component of two-phase pressure gradient
(dP/dz)l pressure gradient for liquid flow alone through tube
(dP/dz)le pressure gradient for entire flow as liquid through tube
(dP/dz)lo pressure gradient for entire flow as liquid through tube
(dP/dz)v pressure gradient for vapor flow alone through tube
D tube diameter
D1* binary diffusion coefficient for more volatile component
D12 binary diffusion coefficient for species 1 and 2
E mass fraction of liquid phase entrained in the core during annular flow
E ′′ rate of entrainment in mass of droplets per unit time per unit of wall area
f bubble frequency
friction factor
fl friction factor for liquid flowing alone in tube
fv friction factor for vapor flowing alone in tube
F Helmholtz function (= U – TS)
force
Chen correlation parameter
FTD Taitel-Dukler flow regime parameter
Frle Froude number [= G 2 /(ρl2 gD)]
g gravitational acceleration
specific Gibbs function
G Gibbs function (= H – TS)
mass flux through tube or channel
h local heat transfer coefficient
h mean heat transfer coefficient
ĥ specific enthalpy on per unit mass basis
h* mass transfer coefficient
hl heat transfer coefficient for the liquid phase flowing alone in the tube
hle heat transfer coefficient for entire flow as liquid
hlo heat transfer coefficient for entire flow as liquid
hlv latent heat of vaporization per unit mass
xiii
xiv Nomenclature
Hf fin height
jl volume flux of liquid [= G (1 − x ) /ρl ]
jv volume flux of vapor [= Gx /ρv ]
J flux of droplet or bubble embryos through size space; rate of generation of embryos per
unit volume
J* dimensionless droplet flux in size space
Ja Jakob number [= c p ∆T /hlv (where the choices of cp and ∆T depend on the circumstances
of interest)]
k B Boltzmann constant (= 1.3805 × 10 −23 J/K)
k d deposition coefficient in model of entrainment and deposition for annular flow
kl thermal conductivity of liquid
kv thermal conductivity of vapor
KTD Taitel-Dukler flow regime parameter
L tube length
Lb { }
bubble or capillary length scale = [σ /g(ρl − ρv )]1/ 2
Lf fin length
m mass of one molecule
m ′ mass flow rate of condensate in liquid film per unit width of surface
m ′′ mass flux
M mass
mass of one molecule
M molecular weight
NA Avogadro’s number (= 6.02 × 1026 molecules/kg mol)
Nl number of liquid molecules per unit volume
Nn number of embryos of n molecules at equilibrium per unit volume
N n′′ number of embryos of n molecules at equilibrium per unit of interface area
P pressure
Pc critical pressure
Pl ambient liquid pressure
Ppi(T) saturation pressure of pure component i in mixture at temperature T
Pr reduced pressure [= P /Pc ]
Pv ambient vapor pressure
Prl liquid Prandtl number
Prt turbulent Prandtl number (= ε M /ε H )
Prv vapor Prandtl number
q ′′ heat flux
′′
qcrit critical heat flux
′′
qmax maximum (critical) heat flux
′′
qmin minimum heat flux on pool boiling curve
′′
qmkc maximum heat flux limit dictated by kinetic theory for condensation
′′
qmkv maximum heat flux limit dictated by kinetic theory for vaporization
q total heat transfer rate
R ideal gas constant on a per unit mass basis
liquid jet radius
R universal gas constant (= 8.3144 kJ/(kg mol K))
Re Reynolds number
ReF film Reynolds number
Rel Reynolds number for liquid phase flowing alone [= G (1 − x ) D /µ l ]
Rele Reynolds number for entire flow as liquid [= GD /µ l ]
Relo Reynolds number for entire flow as liquid [= GD /µ l ]
ReL film Reynolds number [= 4 m ′ /µ l ]
Nomenclature xv
Rev Reynolds number for vapor phase flowing alone [= GxD /µ v ]

s specific entropy
distance between fins in an offset matrix
S entropy
supersaturation ratio  = ( Pv )SSL /Psat ( Tv )
suppression factor in Chen correlation
slip ratio [= uv /ul ]
Sc Schmidt number [= ν /D12 ]
Spls spreading coefficient [= − (∂ F / ∂ Asl )]
St Stanton number (= h /Gc p )
Su subcooling number {= [c pl (Tsat − Tin )/hlv ][(ρl − ρv )/ρv ]}
T temperature
Tbp bubble point temperature
Tc critical temperature
Tdp dew point temperature
Ti interface temperature
Tin fluid temperature at tube inlet
Tr reduced temperature [= T /Tc ]
Tsat saturation temperature
TTD Taitel-Dukler flow regime parameter
Tw wall temperature
u specific internal energy
velocity component in the x direction
ul liquid mean downstream velocity in two-phase flow [= G (1 − x )/ρl (1 − α)]
uv vapor mean downstream velocity in two-phase flow [= Gx /ρv α]
U internal energy
v̂ molar specific volume (volume per kmol)
v specific volume (volume per unit mass)
velocity component in the y direction
vc critical specific volume
vr reduced specific volume [= v /vc or vˆ /vˆc ]
V volume
velocity
w velocity component in the z direction
w mean distance between fins
W wickability
Wg mass fraction of noncondensable gas
Wv mass fraction of condensable vapor
We Weber number [= G 2 D /ρσ ]
x coordinate (downstream coordinate for external flows)
mass quality
xa actual ratio of vapor mass flow rate to total mass flow rate
xcrit dry out quality
xe equilibrium quality
xi mass fraction of species i in liquid binary mixture
x1 mass fraction of more volatile component in liquid binary mixture
x̂i mole fraction of species i in liquid binary mixture
xˆ1 mole fraction of more volatile component in liquid binary mixture
X { }
Martinelli parameter = [(dP /dz )l /(dP /dz ) v ] 1/ 2
Xtt Martinelli parameter for turbulent-turbulent flow
y coordinate, surface normal coordinate for external flows
xvi Nomenclature
yi mass fraction of species i in vapor binary mixture

y1 mass fraction of more volatile component in vapor binary mixture
ŷi mole fraction of species i in vapor binary mixture
yˆ1 mole fraction of more volatile component in vapor binary mixture
y+ dimensionless y coordinate [= y τ 0 / ρl /νl ]
z coordinate (downstream coordinate for tube flows)
α wave number
void fraction
α c critical wave number
α T thermal diffusivity [= k /ρc p ]
α Tl thermal diffusivity of liquid
α Tv thermal diffusivity of vapor
β frequency
volume fraction of vapor
β f volume fraction of liquid flowing in liquid film on tube wall
β max frequency of most rapidly growing disturbance
γ multiplier in Baroczy correlation
δ film thickness
δ + dimensionless film thickness [= δ τ 0 /ρl /νl ]
δ f fin thickness
δ t thermal boundary-layer thickness
∆Tvl temperature difference across liquid-vapor interface
ε emissivity
eddy diffusivity
ε H eddy diffusivity of heat for turbulent flow
ε M eddy diffusivity of momentum for turbulent flow
θ liquid contact angle
angular coordinate
θa advancing contact angle
θr receding contact angle
θrot ,m mean rotational temperature for polyatomic molecule
λ c critical wavelength
λ D most dangerous wavelength
µ absolute viscosity
chemical potential
µ l liquid viscosity
liquid chemical potential
µ̂ l liquid molar chemical potential
µ v vapor viscosity
vapor chemical potential
µ̂ v vapor molar chemical potential
vl liquid kinematic viscosity
vv vapor kinematic viscosity
ρ̂ molar density
ρl liquid density
ρv vapor density
ρn number density
ρN number density
ρN ,l liquid number density
ρN ,v vapor number density
Nomenclature xvii
σ interfacial tension, or equivalently, the

interfacial free energy per unit areas of interface
σ lv interfacial tension of liquid vapor interface at equilibrium
σ̂ accommodation coefficient
σ SB Stefan-Boltzmann constant (= 5.67 × 10 –8 W/m2 K4)
τ shear stress
τi shear stress at interface
τ 0 shear stress at wall
τ w shear stress at wall
φl {
two-phase multiplier = [(dP /dz ) fr /(dP /dz )l ] 1/ 2 }
φlo two-phase multiplier {= [(dP /dz ) fr /(dP /dz )lo ] 1/ 2
}
φ v two-phase multiplier {= [(dP /dz ) /(dP /dz ) v ] 1/ 2
fr }
ξ number of translational and rotational energy storage modes in molecule
ψ volumetric free energy density [= F/V]
ψ S normalized heat transfer coefficient [= h /hl ]
Ω vorticity
angle between tube axis and horizontal
SUBSCRIPTS
a actual value
b bulk
bp bubble point
c properties evaluated at the critical point
dp dew point
ex exit conditions
f film
fin
i interface
in inlet conditions
l liquid
corresponding to the liquid phase flowing alone
le corresponding to the entire flow as liquid
corresponding to liquid flow in equivalent separate cylinder
lo corresponding to the entire flow as liquid
sat corresponding to saturation conditions
SSL supersaturation limit
v vapor
corresponding to the vapor phase flowing alone
ve corresponding to vapor flow in equivalent separate cylinder
w wall value
∞ far ambient conditions
0 wall value
Author Biography
Van P. Carey, a Professor in the Mechanical Engineering Department, holds the A. Richard Newton
Chair in Engineering at the University of California at Berkeley. Carey is widely recognized for his
research in the areas of micro- and nanoscale thermophysics, interfacial phenomena, and transport
in liquid-vapor phase-change processes. His research interests also include development of new
methods for computational modeling and simulation of energy conversion and transport processes.
Carey’s research has covered a variety of applications areas, including solar thermal power systems,
building and vehicle air conditioning, phase-change thermal energy storage, Rankine cycle power
for manned space missions, heat pipes for aerospace applications, high heat flux cooling of electron-
ics, energy efficiency of information processing systems, microgravity boiling, and nanostructured
surfaces for enhancing droplet evaporation and boiling processes.
Carey is a Fellow of the American Society of Mechanical Engineers (ASME) and the American
Association for the Advancement of Science, and he has also served as the Chair of the Heat Transfer
Division of ASME. Carey has received the James Harry Potter Gold Medal in 2004 for his eminent
achievement in thermodynamics and the Heat Transfer Memorial Award in the Science category (2007)
from the ASME. Carey is also a three-time recipient of the Hewlett Packard Research Innovation Award for
his research on electronics thermal management and energy efficiency (2008, 2009, and 2010), and Carey
received the 2014 Thermophysics Award from the American Institute of Aeronautics and Astronautics.
xix
Introductory Remarks
Liquid-vapor phase-change processes play a vital role in many technological applications. The
virtually isothermal heat transfer associated with boiling and condensation processes makes their
inclusion in power and refrigeration cycles highly advantageous from a thermodynamic efficiency
viewpoint. Liquid-vapor phase-change processes are also encountered in petroleum and chemical
processing, liquefaction of nitrogen and other gases at cryogenic temperatures, and during evapora-
tion or precipitation of water in the earth’s atmosphere.
In addition, the high heat transfer coefficients associated with boiling and condensation have
made the use of these processes increasingly attractive in the thermal control of compact devices
having high heat dissipation rates. Applications of this type include the use of boiling heat transfer
to cool electronic components in mainframe computers and the use of compact evaporators and con-
densers for thermal control of aircraft avionics and spacecraft environments. Liquid-vapor phase-
change processes are also of critical importance to nuclear power plant design, both because they
are important in normal operating circumstances, and because they dominate many of the accident
scenarios that are studied in detail as part of the design evaluation.
The heat transfer and fluid flow processes associated with liquid-vapor phase-change phenomena
are typically among the more complex transport circumstances encountered in engineering applica-
tions. These processes may have all the complexity of single-phase convective transport (nonlinear
effects, transition to turbulence, and three-dimensional or time-varying behavior) plus additional
elements resulting from motion of the interface, nonequilibrium effects, or other complex dynamic
interactions between the phases. Due to the highly complex nature of these processes, development
of methods to predict the associated heat and mass transfer has often proved to be a formidable
task. Nevertheless, the research efforts of numerous scientists over several decades have provided
a fairly clear understanding of many aspects of vaporization and condensation processes in power
and refrigeration systems. On the other hand, some elements of vaporization and condensation
phenomena are not well understood, and research in these areas continues.
There is a vast quantity of published information on liquid-vapor phase-change phenomena in
textbooks, monographs, and journal articles. Because such processes occur in a wide variety of
applications and because the thermodynamic, fluid mechanics, and heat transfer aspects of these
processes appeal to different groups of investigators, technical papers on various aspects of vapor-
ization and condensation processes are found in a number of journals, serial publications, and con-
ference proceedings. English-language publications frequently containing information related to
liquid-vapor phase-change phenomena include the following:
International Journal of Heat and Mass Transfer, published by Elsevier.

International Communications in Heat and Mass Transfer, published by Elsevier.
Journal of Heat Transfer, published by the American Society of Mechanical Engineers.
AIChE Journal, published by the American Institute of Chemical Engineers.
Journal of Fluid Mechanics, published by Cambridge University Press.
International Journal of Multiphase Flow, published by Elsevier.
Heat Transfer Engineering, published by Taylor & Francis.
Numerical Heat Transfer (Parts A & B), published by Taylor & Francis.
ASHRAE Transactions, published by the American Society of Heating, Refrigerating and
Air-Conditioning Engineers.
International Journal of Heat and Fluid Flow, published by Elsevier.
Advances in Heat Transfer, published by Academic Press—Elsevier.
Advances in Chemical Engineering, published by Academic Press—Elsevier.
Experimental Heat Transfer, published by Taylor & Francis.
Journal of Thermophysics and Heat Transfer, published by the American Institute of
Aeronautics and Astronautics.
xxi
xxii Introductory Remarks
Experimental Thermal and Fluid Science, published by Elsevier.

Proceedings of the International Heat Transfer Conferences, various publishers.
Journal of Physical Chemistry, published by the American Chemical Society.
Multiphase Science and Technology, published by Taylor & Francis.
Nuclear Engineering and Design, published by Elsevier.
Nuclear Science and Engineering, published by the American Nuclear Society.
Nanoscale and Microscale Thermophysical Engineering, published by Taylor & Francis.
Thermal Science and Engineering, published by the Heat Transfer Society of Japan.
Heat and Mass Transfer, published by Springer-Verlag.
Journal of Enhanced Transfer, published by Begell House Publishing.
Journal of Colloid and Interface Science, published by Elsevier.
Langmuir, published by the American Chemical Society.
Journal of Chemical Physics, American Institute of Physics.
Physics of Fluids, published by the American Physical Society.
Soft Matter, published by the Royal Society of Chemistry.
ACS Nano, published by the American Chemical Society.
Applied Physics Letters, American Institute of Physics.
Physical Review Letters, American Physical Society.
Nanoletters, published by the American Chemical Society.
Proceedings of the Royal Society, The Royal Society Publishing.
The above list is intended to provide a starting point for exploration of this area. There are many other
special conference proceedings and publications in applications areas such as electronics cooling,
automotive and aerospace applications that also have content relating to liquid-vapor phase-change
processes.
In addition to the sources listed above, useful information on liquid-vapor phase-change processes
may also be obtained from government agency reports (from, e.g., NASA, the National Bureau of
Standards, or the Nuclear Regulatory Commission) and the reports of research laboratories such as
Sandia National Laboratory, Argonne National Laboratory, and the Electric Power Research Institute.
The presentation of material in this text assumes that the reader is familiar with the basic ele-
ments of classical thermodynamics, fluid dynamics, heat transfer, and interfacial phenomena at
the level of typical coverage in undergraduate mechanical engineering or chemical engineering
programs. Throughout this book, facts from these fields will be recalled as needed for explana-
tion of phenomena of interest. It may be useful to refer to basic texts in these fields, if the reader is
unfamiliar with the concepts discussed. References [0.1–0.18] are useful resources for background
information in these areas.
A word regarding notation in this text is also warranted. The physical diversity of the mecha-
nisms involved in vaporization and condensation processes also makes selection of a consistent
nomenclature a difficult problem. For example, symbols traditionally used for properties in thermo-
dynamic analysis are commonly used to denote other physical quantities in fluid mechanics analysis
or in analysis of heat exchanger performance. To avoid confusion, every effort has been made to
make the definition of variables clear at the location in the text where they are introduced. In addi-
tion, a listing of the nomenclature for the text is provided in the back of the book to provide a quick
means of checking variable definitions.
In macroscopic treatments of systems in which liquid and vapor phases coexist, the boundary
between the bulk phases is usually idealized as a surface at which a discontinuity in properties
occurs. Interfaces between phases are invariably the locations where the net conversion of one phase
into the other occurs in vaporization and condensation processes. For that reason, the thermophysics
of the liquid-vapor interface is of primary importance in many phase-change processes in nature
and in important technological applications. We begin our exploration of liquid-vapor phase-change
processes in Chapter 1 by exploring the nanoscale features of the near-interface region in detail.
Introductory Remarks xxiii
REFERENCES
0.1 Van Wylen, G., and Sonntag, R. E., Introduction to Thermodynamics—Classical and Statistical,
3rd ed., Wiley, New York, NY, 1991.
0.2 Bejan, A., Advanced Engineering Thermodynamics, 4th ed., Wiley, New York, NY, 2016.
0.3 Wark, K., Advanced Thermodynamics for Engineers, McGraw-Hill, New York, NY, 1995.
0.4 Carey, V. P., Statistical Thermodynamics and Microscale Thermophysics, Cambridge University Press,
New York, NY, 1999.
0.5 Cengel, Y. A., and Boles, M. A., Thermodynamics—An Engineering Approach, 8th ed., McGraw-Hill,
New York, NY, 2014.
0.6 Moran, M. J., and Shapiro, H. N., Fundamentals of Engineering Thermodynamics, 7th ed., Wiley,
New York, NY, 2010.
0.7 Carslaw, H. S., and Jaeger, J. C., Conduction of Heat in Solids, 2nd ed., Oxford University Press,
Oxford, 1959.
0.8 Ozisik, M. N., Heat Conduction, Wiley, New York, NY, 1980.
0.9 Arpaci, V. S., Conduction Heat Transfer, Addison-Wesley, Reading, MA, 1966.
0.10 Bird, R. B., Stewart, W. E., and Lightfoot, E. N., Transport Phenomena, 2nd ed., Wiley, New York,
NY, 2001.
0.11 Kays, W. M., Crawford, M. E., and Weigand, B., Convective Heat and Mass Transfer, 4th ed.,
McGraw-Hill, New York, NY, 2004.
0.12 Howell, J. R., Siegel, R., and Menguc, M. P., Thermal Radiation Heat Transfer, 5th ed., CRC Press,
Taylor & Francis, New York, NY, 2011.
0.13 Incropera, F. P., DeWitt, D. P., Bergman, T. L., and Lavine, A., Fundamentals of Heat and Mass
Transfer, 6th ed., Wiley, New York, NY, 2006.
0.14 Mills, A. F., and Coimbra, C. F. M., Basic Heat and Mass Transfer, 3rd ed., Temporal Publishing, LLC,
San Diego, CA, 2015.
0.15 Baehr, H. D., Park, N. J., and Stephan, K., Heat and Mass Transfer, Springer-Verlag, New York, NY,
2006.
0.16 Miller, C. A., and Neogi, P., Interfacial Phenomena—Equilibrium and Dynamic Effects, 2nd ed.,
CRC Press, Boca Raton, FL, 2007.
0.17 Israelachvilli, J. N., Intermolecular and Surface Forces, 3rd ed., Academic Press, Waltham, MA, 2011.
0.18 Sadhal, S. S., Ayyaswamy, P. S., and Chung, J. N., Transport Phenomena with Drops and Bubbles,
Springer-Verlag, New York, NY, 1997.
Part I
Thermodynamic and Mechanical
Aspects of Interfacial Phenomena
and Phase Transitions
1 The Liquid-Vapor
Interfacial Region:
A Nanoscale Perspective
1.1 A MOLECULAR PERSPECTIVE ON LIQUID-VAPOR TRANSITIONS

Before considering the mechanisms of vaporization and condensation processes, it is useful to
examine the nature of the liquid and vapor states, and the transition between them, from a molecu-
lar point of view. In macroscopic treatments of systems in which liquid and vapor phases coexist,
the boundary between the bulk phases is usually idealized as a surface at which a discontinuity in
properties occurs. Interfaces between phases are invariably the locations where the net conversion
of one phase into the other occurs during vaporization and condensation processes. For that reason,
the thermophysics of the liquid-vapor interface is of primary importance in many phase-change
processes in nature and in important technological applications.
At the nanoscale level, there is a region between the bulk phases across which the mean molecu-
lar density exhibits a transition between bulk vapor and bulk liquid values. As we will see, the
nature of this transition strongly affects the thermophysics and transport in this region. In analyz-
ing vaporization and condensation processes, it will frequently be useful to model the boundary
between bulk liquid and vapor phases as a surface. However, to fully understand such processes,
we must first establish an understanding of the nanoscale thermophysics in this region. In addition,
we will find that in liquid-vapor phase-change processes in microscale and nanoscale systems, the
impact of nanoscale features of the interfacial region is especially important. Coverage of the fun-
damentals of liquid-vapor phase-change phenomena begins in this chapter with a molecular-level
examination of the bulk liquid and vapor phases and the interfacial region that exists between them.
The mechanisms that give rise to interaction forces between molecules vary widely in character.
The forces can be attractive or repulsive in nature and one type may or may not act independently
of others. At very short range, two molecules generally exert a repulsive force on one another. This
repulsion is a consequence of the interference of the electron orbits of one molecule with those of the
other. For polyatomic molecules, the force of interaction and associated potential function may vary
with orientation as well as separation distance. These effects may be weak in simple polyatomic
molecules and, in general, they may tend to average-out when analyzing the mean behavior of large
numbers of molecules. For the purposes of this introductory exploration, we will adopt the simplify-
ing assumption that orientation effects are small and, to a first approximation, the potential function
is only a function of separation distance.
Although the exact nature of short-range force interactions varies with the types of molecules
involved, the resulting repulsive force generally increases rapidly as the center-to-center spacing r
decreases. Consequently, they are often represented by a repulsive potential of the form
λ0 (1.1)
φ R (r ) = , 9 ≤ k ≤ 15
rk
where λ0 is a constant that varies depending on the type of molecule. Note that by definition, the
potential function is the energy that must be input to bring two molecules from infinite distance
apart to center-to-center spacing r. For a specified interaction potential ϕ, the force between
the molecules at any separation distance r is –dϕ/dr.
3
4 Liquid-Vapor Phase-Change Phenomena
At somewhat larger distances, the forces acting between molecules generally fall into one of the
three categories: (1) electrostatic forces, (2) induction forces, or (3) dispersion forces. Electrostatic
forces between molecules often arise because the molecules have a finite dipole moment (i.e., opposite
sides of the molecule have opposite charges). Common polar molecules (those having non-zero dipole
moments) include water and alcohols. Because the potential function for electrostatic interactions rap-
idly becomes small as r increases, dipole interactions are generally significant only at very short range.
Induction forces arise when a permanently charged particle or dipole induces a dipole in a nearby
neutral molecule. The strength of induction forces depends directly on how easily the initially neu-
tral molecule is polarized. The potential function associated with the induction force interaction
between a dipole molecule and a neutral molecule is inversely proportional to r6.
Dispersion forces are a consequence of transient dipoles that can be induced in molecules or
atoms. Such transient dipoles are mutually induced in adjacent molecules as a result of instanta-
neous asymmetries in the electric field due to moving electrons in each molecule. This type of force
interaction occurs in molecular species of all types and produces an attractive force between the
molecules. The associated potential function for dispersion force interactions is proportional to r–6,
λ DIS α 2p
φ DIS = − (1.2)
r6
where αp is the polarizability of the molecules and λDIS is a constant that varies with the type of mol-
ecule. Short-range attractive dispersion forces play an important role in the thermophysical behavior
of virtually all liquids and vapors near saturation conditions.
For real molecules, multiple force interaction mechanisms may come into play. Hence, the overall
potential function ϕ(r) is generally assumed to reflect the repulsive force behavior at small spacing
and the attractive behavior due to electrostatic, induction and/or dispersion forces at intermediate
distances. Several model variations of ϕ(r) have been proposed which more or less conform to this
general behavior. Perhaps the most well-known of these models is the Lennard-Jones 6–12 potential
φ LJ (r ) = 4ε[(r0 /r )12 − (r0 /r )6 ] (1.3)
which is plotted in Fig. 1.1. Appropriate values of the parameters ε and r0 vary with the type of molecule.
A study of all the implications of the Lennard-Jones potential, and other models like it, is
beyond the scope of this book. The interested reader can find more information on this subject in
references [1.1–1.5]. It is sufficient for our current purposes to note that this variation of the potential
FIGURE 1.1 The Lennard-Jones 6–12 potential.

The Liquid-Vapor Interfacial Region 5
implies that to bring two molecules that are initially very far apart into closer proximity, we must
remove energy. Conversely, if two molecules are close enough to feel attractive forces, but not so
close that repulsive forces come into play, then energy must be supplied to increase the spacing of
the molecules. Clearly, the energy exchanges associated with these processes are consistent with
the input or removal of the latent heat of vaporization during vaporization (moving closely spaced
molecules apart) or condensation (moving widely spaced molecules closer) processes.
The force interactions among molecules largely dictate the thermophysical properties of the sub-
stance. For fluids containing molecules that obey a spherically symmetric potential function ϕ(r),
statistical thermodynamic theory can used to generate relations among thermodynamic properties.
For a system of volume V containing N molecules with a spherically symmetric interaction function,
this type of theoretical model can be used to derive the following relation for the logarithm of the
canonical partition function:
3 N   2πMk B T (V − Nbv′ )2/3   (ξ − 5) 

ln Q = N +  ln  + N  2 ln π − ln σ s 
 2   N 2/3 h 2    (1.4)
(ξ − 3) N  T  av′ N 2
+ ln  +
2  θrot ,m  Vk B T
where
∞
∫
av′ = −2π r 2φ(r )dr
D
(1.5)
and bv′ is a mean volume occupied per molecule in the system. In Eq. (1.4), kB is the Boltzmann con-
stant, h is Planck’s constant, M is the molecular mass of the molecule, ξ is the number of translational
and rotational molecular energy storage modes, σs is the symmetry number for the molecule, and θrot,m
is the mean rotational temperature for the molecule if it is a polyatomic species. In Eq. (1.5), D is the
effective diameter of the molecule. When the Lennard-Jones potential function is used, D is usually
taken to be about equal to r0. A simple model to relate bv′ to D is to treat the molecules as hard spheres
of diameter D and make two additional idealizations. The first is to interpret bv′ as the volume per mol-
ecule in the densest possible condition. The second is to take the densest condition to be cubic close
packing of the molecules. Geometry then requires that bv′ is related to the diameter D as
bv′ = 1.350 ( π / 6 ) D 3 (1.6)
Note that the constant 1.350 in the above relation is the ratio of system volume to volume occupied
by molecules for cubic close packing of spheres. A complete discussion of the derivation of the rela-
tion (1.4) for ln Q for a van der Waals fluid can be found in Carey [1.1].
With the following relations from statistical thermodynamic theory, the equation for ln Q can be
used to generate relations for thermodynamic properties:
 ∂ln Q 
P = k BT  (1.7)
 ∂V  T , N
 ∂(ln Q) 
µ = − k BT  (1.8)
 ∂ N  V ,T
 ∂(ln Q) 
U = − k BT 2  (1.9)
 ∂T  V , N
Substituting Eq. (1.4) into the equations above yields the relations
Nk B T a′ N 2
P= − v 2 (1.10)
V − Nbv′ V
µ Nbv′ 3   2πMk B T (V − Nbv′ )2/3   (ξ − 5) 

= −   ln   − ln π + ln σ s 
k B T V − Nbv′  2  
2/3 2
N h   2 
(1.11)
(ξ − 3)  T  2av′ N
− ln  −
2  θrot ,m  Vk B T
ξN a′ N 2
U= k BT − v (1.12)
2 V
Equation (1.10) is the well-known van der Waals equation of state that can be reorganized to the
form
RT aˆ
P= − v2 (1.13)
vˆ − bˆv vˆ
where v̂ is the molar specific volume, NA is Avogadro’s number, R = NAkB is the universal gas con-
stant, and âv and b̂v are the molar van der Waals constants:
aˆ v = av′ N A2 (1.14a)
b̂v = bv′ N A (1.14b)
The relation for chemical potential can similarly be written in terms of molar specific chemical
potential and molar specific volume:
µˆ bˆv 3   2πMk B T ( vˆ − bˆv )2/3   (ξ − 5) 

= −   ln  − ln π + ln σ s 
RT vˆ − bˆv  2   N A2/3 h 2   2 
(1.15)
(ξ − 3)  T  2aˆ v
− ln  −
2  θrot ,m  vRT
ˆ
Equation (1.13) can be reorganized in terms of the mass specific volume v, leading to
RT a
P= − v (1.16)
v − bv v 2
Here M is the molecular mass, R = R / M is the specific gas constant, and av and bv are the mass-
based van der Waals constants:
av = aˆ v / M 2 (1.17a)
bv = bˆv / M (1.17b)
This model analysis thus leads to property relations for a van der Waals fluid. Although it incorpo-
rates many idealizations, the van der Waals model analysis provides a workable framework for pre-
dicting properties of dense gases and liquids that relates macroscopic thermodynamic properties to
molecular characteristics. In particular, it relates the van der Waals constants to the physical size of
the molecules and the intermolecular potential function that characterizes force interactions among
molecules. Consistency of the thermodynamic properties with the critical point conditions requires
that the van der Waals constants must be related to the critical pressure Pc and temperature Tc as
27( R / M )2 Tc2
av = (1.18a)
64 Pc
( R / M )Tc
bv = (1.18b)
8 Pc
The model analysis for a fluid of interacting molecules described above incorporates several ide-
alizations. While its property predictions do not exactly match the behavior of real fluids, they
are qualitatively consistent with the behavior of real fluids. Improved property predictions of this
type can be developed by incorporating more accurate non-symmetric potential function models
(see the discussions in references [1.2–1.5]).
Because the predictions of the van der Waals model are expected to be qualitatively consistent with
the behavior of many fluids, and the resulting relations are mathematically simple, we will use it here
to explore the main thermodynamic features of liquid-vapor phase change for a pure fluid system. The
van der Waals equation of state (1.16) can be used to predict the isotherm shapes on a P–v diagram.
Introducing the following reduced properties normalized with their critical point values
Tr = T /Tc (1.19a)
Pr = P /Pc (1.19b)
vr = v /vc (l.19c)
the van der Waals equation of state can be written in the dimensionless form
8Tr 3
Pr = − (1.20)
3vr − 1 vr2
Note that in Eqs. (1.19a)–(1.19c), temperatures are absolute (K) and vc is the critical specific volume.
Using Eq. (1.20), the variation of Pr with vr for fixed reduced temperature Tr defines a dimension-
less van der Waals isotherm on the plot of Pr versus vr . Reduced isotherms of this type are plotted
in Fig. 1.2.
Below the critical temperature (Tr < 1), the van der Waals model predicts that isotherms exhibit
a local minimum and maximum, as indicated in Fig. 1.2. For coexisting liquid and vapor phases,
thermodynamics theory dictates that the necessary conditions for equilibrium are that the tempera-
ture, pressure, and chemical potential in the two phases must be equal.
Tl = Tv , Pl = Pv , µˆ l = µˆ v (1.21)
In reduced properties, these requirements become
Tr ,l = Tr ,v , Pr ,l = Pr ,v , µ r ,l = µˆ l / RTc = µ r ,v = µˆ v / RTc (1.22)
In Fig. 1.2, this implies that the points corresponding to the reduced specific volume of liquid, vr ,l
and vapor, vr ,v must lie on a line of constant pressure (horizontal line) and be on the same isotherm.
The additional constraint that the chemical potentials be equal is implemented by using Eq. (1.15) to
FIGURE 1.2 Reduced property van der Waals isotherms.
evaluate µˆ l and µˆ v and requiring that Psat = Pl = Pv be chosen so that the computed µˆ l and µˆ v values
are equal. This defines the link between the vapor pressure Psat and the specified temperature as
well as the temperature dependence of the saturation specific volumes.
It should be noted that if a liquid is depressurized isothermally in a quasi-equilibrium process
from initial state A in Fig. 1.2, classical equilibrium thermodynamics predicts that the state point of
the system follows the isotherm (constant Tr line) down until it reaches state point B. Upon reach-
ing point B, classical theory implies that further reduction in pressure can only occur after a phase
change occurs. Heat must be input to convert liquid into vapor as the state point shifts from B to F.
Once all liquid is converted to saturated vapor at point F, further reduction in pressure will cause
the state point to move along the isotherm toward point G. Note that this implies that at specific vol-
umes between vr ,l and vr ,v , the system contains a mixture of two coexisting phases: saturated liquid
at vr ,l and saturated vapor at vr ,v. Classical theory further implies that state points on the equation of
state isotherm between B and F are not observed in an equilibrium system. We will see, however,
that real systems in applications often depart from equilibrium, and it is sometimes possible for the
system to exist in some states on the isotherm between B and F. In fact, these departures from equi-
librium will be shown to play a central role in the onset of phase-change processes.
The relationship between the molecular behavior and macroscopic characteristics for the vapor
phase can, at least qualitatively, be understood from the kinetic theory of gases. Basic elements of the
kinetic theory are developed in Appendix I. Readers unfamiliar with at least the basic aspects of the
kinetic theory of gases are advised to review this appendix before proceeding further in this section.
In Appendix I, the following Maxwell-Boltzmann speed distribution for molecules in a gas is
derived from the kinetic theory of gases:
3/2
 m  2
dN c = 4 πN  c 2e − mc /2 k B T
dc (1.23)
 2πk B T 
The relation ε = (1/2)mc2 for the kinetic energy of a molecule can be inverted to obtain
c = (2ε /m)1/2 (1.24)
Differentiating this relation yields
dc = (1/2m)1/2 ε −1/2 dε (1.25)
Substituting Eqs. (1.24) and (1.25) into Eq. (1.23), the following energy distribution is obtained
dN ε = 2πN (πk B T )−3/2 ε1/2e −ε / k BT dε (1.26)
In the above relation, dNε is interpreted as the number of molecules having kinetic energies between
ε and ε + dε.
It is often useful to know the fraction of the molecules in the gas that have energies exceeding
a specified value ε*. The number of molecules in the gas with energies above ε*, N>ε* , is given by
∞
N >ε* = dN ε
∫
ε*
(1.27)
The fraction of molecules with energies above ε* is just N >ε* / N . Substituting Eq. (1.26) for the
integrand in Eq. (1.27), dividing both sides by N and evaluating the integral yields
1/2
N >ε*  4 ε* 
N
=
 πk B T 
e −ε*/ k BT + erfc ( ε* k B T ) (1.28)
When the threshold energy ε* is much larger than kBT, the complementary error function term will
be very small and can be neglected. For such conditions N>ε*/N is given by
1/2
N >ε*  4 ε* 
= e −ε*/ k BT (ε* >> k B T ) (1.29)
N  πk B T 
Perhaps the most significant aspect of Eq. (1.29) is that it predicts that the fraction of molecules hav-
ing energies above the threshold value ε* increases rapidly with temperature. This behavior, which
is characteristic of the kinetic energy of molecules in liquids as well as in gases, plays an important
role in determining chemical reaction rates and the equilibrium conditions in two-phase systems.
The equilibrium vapor pressure and its variation with temperature in a system containing satu-
rated liquid and vapor are also consequences of the fact that the energy distribution among the mol-
ecules in the liquid and vapor phases is similar to the Maxwell-Boltzmann distribution. Because the
system exhibits this energy distribution, even at low temperatures some fraction of the molecules
in the liquid will have sufficient energy to escape the cohesive forces of other liquid molecules at
the liquid-vapor interface. If the kinetic energy distribution in the liquid is similar to the Maxwell-
Boltzmann result given by Eq. (1.29), the fraction capable of escaping in this manner will increase
rapidly with temperature.
The rapid increase of the equilibrium vapor pressure suggested by these arguments is character-
istic of most substances. This line of reasoning also suggests that at a given temperature, liquid with
a small cohesive energy will have a higher vapor pressure than one with a large cohesive energy.
Note that if a Lennard-Jones potential is used to model force interactions among molecules in the
fluids, the cohesive energy is expected to vary proportional to the depth of the potential well (ε in
Eq. (1.3)). Since the latent heat of vaporization is also a macroscopic indicator of the cohesive energy
of the liquid, it follows that at the same temperature, a liquid with a high latent heat of vaporiza-
tion should have a lower vapor pressure than a liquid with a smaller latent heat. This trend is also
observed for most liquids.
It is clear from this development that the constant bv in the van der Waals equation is associated
with the volume occupied by the molecules themselves and the av/v2 term accounts for attractive forces
between the molecules. These attractive forces, sometimes referred to as van der Waals forces, may in
general be a combination of the dispersion, electrostatic, and induction forces described above.
Because the attractive forces represented by the av /v2 term are the same forces that must be over-
come to separate molecules that are initially closely spaced, the constant av is roughly proportional
to the latent heat of vaporization of the liquid. Note also that the contribution of the av /v2 term varies
strongly with the density (and therefore the spacing) of the molecules. For low-density gases v is
large and the contribution of av /v2 is small. For a liquid, the specific volume is very small and the
contribution of av /v2 will be much larger than for the vapor phase of the same substance.
These arguments can be made more concrete by considering a specific example. It can easily be
shown using density and molecular weight data from Appendix II that for saturated liquid water at
atmospheric pressure (101 kPa) the mean volume occupied per molecule is about 3.1 × 10 –29 m3. If
we envision the molecules as being evenly spaced in a cubic lattice, the mean spacing is approxi-
mately the cube root of the mean volume, or 3.1 × 10 –10 m apart. Since the diameter of a water
molecule is about 2Å (2.0 × 10 –10 m), the center-to-center spacing of the molecules is only about
1.5 molecular diameters in the saturated liquid.
For saturated water vapor at 101 kPa, the same line of reasoning suggests that the volume per
molecule is 5.0 × 10 –26 m3 and the molecular spacing is 3.7 × 10 –9 m or about 19 molecular diam-
eters. If r0 in the Lennard-Jones potential shown in Fig. 1.1 is taken as being about 1 molecular
diameter, then it is clear from these numbers that attractive forces will be very small in the saturated
vapor, but very important in the saturated liquid. This is completely consistent with the magnitude
of these forces implied by the av/v2 term in the van der Waals equation.
Example 1.1
To model nitrogen molecule force interaction with the Lennard-Jones potential (Eq. (1.3)), a value
of 1.31 × 10 –21 J is recommended for ε. Note that this sets the depth of the potential well (Fig. 1.1),
and the value of ε is the energy that must be input for one molecule to escape the attractive pull
of another. In a two-phase system, escape of molecules from a liquid phase into a vapor phase
at the interface is more probable if the translational kinetic energy is larger than ε. For saturated
nitrogen at 77 K, estimate the fraction of the molecules that have translational kinetic energies
larger than ε = 1.31 × 10 –21 J.
Equation (1.28) can be used to predict the fraction of molecules with translational energies
greater than ε. In the equation, we set ε* = ε = 1.31 × 10 –21 J and T = 77 K.
ε* 1.31× 10 −21
= = 1.23
kBT 1.38 × 10 −23 (77)
Substituting into Eq. (1.28) yields
1/ 2
N>ε *  4ε* 
N
=
 πkBT 
e −ε */ kBT + erfc ( ε* / kBT )
1/ 2
N>ε *  4(1.23) 
N
=
 π 
e −1.23 + erfc ( )
1.23 = 0.366 + 0.117 = 0.483
Thus, the Boltzmann distribution predicts that almost half the molecules have translation energy
values greater than ε = 1.31 × 10 –21 J.
For molecules in the center of the large body of liquid, the attractive forces from surrounding mol-
ecules are nominally spherically symmetric and hence they balance out to zero. Near a liquid-vapor
interface, however, things are quite different. Within a few molecular diameters of the interface,
molecules in the liquid must redistribute themselves to accommodate the lack of spherical sym-
metry in the molecular force interactions. Liquid-vapor phase-change processes necessarily involve
the coexistence of a liquid and vapor phase, and the conversion of one phase to the other typically
occurs at the boundary between the bulk phases. This boundary region is usually of central impor-
tance in such processes. To gain a better understanding of the thermophysics of this region, in the
following sections we will examine its characteristics in detail. In the remaining sections of this
chapter we will consider it from a molecular perspective. In Chapter 2, we will examine how the
effects of this region can be treated from a macroscopic point of view.
1.2 THE INTERFACIAL REGION - MOLECULAR THEORIES OF CAPILLARITY

Macroscopic thermodynamic and fluid mechanics treatments of the boundary between two phases
invariably assume a sharp discontinuity in density and/or composition across the boundary or inter-
face. In considering the details of physical processes at the interface, however, it is important to
recognize that at a molecular level, changes in fluid or material properties actually occur over a thin
interfacial region that separates the bulk liquid and vapor phases. Consideration of molecular inter-
actions in this interfacial region has led to a better understanding of several aspects of interfacial
phenomena. Although it will often be more convenient to treat the boundary between the phases
as if it were a two-dimensional surface, in this and the next section we will examine the nanoscale
features of the interfacial region.
Anyone who has watched small bubbles rise in a carbonated beverage or a pot of boiling water
has undoubtedly noted that the bubbles are almost perfectly spherical, as if an elastic membrane
were present at the interface to pull the vapor into a spherical shape. From a thermodynamic point of
view, this apparent interfacial tension may be interpreted in terms of energy stored in the molecules
near the interfacial region separating the bulk phases.
Figure 1.3 schematically shows the density distribution near a liquid-vapor interface. On the liq-
uid side of the interfacial region, the density is lower than that in the bulk liquid phase. As described
in the previous section, because the molecules attract one another, energy must be supplied to move
them apart. Hence, the energy per molecule is greater in the interfacial region than in the bulk liq-
uid. The system thus has an additional free energy per unit area of interface due to the presence of
the interface.
There is also the more obvious mechanical interpretation of the interfacial tension as a force per
unit length parallel to the interface (and perpendicular to the density gradient). This interpretation
can also be viewed as being a consequence of attractive and repulsive interactions among molecules
that result from the molecular forces described in the previous section. In the bulk liquid, molecules
are subject to forces of repulsion from their close neighbors and forces of attraction from all others.
The repulsive forces are generally stronger, but since both types of forces act symmetrically in all
directions, on the average, the resultant on each molecule is zero.
As indicated in Fig. 1.3, the mean spacing of the molecules in the liquid near the interface is
greater than in the bulk liquid. Note that the potential functions discussed in the previous section
imply that the close-range repulsive force (force being –dϕ/dr) varies more rapidly with spacing than
the longer-range attractive forces. Hence, for a given molecule, this slightly increased spacing would
significantly weaken the repulsive force it feels from its immediate neighbors, but would likely pro-
duce only a small change in the attractive force between it and more distant surrounding molecules.
In the direction normal to the interface, this combination of effects would produce a force imbal-
ance that would draw the molecules toward the bulk liquid. The mean spacing of the molecules in
the direction normal to the interface could decrease slightly to establish a balance between long-
range attractive forces and repulsion from close neighboring molecules.
FIGURE 1.3 Variation of the molecular density across the interfacial region.
In the directions parallel to the interface, however, the decrease in repulsion force between mol-
ecules produced by the increased spacing does not create a force imbalance because of the radial
symmetry of the force interactions. Consequently, there is no impetus to decrease the mean spac-
ing in this direction. The decrease in repulsive forces between immediate neighbors, with little
change in the longer-range attractive forces may thus produce a net tension force among molecules
in the interface region acting equally in all directions parallel to the interface. Although crude, these
arguments clearly imply that the existence of a net tension force on the molecules is a direct con-
sequence of the increased mean molecular spacing and the density gradient in the interface region.
As discussed in the previous section, the intermolecular attractions that give rise to interfacial ten-
sion may result from several different types of molecular forces. These may include forces that are
specific to particular types of molecules, such as the metallic bond or the hydrogen bond, as well as
dispersion forces, which exist in all types of matter and always give an attractive force between adja-
cent atoms or molecules no matter how dissimilar they are chemically. The dispersion forces vary with
the electrical properties of the substances involved and the distance between interacting elements, but
they are independent of temperature. While the magnitude of the attractive force between molecules
may vary, virtually all molecules exhibit long-range attractive force interactions and short-range repul-
sive interactions that can give rise to the increased interfacial free energy described above.
The characteristics of the interfacial region can be explored in a more quantitative way by extend-
ing classical thermodynamic analysis to the interfacial region with the idealization that properties
vary continuously across the region and that local thermodynamic equilibrium applies in a time
averaged sense within small control volumes within the interfacial region. This approach was pio-
neered by van der Waals [1.6] and is usually referred to as the van der Waals theory of capillarity or
the molecular theory of capillarity. It is also sometimes referred to as a mean field theory because
it is based on the idealization that the behavior of each molecule in a localized region is dictated by
the mean field associated with the surrounding molecules.
FIGURE 1.4 Variation of mean molar density and volumetric free energy ψ = F/V across the interfacial
region.
The classical van der Waals mean field theory of capillarity is based on the postulate that
the mean properties vary continuously across the transition region between the bulk phases
(see the discussions in Rowlinson [1.6] and Rowlinson and Widom [1.7]). Specifically, the van
der Waals model postulates a continuous variation of mean local density (number density ρn
or molar density ρ̂ = ρn/NA) across the interfacial region, as indicated in Fig. 1.4. The van der
Waals analysis leads to the conclusion that the interfacial tension is equivalent to the excess
interfacial free energy per unit area σ, which is the free energy per unit area above that for
step changes in ρ̂ and the free energy per unit volume at z = 0 (Fig. 1.4). The model postulates
that, in accordance with mass conservation and the second law of thermodynamics, the density
distribution spontaneously adjusts to minimize the total excess free energy (per unit area) in
the interfacial region.
In the van der Waals theory of capillarity, the z = 0 location in the interfacial region is chosen so that
0 ∞
∫
−∞
(ρˆ − ρˆ v ) dz + ∫ (ρˆ − ρˆ ) dz = 0
0
l (1.30)
Equation (1.30) ensures that the mass in the interfacial region with a distributed density profile is the
same as would exist in the region with a discontinuous density step change at z = 0. The free energy
per unit volume is defined as
ψ = F /V (1.31)
Here F is the Helmholtz free energy and V represents the volume of a local system within the inter-
facial region. The relation below stipulates that σ is the free energy per unit area of interface in
excess of that for step changes in ρ̂ and ψ at the interface at z = 0 (Fig. 1.4).
0 ∞
σ=
∫
−∞
 ψ − ψ ( ρˆ v )  dz +
∫ ψ − ψ (ρˆ ) dz
0
l (1.32)
The van der Waals model of capillarity is postulated to apply to a system held at constant tempera-
ture with a volume that encompasses the interfacial region over a unit area of the interface. The
second law of thermodynamics requires that for such a system (with fixed V and T), equilibrium cor-
responds to a minimum in the Helmholtz free energy. Since volume is fixed, this also corresponds
to a minimum in volumetric free energy ψ = F/V. This equilibrium free energy σlv is the property
commonly referred to as interfacial tension or surface tension.
Determination of the equilibrium interfacial tension using van der Waals theory thus
requires solution of a constrained minimization problem. We must determine the mean density
variation ρˆ ( z ) that minimizes the right side of Eq. (1.32). The interfacial tension or interfacial
free energy σlv is the value of the integral on the right side of Eq. (1.32) for ρˆ ( z ) that satisfies
Eq. (1.30) and minimizes the integral. To execute this scheme requires a means of predicting
ψ ( ρˆ , z ) in the interfacial region that accounts for the effects of the density gradient there. The
classical van der Waals theory of capillarity extends the statistical thermodynamics model
for properties of a van der Waals fluid described in the previous section to evaluate ψ and
other properties in the interfacial region. Once property relations are generated, one of the two
approaches can be used:
1. An empirical relation with an adjustable constant can be postulated for the density profile
and the integrals on the right side of Eq. (1.32) can be numerically evaluated for chosen
values of the adjustable constant to determine the value that minimizes σ.
2. The calculus of variations [1.8] can be applied to derive an integral relation for the mini-
mum σ and the density variation across the interface. Numerical evaluation of the integral
relation predicts the interfacial tension σlv and the density variation across the interfacial
region.
A more detailed discussion of the two methods described above can be found in Appendix III.
Using one of these methods, it is therefore possible to compute predictions of the surface ten-
sion and density profile in the interfacial region for a van der Waals fluid using Eqs. (1.30) and
(1.32), together with the Lennard-Jones model constants and other molecular parameters for
the fluid.
The classic van der Waals mean field theory of capillarity described above has generally been
viewed as an approximate theory. Its predictions are qualitatively similar to real fluid behavior,
but its numerical predictions are inaccurate. The predicted property values and the trends in the
variations of properties with temperature do not agree with those observed for real fluids. Near the
critical point, it is well known that the corresponding states correlation for surface tension that best
matches data for real fluids typically varies proportional to (1 − T/Tc) to an exponential power of
about 1.22 (see the discussion in Poling et al. [1.9]). The van der Waals mean field model predicts
that surface tension varies proportional to (1 − T/Tc)3/2. The van der Waals model also predicts that
the interfacial region thickness varies proportional to (1 − T/Tc) –1/2, whereas recent measurements
(by, for example, Beysens and Robert [1.10]) indicate that the interfacial region thickness varies
about proportional to (1 − T/Tc) –0.62. Despite its shortcomings, the van der Waals theory of capillar-
ity provides useful insight into the connection between molecular properties and interfacial region
thermophysics. In particular, it clearly indicates that interfacial free energy is a consequence of the
attractive force interactions among molecules and the density gradient that exists in the interfacial
region. However, the crudeness of the van der Waals model limits the usefulness of its quantitative
predictions.
In a recent investigation, Carey [1.11] has developed an alternative version of the molecular
theory of capillarity that incorporates a Redlich-Kwong model of fluid properties. The Redlich-
Kwong fluid model was chosen because it is a simple model and its predictions generally agree
better with real fluid saturation property data than predictions of the van der Waals model. The
formulation of Carey [1.11] used the calculus of variations method described in Appendix III
with properties determined using the Redlich-Kwong property model extended to the conditions
in the interfacial region. Using this model analysis, Carey [1.11] obtained integral relations for
the interfacial tension and the density variation across the interfacial region that can be cast in
the following dimensionless forms:
ρr ,l
σ lv 1.929  1  Pr ,sat  ρr ,v (1 − ρr br ) 
Pc Li
= 1/4
Tr (1 − Tr )
0.17 ∫ 

ρr , v 
( 
1 + br ρr )  3
− ρr Tr ln 


 − ρr Tr
ρr (1 − ρr ,v br ) 
(1.33)
1/2
ar ρr  1 + ρr br  br Tr ρr ,v ρr aρ  ρr ,v br   
– ln – + r r  1 + ρ b    dρr
3br Tr1/2  1 + ρr ,v br  1 − ρr ,v br 3br Tr1/2  
r ,v r 
ρr
z − zv 0.1639 ar   P  ρr ,v (1 − ρr br ) 
Li
= 1/4
Tr (1 − Tr )
0.17 ∫ (1 + br ρr )  r ,sat − ρr Tr ln 

ρr , v +δρr 
 3

 ρr (1 − ρr ,v br ) 
(1.34)
−1/2
a ρr  1 + ρr br  br Tr ρr ,v ρr a ρr  ρr ,v br   
−ρr Tr − r 1/2 ln  − + r 1/2  dρr
3br Tr  1 + ρr ,v br  1 − ρr ,v br 3br Tr  1 + ρr ,v br   

In these relations, the earlier definitions of Pr and Tr apply and
ρr = ρˆ / ρˆ c (1.35)
ar = 3.84732 (1.36)
br = 0.25992 (1.37)
Li = [ k B Tc /Pc ]1/3 (1.38)
In the above formulation, Li is a characteristic length associated with the size of the interfacial
region. Note that to compute the dimensionless interfacial tension and density profile for a specified
Tr , the values of the dimensionless saturation properties must first be determined. The dimension-
less saturation pressure can be computed using the following theoretically based curve-fit to the
saturation pressure predictions for a Redlich-Kwong fluid [1.11]:
{ (
Pr ,sat = Tr exp −2.9327 Tr−3/2 − 1 )} (1.39)
The above relation predicts values of the saturation pressure that agree closely with full calculations
of Pr,sat for a Redlich-Kwong fluid. If the predicted Pr,sat value from Eq. (1.39) is used, the reduced
saturation density for the liquid and vapor are determined by solving the Redlich-Kwong equation
of state
3Tr a
Pr = − 1/2 r (1.40)
vr − br Tr vr ( vr + br )
for three density values that satisfy the equation for the specified Tr and computed Pr,sat. The
highest and lowest density solutions are the liquid and vapor saturation densities. The saturation
properties can be determined to higher accuracy if Pr,sat and the subsequent density calculations
are iterated to find the values that, when substituted in the chemical potential relations, more
accurately satisfy the equilibrium requirement that µˆ v / RTc = µˆ l / RTc (see reference [1.11] for
details).
Carey [1.11] used Redlich-Kwong thermodynamic property relations to determine the saturation
properties, and then determined the dimensionless density profile and interfacial tension by numer-
ically integrating the dimensionless Eqs. (1.33) and (1.34). Asymptotic analysis of the Redlich-
Kwong property relations (1.33) and (1.34) indicates the following power-law dependence of the
surface tension at small 1 − Tr:
σ lv
∼ (1 − Tr )
1.33
Pc ( k B Tc Pc )
1/3
In fact, the relation
σ lv
= 14.65 (1 − Tr )
1.33
(1.41)
Pc ( k B Tc Pc )
1/3
closely matches the theoretical predictions computed by Carey [1.11] for Tr between 0.6 and 0.98
shown as the solid line in Fig. 1.5. Also shown in Fig. 1.5, are recommended surface tension values
for a variety of fluids from the ASHRAE Fundamentals Handbook [1.12]. It can be seen that the
recommended dimensionless surface tension values exhibit a power-law dependence proportional
to about (1 − Tr)1.25. In contrast, the van der Waals model predicts that surface tension varies pro-
portional to (1 − Tr)1.5. Although the agreement is not perfect, the modified Redlich-Kwong model
agrees fairly well with the recommended values and is a better fit than the classical van der Waals
model.
FIGURE 1.5 Theory prediction of interfacial tension for a Redlich-Kwong fluid computed using Eqs. (1.33)
and (1.34). Also shown are recommended values from the ASHRAE Fundamentals Handbook [1.12].
In addition to providing a prediction of the interfacial tension, molecular theories of capillarity

also provide insight into the structure of the interfacial region. This is explored further in the next
section.
1.3 NANOSCALE FEATURES OF THE INTERFACIAL REGION

As noted in the previous section, Eq. (1.34) can be integrated to determine the correspondence
between density and z location in the interfacial region. The density profiles predicted in this man-
ner using Carey’s [1.11] model are plotted in Fig. 1.6. A dimensionless thickness of the interfacial
region δzi/Li can be defined as
δzi
=
(ρr ,l − ρr ,v )
Li ( dρr dz )z = 0
(1.42)
Li
where the derivative is evaluated at the z = 0 location determined from the integral computation of
the density profile. Differentiating Eq. (1.34) to evaluate the derivative, this equation can be written
in the form
δzi 0.1639 ( ρr ,l − ρr ,v ) ar   P  ρr ,v (1 − ρr br ) 
= (1 + br ρr )  r ,sat − ρr Tr ln  
Li Tr (1 − Tr )  ρr (1 − ρr ,v br ) 
1/4 0.17
Li   3
−1/2
(1.43)
ar ρr  1 + ρr br  br Tr ρr ,v ρr a ρr  ρr ,v br   
−ρr T − ln  − + r 1/2 
3br Tr1/2  1 + ρr ,v br  1 − ρr ,v br 3br Tr  1 + ρr ,v br   

z=0
It should be noted that the subscript z = 0 on the right side of Eq. (1.43) implies that the expression
in the square brackets is to be evaluated at the ρr value at z = 0. Full application of this relation thus
requires that the density profile be determined first to establish the ρr value at z = 0. Alternatively, a
good approximate value for δzi/Li can be computed using Eq. (1.43) if the ρr value at z = 0 is taken
to be (ρr,v + ρr,l)/2. This is a good approximation since the density at z = 0 is generally close to the
average for the two phases (Fig. 1.6).
FIGURE 1.6 Reduced density profiles across the interfacial region predicted for a Redlich-Kwong fluid at
various reduced temperatures.
FIGURE 1.7 Variation of interfacial region thickness with reduced temperature.
The variation of the interfacial region thickness with reduced temperature determined using
Eq. (1.43) with the ρr value at z = 0 determined from the density profile is plotted in Fig. 1.7. The
length scale Li used to normalize z in Figs. 1.6 and 1.7 is on the order of one nanometer for many
common fluids (Table 1.1). Consequently, the thickness of the interfacial region for many fluids is
predicted to be on the order of a few nanometers for temperatures corresponding to 0.6 ≤ Tr ≤ 0.98.
As indicated in Fig. 1.7, the variation of interfacial region thickness predicted by the theory is well
represented by the power-law relation
δzi
= 0.683 (1 − Tr )
−0.67
(1.44)
Li
This relation provides a means of estimating the interfacial region thickness for coexisting vapor
and liquid phases of a pure substance at a specified saturation temperature.
While not exact, molecular theories of capillarity provide a theoretical understanding of the vari-
ations of surface tension and interfacial region thickness with temperature that are observed in real
fluids. Note that the molecular capillarity theories described above indicate that interfacial tension
TABLE 1.1
Values of Li for Various Fluids
Tc(K) Pc (MPa) Li (nm)
N2 126.2 3.400 0.800
CH4 190.6 4.599 0.830
Ar 150.7 4.865 0.753
O2 154.5 5.043 0.751
H2O 647.3 22.129 0.739
NH3 405.6 11.290 0.793
C3H8 (propane) 369.9 4.248 1.063
SF6 318.7 3.760 1.054
R-134a 374.3 4.059 1.084
Hg 1763.2 151.0 0.544
and interfacial region thickness are only a function of temperature for a pure fluid. They indicate
that the surface tension vanishes at the critical point and varies about proportional to (1 − Tr)n where
n is about 1.2–1.5. They similarly indicate that the thickness of the interfacial region varies about
proportional to (1 − Tr) –m where m is about 0.5–0.6. The theories predict that the thickness of the
interfacial region grows without bound as T → Tc. These theories further imply that the variation
of these properties conforms to thermodynamic similitude. This suggests that relations among the
properties for different fluids can be reduced to a single relation in terms of properties normalized
with critical point parameters. This insight is useful in developing relations that can be used to pre-
dict surface tension values for different fluids systems.
Molecular theories of capillarity also predict the physical size of the interfacial region. From
Figs. 1.6 and 1.7 and Table 1.1, it can be surmised that the thickness of the interfacial region is on
the order of a few nanometers for a wide variety of fluids under commonly encountered condi-
tions. This suggests that for systems in which characteristic length scales are on the order of a
few nanometers, the properties associated with the interfacial region, including surface tension,
will be altered from those observed in an interface between two extensive bulk phases. This may
be particularly important in interfacial phenomena that occur in micro- and nanoscale system
applications.
Carey [1.11] also noted that the molecular theory of capillarity predicts that the center of the
interfacial region lacks intrinsic stability, suggesting that the interior of the interfacial region
may exhibit high levels of property fluctuations. As discussed in the next section, the interfacial
region property statistics for molecular dynamic simulations appear to be consistent with this
observation.
Example 1.2
For water at atmospheric pressure, use the Redlich-Kwong capillarity theory to estimate the sur-
face tension and the interfacial region thickness. Compare the surface tension value to the tabu-
lated value in Appendix II.
For water, from Table 1.1, Tc = 647.3 K, Pc = 22.1 MPa and Li = 0.739 nm. It follows that
Tr = T /Tc = (100 + 273.2) / 647.3 = 0.577
Solving Eq. (1.41) for σlv and substituting
σ lv = 14.65Pc (kBTc /Pc )1/ 3 (1− Tr )

1.33
= 14.65 (22.1× 106 )[1.38 × 10 −23 (647.3) / 22.1× 106 ]1/ 3 (1− 0.577)1.33
= 0.076246 N/m
Solving Eq. (1.44) for δzi and substituting
δzi = 0.683Li (1− Tr )−0.67 = 0.683(0.739)(1− 0.577)−0.67 = 0.906 nm
The computed surface tension is within about 29% of the tabulated value of 0.0589 N/m in
Appendix II for water at these conditions. Also, the effective diameter of a water molecule is
estimated to be about 0.28 nm, which implies that the thickness of the interfacial region is about
3 molecular diameters.
Another noteworthy outcome from the molecular theory of capillarity is that it predicts specific
interrelationships among bulk fluid properties and interfacial region properties. Based on the results
of molecular capillarity theory for a Redlich-Kwong fluid, Carey and Wemhoff [1.13] derived the
FIGURE 1.8 Variation of interfacial region thickness with reduced temperature predicted using recom-
mended property values from the ASHRAE Fundamentals Handbook [1.12].
following relation relating interfacial region thickness to temperature, interfacial tension and the
changes in molar density and internal energy between the two bulk phases:
 ρˆ l − ρˆ v 
δzi = 0.071L2i (1 − T / Tc )
−0.34
 σ  uˆlv (1.45)
lv
This relation can be used to predict interfacial region thickness from the other properties that can be
more directly measured. Figure 1.8 shows a plot of the interfacial region thickness predicted using
Eq. (1.45) for a variety of fluids. The data plotted in this figure were computed using saturation prop-
erties at several temperatures for each fluid. The saturation property data were taken from recom-
mended values in the ASHRAE Fundamentals Handbook [1.12]. The computed δzi values plotted in
Fig. 1.8 indicate that for a variety of common fluids under commonly encountered saturation condi-
tions, the theory described here predicts that the interfacial region thickness is in the range of 1–10
nm. This result, which is consistent with the observed trends in a similar model analysis devised by
Hey and Wood [1.14], is remarkable, given that it seems to apply to molecular species with widely
different molecular structures and interaction potentials.
Example 1.3
Use the property relation (1.45) to predict the interfacial region thickness for saturated nitrogen at
atmospheric pressure using property data from Appendix II.
For nitrogen, from Table 1.1, Tc = 126.2 K, Li = 0.800 nm and
Tr = Tsat /Tc = 77.4 / 126.2 = 0.613

ρˆ l − ρˆ v = (807.1− 4.621) / 28.0 = 28.66 kmol / m3
uˆ lv =  hlv − Psat (1/ ρv − 1/ ρl )  M = 197.6 − 101.3 (1/ 4.621− 1/ 807.1)  28.0
= 4923 kJ/kmol
σ lv = 0.00885 N/m
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pelele, or lip ring, as mentioned by Dr. Weule, who never came
across the Mavia for himself. Of their wearing their hair in pig-tails,
Mr. O’Neill says nothing—in fact, beyond the pelele, there was little
to distinguish them from neighbouring tribes, and he was disposed
to consider them a branch of the Makonde. His description of their
villages hidden away in the thorny jungle and approached by
circuitous paths recalls what Dr. Weule says as to the difficulty of
finding the Makonde settlements without a guide. In the course of
this journey Mr. O’Neill discovered Lake Lidede, and at one point of
his march he looked down on the Rovuma Valley from the edge of
the Mavia Plateau at almost the same point as that where Dr. Weule
saw it from the opposite escarpment, as described on pp. 343–4. It is
interesting to compare the two accounts:—Mr. O’Neill’s is to be
found in the Proceedings of the R.G.S. for 1882, p. 30.
Mr. J. T. Last, starting from Lindi on the 28th of October, 1885,
made his way overland to Blantyre, via Newala, Ngomano and the
Lujende Valley, in eleven weeks. He remarks on the “desolation of
the country which was formerly well populated, as the sites of the old
villages show; but now there is not a house to be seen”—through the
raids of the Magwangara and others. Lions were as numerous as they
appear to have been in 1906, and for a similar reason. One of Mr.
Last’s carriers was dragged out of the grass shelter where the men
were sleeping, thus affording an almost exact parallel to the incident
related by Dr. Weule on pp. 394–8.
At this time the country was under the nominal rule of the Sultan
of Zanzibar, who stationed his officials at some of the places near the
coast and exercised a somewhat intermittent and uncertain authority
over the chiefs in the interior. By the treaty of 1890 the whole of the
mainland as far back as Lakes Victoria and Tanganyika, between the
Rovuma on the south, and the Umba River on the north, was handed
over to Germany, while the protectorate over what remained of the
Sultan’s dominions (viz., the islands of Zanzibar and Pemba) was
taken over by the British Government.
It seems improbable that this immense territory can ever be
colonised by Germans in the same way in which Canada and
Australia have been colonised by ourselves. There are few if any parts
where German peasants and workmen could expect to live, labour,
and bring up families. So far as the country has been settled at all, it
is on the plantation system: European capitalists cultivating large
tracts of land by means of native labour. Some coffee plantations in
Usambara are, we understand, flourishing fairly well, though not
producing wealth beyond the dreams of avarice; but the system, if it
is to be extended to the whole territory, does not augur well for the
future. It is not a healthy one for employer or employed; it always
tends in the direction of forced labour and more or less disguised
slavery; and, in the end, to the creation of a miserable and degraded
proletariat. Much more satisfactory is the method to which Dr.
Weule extends a somewhat qualified approval (though there can be
no doubt that it has his sympathies) of securing to the native his own
small holding and buying his produce from him, as has been done, to
some extent, with the best results, in our own Gold Coast Colony. Dr.
Weule remarks, somewhat naively, that a wholesale immigration
from Germany would be interfered with if the native “claimed the
best parts of his own country for himself.” But surely a ver sacrum of
the kind contemplated is unthinkable in the case of East Africa.
It is possible that the reader may be somewhat perplexed by Dr.
Weule’s estimate—or estimates—of the native character. The
recurring contradictions apparent in various parts of his book arise
from the plan on which it is written. In the original edition, the
traveller’s narrative takes the form of letters addressed to his wife
and friends from the successive stages of his journey. This form has
been dispensed with (beyond the dates at the head of each chapter)
in translation,[1] because the personal allusions, in a foreign dress,
rather detract from than add to the interest of the narrative, and all
the more so, as they are not, in a sense, genuine, but have been
added, après coup, to impart an air of verisimilitude to the letters.
The latter, in fact, were not written from the places at which they are
dated, but were put into shape after the author’s return to Europe,
from notes made on the spot, together with extracts from actual
letters, not printed as a whole. This material, in order not to sacrifice
the freshness of first impressions, has been used very much as it
stood, and it will be noticed that, in many cases, the observations
made at different places correct and qualify one another.
I am glad to find that Dr. Weule stands up for the native in respect
of the old accusation of laziness. He shows that the people of the
Makonde Plateau, at any rate, work pretty hard (in some points, as in
their water-carrying, unnecessarily hard) for a living. He also
defends them against the charge of improvidence, making it quite
plain that they take infinite pains in storing their seed-corn for next
season, and that, if they do not save more of their crops against a
year of famine, instead of making the surplus into beer, it is because
they have, under present circumstances, absolutely no means of
keeping them. It is true that, in one passage, he seems to depreciate
the industry of native women, by comparison with the work done by
German maid-servants and farmers’ wives. But he forgets to make
allowance for the difference of climate—and, perhaps, one may be
permitted to doubt whether any human being really ought to work as
hard as most German women do in town or country.
On the whole, Dr. Weule is kindly disposed towards the native. He
does not seem entirely to have escaped the danger deprecated on p.
41—at least it strikes one that some of the (doubtless not unmerited)
castigations bestowed in the course of his pages might have been
dispensed with by the exercise of a little more patience and tact; but
he remained throughout on the best of terms with his carriers, and
appears to have parted from Moritz, Kibwana and Omari, in spite of
the trials to which they had subjected him in the exercise of their
several functions, with no ill-feeling on either side. More than once
he bears testimony to the uniform good manners of the people whose
villages he visited, and to their homely virtues—their unfailing
cheerfulness, their family affection, and their respect for parents. At
the same time, he relates various incidents calculated to leave a less
pleasant impression, though it must be remembered that the
proportion they bear to the whole of native life is probably less than
that borne by the criminal cases reported in our newspapers to the
daily life and conduct of our population in general. Dr. Weule’s stay
in Africa was surely long enough for him to see that the Bantu native
is not in general bloodthirsty or ferocious; that, on the contrary,
when not maddened by terror or resentment, he is gentle,
reasonable, and even somewhat lacking in vindictiveness compared
with other races. Yet, in the scientific report on the expedition (a
publication several times alluded to in the course of the work before
us) the author is, it seems to me, guilty of a grave injustice.
The reader will note that, on his return to the coast (see pp. 27–9),
he spent some time in studying the records of the Criminal Court at
Lindi, though he does not here tell us anything about the results of
his examination. Now these records certainly afford valuable
material for the study of social conditions; but they should be used
with discrimination. Dr. Weule does not give what is of the very first
importance, the number of criminal cases and their proportion to the
population, especially as the serious cases, which are brought for
trial to Lindi, represent the whole of an extensive province. But he
mentions two atrocities as a proof of the ignorance shown by certain
German newspapers, which “during the last two years have thought
it necessary to insist, over and over again, on the noble traits in the
negro character,” and of the “predominance of low instincts in those
sons of untamed nature” who have “an innate disposition to
violence.” One of the cases in question was that of a woman who
killed her own mother by a blow with the pestle used for pounding
corn. But it is hardly fair to place this murder on the same footing as
a crime committed out of mere brutal passion: the woman’s children
had died, and she believed her mother to have caused their death by
witchcraft. We know what horrible cruelties this belief has induced
people not otherwise depraved to commit: an instance occurred only
twelve or thirteen years ago, no further off than Clonmel. The other
case, which is certainly revolting enough, was the revenge of a
husband on a guilty wife. But both of them together prove absolutely
nothing without information which would enable us to see whether
they are to be regarded as exceptional, or as in any sense typical. The
other incident given by way of proving that violence and brutality are
“in the blood” of the native, is that of an unfortunate woman who,
unsuspiciously passing through the bush, fell in with a band of
unyago boys, and was by them seized and put into a slave-stick “out
of mere mischief and enjoyment of violence.” The comment on this is
that, unless the woman had been a stranger from a distance (who,
under ordinary circumstances would not be very likely to travel
alone), she must have known that there was an unyago in the
neighbourhood, that if she traversed the bush in that direction she
would do so at her peril, and that her trespassing on the forbidden
ground was an act of the grossest impropriety combined with
sacrilege. As for “delight in violence”—surely that, in one form or
another, is an inherent attribute of the “human boy” in every part of
the world, above all when he conceives himself to have a legitimate
excuse?
The mention of the unyago mysteries suggests a subject on which
Dr. Weule has obtained fuller information than any previous writer—
at any rate on this part of Africa. It is surprising that he should have
been able to secure so many photographs of the dances—especially
those of the women—but these only constitute the more public part
of the ceremonial. As to the instruction given to the younger
generation, he does not seem to have got beyond generalities except
in the case of the two old men who, when very drunk, began to
dictate the actual formula in use, though they did not get to the end
of it. Whether any tribal traditions, any myths, embodying the
religious ideas of a far distant past, are handed down along with such
practical teaching about life as the elders are able to give, does not
appear—but from what we know about other tribes it seems highly
probable. Among the Anyanja (Wanyasa) of Lake Nyasa, e.g., a story
accounting for the origin of that lake is told. But perhaps many of the
Makonde and Makua traditions have by this time been forgotten. It
is evident that they have led a very unsettled life for the past forty or
fifty years, besides being decimated by the slave-trade. (This
circumstance, by the by, should always be remembered in connection
with Dr. Weule’s pictures of native life, which leave a painfully
squalid impression. I am far from wishing to idealize the “state of
nature”; but neither the Zulus, nor the Anyanja, nor the Yaos of the
Shire Highlands are so ignorant and careless of hygiene or so
neglectful of their babies as the poor women of Chingulungulu and
Masasi are represented by him to be.)
These “mysteries” are universal—or practically so—among the
Bantu tribes of Africa, and no doubt most others as well. Usually they
are spoken of as an unmixed evil, which Christian missionaries do all
in their power to combat, and some are not backward in calling out
for the civil power (in countries under British administration) to put
them down. The subject is a difficult and far-reaching one, and
cannot adequately be discussed here. My own conviction, which I
only give for what it is worth, is that it is a great mistake to interfere
with an institution of this sort, unless, perhaps, when the people
themselves are ceasing to believe in it, in which case there is danger
of its becoming a mere excuse for immorality. Otherwise, even the
features which to our feelings seem most revolting are entwined with
beliefs rooted in a conception of nature, which only the gradual
advance of knowledge can modify or overthrow. And we must
remember that the problem which these poor people have tried to
solve in their own way is one which presses hardly on civilized
nations as well. Parents and teachers have discovered the evil of
keeping the young in ignorance, or leaving them to discover for
themselves the realities of life; but many of them appear helplessly
perplexed as to the best way of imparting that instruction.
As regards missions, Dr. Weule has not very much to say, but I am
sorry to find that he cannot refrain from the cheap sneer about
“Christianity not suiting the native,” which seems to be fashionable
in some quarters. It seems to be a mere obiter dictum on his part—
perhaps unthinkingly adopted from others—for he brings no
arguments in support of his view, beyond remarking that Islam suits
the African much better, as it does not interfere with his freedom.
But some excuse may be found for those who hold that view in the
erroneous conceptions of Christianity which have prompted various
mistakes on the part of missionaries. It is quite true that such or such
a system of complicated doctrinal belief, the product of long ages and
a special environment, may not suit the African. It is also true that, if
Christianity means Europeanisation—if it means that the African is
to be made over into a bad imitation of an Englishman or German—it
is impossible that it should gain any real hold on him. But it is no
exaggeration to say that no people on earth are more capable—many
are not so capable—of appreciating and acting on the spirit of the
Gospel, of simple love and trust in the Eternal Goodness and
goodwill towards their fellow-men.
The question is a wide one, which cannot be fully discussed within
these limits. Missionaries have often made mistakes and acted
injudiciously; they have in some cases done serious harm, not from
failure to act up to their principles, but from error in those very
principles and a fatal fidelity to them. They may have interfered
between chiefs and people, and broken down customs better left
alone, or may unwittingly have encouraged the wrong sort of
converts by welcoming all and sundry, including fugitives from
justice or people discontented with their home surroundings for
reasons quite unconnected with high spiritual aspirations. Or again,
they may incur blame for the deficiencies of alleged converts who,
after honouring the mission with their presence for a time, depart
(usually under a cloud) and victimise the first European who can be
induced to employ them.
But there is another side to the matter. A man—whether
consciously a follower of the Nietzschean doctrine or not—who
thinks that “the lower races” exist to supply him with labour on his
own terms, is naturally impatient of a religion which upholds the
claims of the weak, and recognizes the status of man as man. Hinc
illæ lacrymæ, in a good many cases. Honestly, I do not think this is
Dr. Weule’s view. But I cannot quite get rid of the suspicion that he
was repeating what he had heard from a planter, and that it was, in
strict accuracy, the planter’s convenience, and not the native, that
Christianity failed to “suit.” Anyone who has read a certain pamphlet
by Dr. Oetker, or Herr von St. Paul Illaire’s Caveant Consules, or
Herr Woldemar Schütze’s Schwarz gegen Weiss will not think this
remark too strong.
It would be deplorable, indeed, if those writers had to be taken as
typifying the spirit of German colonial administration in Africa, or
indeed anywhere else. But I do not think we have any right to
suppose that this is so. There has been, I think, too much militarism
—and very brutal militarism, in some cases—in that administration;
but this is an evil which appears to be diminishing. There is a
tendency, perhaps, to worry the native with over-minute government
regulations, which, no doubt, will as time goes on be corrected by
experience. And there is no lack of humane and able rulers who bring
to their task the same conscientious, patient labour which their
countrymen have bestowed on scientific research; who are trained
for their posts with admirable care and thoroughness, and grudge no
amount of trouble to understand and do justice to the people under
their care. They shall in no wise lose their reward.
A. WERNER.
CAPE GUARDAFUI
Native Life in East Africa
CHAPTER I
OUTWARD BOUND
Dar es Salam, Whit-Sunday, 1906.
Six months ago it would not have entered my head in my wildest

dreams that I should spend my favourite festival, Whitsuntide, under
the shade of African palms. But it is the fact, nevertheless. I have now
been two days in the capital of German East Africa, a spot which may
well fascinate even older travellers than myself. Not that the scenery
is strikingly grand or majestic—on the contrary, lofty mountain-
masses and mighty rivers are conspicuous by their absence, and the
wide expanse of the open ocean contributes nothing directly to the
picture, for Dar es Salam lies inland and has no seaview worth
mentioning. The charm of the landscape lies rather in one of the
happiest combinations of flashing waters, bright foliage, and radiant
sunshine that can be imagined.
The entrance to the harbour gives to the uninitiated no hint of the
beauty to come. A narrow channel, choked with coral reefs, and, by
its abrupt turns, making severe demands on the skill of the pilot,
leads to the central point of a shallow bay which seems to have no
outlet. Suddenly, however, the vessel glides past this central point
into an extraordinarily narrow channel, with steep green banks on
either side, which opens out, before the traveller has had time to
recover from his astonishment, into a wide, glittering expanse,
covered with ships. That is the famous bay of Dar es Salam. In
presence of the obvious advantages of this locality, one need not have
lived for years in the country to understand why the Germans should
have been willing to give up the old caravan emporium of Bagamoyo
with its open roadstead for this splendid harbour, and thus make the
almost unknown native village of Dar es Salam the principal place in
the colony.[2]
DAR ES SALAM HARBOUR
On the voyage out, I visited with much enjoyment both Mombasa

and Zanzibar, though unfortunately prevented by an accident (an
injury to my foot) from going ashore at the German port of Tanga. Of
these two English centres, Zanzibar represents the past, Mombasa
the present, and still more the future. It is true that Zanzibar has the
advantage in its situation on an island at a considerable distance
from the mainland, an advantage of which the mainland towns,
however splendid their future development, will never be able to
deprive it, since their lines of communication, both economic and
intellectual, will always converge on Zanzibar. But since the
completion of the Uganda Railway, Mombasa forms the real gateway
to the interior, and will do so in an increasing degree, as the
economic development of Central Africa—now only in its infancy—
goes on. Whether our two great German railways—as yet only
projected—can ever recover the immense advantage gained by
Mombasa, the future will show. We must hope for the best.
NATIVE DANCE AT DAR ES SALAM
Mombasa and Zanzibar interested me more from a historical than

from a political point of view. How little do our educated and even
learned circles know of the exploration and development, the varied
political fortunes of this corner of the earth on the western shore of
the Indian Ocean! Only specialists, indeed, can be expected to know
that this year is the jubilee of the French Admiral Guillain’s epoch-
making work, Documents sur l’Histoire, la Géographie, et le
Commerce de l’Afrique Orientale, but it is extremely distressing to
find that our countryman, Justus Strandes’ Die Portugiesenzeit in
Deutsch- und Englisch-Ostafrika (1899) is not better known. Most of
us think that Eastern Equatorial Africa, considered as a field for
colonization, is as much virgin soil as Togo, Kamerun and German
South-West Africa, or the greater part of our possessions in the
South Seas. How few of us realise that, before us and before the
English, the Arabs had, a thousand years ago, shown the most
brilliant capacity for gaining and keeping colonies, and that after
them the Portuguese, in connection with and as a consequence of
Vasco da Gama’s voyage to India round the Cape of Good Hope in
1498, occupied an extensive strip of the long coast, and maintained
their hold on it for centuries? And yet these events—these struggles
for East Africa form one of the most interesting chapters in the
history of modern colonization. Here for the first time the young
European culture-element meets with an Eastern opponent worthy
of its steel. In fact that struggle for the north-western shores of the
Indian Ocean stands for nothing less than the beginning of that far
more serious struggle which the white race has waged for the
supremacy over the earth in general, and in which they already
seemed to be victorious, when, a few years ago, the unexpected rise
of Japan showed the fallacious nature of the belief so long
entertained, and perhaps also the opening of a new era.
Anyone who does not travel
merely for the sake of present
impressions, but is accustomed
to see the past behind the
phenomena of the moment, and,
like myself, leaves the area of
European culture with the
express object of using his
STREET IN THE NATIVE QUARTER, results to help in solving the
DAR ES SALAM great problem of man’s
intellectual evolution in all its
details, will find in the voyage to
German East Africa a better opportunity for survey and retrospect
than in many other great routes of modern travel.
This is the case as soon as one has crossed the Alps. It is true that
even the very moderate speed of the Italian express gives one no
chance for anthropological studies. In order to observe the
unmistakable Teutonic strain in the population of Northern Italy, it
would be necessary to traverse the plain of Lombardy at one’s
leisure. But already in the Adige Valley, and still more as one
advances through Northern and Central Italy, the stratification of
successive races seems to me to be symbolized by the three strata of
culture visible in the fields: corn below, fruit-trees planted between
it, and vines covering them above. Just so the Lombards, Goths and
other nations, superimposed themselves on the ancient Italian and
Etruscan stocks. On the long journey from Modena to Naples, it is
borne in upon one that the Apennines are really the determining
feature of the whole Italian peninsula, and that the Romans were
originally started on their career of conquest by want of space in
their own country. The only place which, in May, 1906, produced an
impression of spaciousness was the Bay of Naples, of which we never
had a clear view during our four or five days’ stay. A faint haze,
caused by the volcanic dust remaining in the air from the eruption of
the previous month, veiled all the distances, while the streets and
houses, covered with a layer of ashes, appeared grey on a grey
background—a depressing and incongruous spectacle. The careless
indolence of the Neapolitans, which as a rule strikes the industrious
denizens of Central Europe as rather comical than offensive, requires
the clear sky and bright sunshine, celebrated by all travellers (but of
which we could see little or nothing), to set it off.
From our school-days we have been familiar with the fact that the
countries bordering the Mediterranean—the seats of ancient
civilisation—are now practically denuded of forests. Yet the
landscape of Southern Italy and Sicily seems to the traveller still
more unfamiliar than that of the northern and central districts; it is
even more treeless, and therefore sharper in contour than the
Etruscan and Roman Apennines and the Abruzzi. But the most
striking feature to us inhabitants of the North-German plain are the
river-valleys opening into the Strait of Messina, leading up by steep
gradients into the interior of the country. At this season they seem
either to be quite dry or to contain very little water, so that they are
calculated to produce the impression of broad highways. But how
terrible must be the force with which the mass of water collecting in
the torrent-bed after heavy rains, with no forest-soil to keep it back,
rushes down these channels to the sea! To the right and left of
Reggio, opposite Messina, numbers of sinuous ravines slope down to
the coast, all piled high with débris and crossed by bridges whose
arches have the height and span of the loftiest railway viaducts.
It is scarcely necessary to say anything about Port Said and the
Suez Canal. Entering the Red Sea, I entered at the same time a
familiar region—I might almost say, one which I have made
peculiarly my own—it having fallen to my share to write the
monographs on the three oceans included in Helmolt’s
Weltgeschichte.[3] Of these monographs, that dealing with the
Atlantic seems, in the opinion of the general reader, to be the most
successful; but that on the Indian Ocean is undoubtedly more
interesting from the point of view of human history. In the first
place, this sea has this advantage over its eastern and western
neighbours, that its action on the races and peoples adjacent to it was
continued through a long period. The Pacific has historic peoples
(historic, that is to say, in the somewhat restricted and one-sided
sense in which we have hitherto used that term) on its north-western
margin, in eastern Asia; but the rest of its huge circumference has
remained dead and empty, historically speaking, almost up to the
present day. The Atlantic exactly reverses these conditions: its
historical density is limited to the north-eastern region, the west
coast of Africa, and the east coast of the Americas being (with the
exception of the United States) of the utmost insignificance from a
historical point of view.
Now the Indian Ocean formed the connecting link between these
two centres—the Mediterranean culture-circle in the west, and that
of India and Eastern Asia in the east,—at a time when both Atlantic
and Pacific were still empty and untraversed wastes of water. This,
however, is true, not of the whole Indian Ocean, but only as regards
its northern part, and in particular the two indentations running far
inland in a north-westerly direction, which we call the Red Sea and
the Persian Gulf. To-day, when we carry our railways across whole
continents, and even mountain ranges present no insuperable
obstacles to our canals, we imagine that masses of land as wide as the
Isthmus of Suez or the much greater extent of the “Syrian Porte”—
the route between the Persian Gulf and the Eastern Mediterranean—
must have been absolute deterrents to the sea-traffic of the ancients.
In a sense, indeed, this was the case; otherwise so many ancient
rulers would not have attempted to anticipate us in the construction
of the Suez Canal. But where technical skill is insufficient to
overcome such impediments, and where at the same time the
demand for the treasures of the East is so enormous as it was in
classical and mediæval times, people adapt themselves to existing
conditions and make use of navigable water wherever it is to be
found. Only thus can be explained the uninterrupted navigation of
the Red Sea during a period of several thousand years, in spite of its
dangerous reefs and the prevailing winds, which are anything but
favourable to sailing vessels.
Only one period of repose—one might almost say, of enchanted
sleep—has fallen to the lot of the Red Sea. This was the time when
Islam, just awakened to the consciousness of its power, succeeded in
laying its heavy hand on the transition zone between West and East.
With the cutting of the Suez Canal, the last shadow of this ancient
barrier has disappeared, and the Red Sea and North Indian Ocean
have regained at a stroke, in fullest measure, their old place in the
common life of mankind.
The passengers on board our steamer, the Prinzregent, were
chiefly German and English; and at first a certain constraint was
perceptible between the members of the two nationalities, the latter
of whom seemed to be influenced by the dread and distrust
expressed in numerous publications of the last few years. Mr.
William Le Queux’s Invasion of 1910 was the book most in demand
in the ship’s library.
A more sociable state of things gradually came about during the
latter part of the voyage; and this largely through the agency of an
unpretending instrument forming part of my anthropological
equipment. One day, when we were nearing the Straits of Bab el
Mandeb, partly in order to relieve the tedium of the voyage, and
partly in order to obtain statistics of comparative strength, I
produced my Collin’s dynamometer. This is an oval piece of polished
steel, small enough to be held flat in the hand and compressed in a
greater or less degree, according to the amount of force expended,
the pressure being registered by means of cogged wheels acting on an
index which in its turn moves a second index on a dial-plate. On
relaxing the pressure, the first index springs back to its original
position, while the second remains in the position it has taken up
and shows the weight in kilogrammes equivalent to the pressure. The
apparatus, really a medical one, is well adapted for ascertaining the
comparative strength of different races; but its more immediate
usefulness appears to lie in establishing cordial relations between
total strangers in the shortest possible time. On that particular hot
morning, I had scarcely begun testing my own strength, when all the
English male passengers gathered round me, scenting some form of
sport, which never fails to attract them, young or old. In the
subsequent peaceful rivalry between the two nations, I may remark
that our compatriots by no means came off worst; which may serve
to show that our German system of physical training is not so much
to be despised as has been recently suggested by many competent to
judge, and by still more who are not so competent.
In his general attitude on board ship, the present-day German
does not, so far as my observations go, contrast in the least
unfavourably with the more experienced voyagers of other
nationalities. It is true that almost every Englishman shows in his
behaviour some trace of the national assumption that the supremacy
of the seas belongs to him by right of birth. Our existence, however,
is beginning to be recognized—not out of any strong affection for
“our German cousins,” but as a simple matter of necessity. If, for
comfort in travel, one must have recourse to German ships; and
when, at home and abroad, there is a German merchant-fleet and a
German navy to be reckoned with, the first of which keeps up an
assiduous competition, while the second is slowly but steadily
increasing, these things cannot fail to impress even the less cultured
members of the British nation. Only one thing is, and will be for
many years to come, calculated to make us ridiculous in the eyes of
Old England—and that is the Zanzibar Treaty. Never shall I forget
the looks of malicious triumph and the sarcastic condolences which
greeted us—the unfortunate contemporaries of the late Caprivi—
when we came in sight of Zanzibar. My friend Hiram Rhodes, of
Liverpool, the ever-smiling and universally popular, usually known
as “the laughing philosopher,” from his cheerful view of life, was not
as a rule given to sharp sayings, but with regard to the famous
political transaction, I distinctly remember to have heard him use the
expression, “Children in politics.” Caustic, but not undeserved!
Another remark of his, after viewing Dar es Salam: “That is the finest
colony I have ever seen!” served, it is true, as a touch of healing balm
—but no amount of conciliatory speeches will give us back Zanzibar!
MAP OF THE MAIN CARAVAN ROAD, WITH ITS PRINCIPAL
BRANCHES. DRAWN BY SABATELE, A MMAMBWE
The object of the journey on which I have embarked may now be

briefly stated. Several decades since, and therefore before the
beginning of our colonial era, the Reichstag voted an annual grant of
some 200,000 marks for purposes of scientific research in Africa—
purely in the interests of knowledge and without any ulterior
intentions from a narrowly nationalist point of view. One might have
expected that, after the establishment of our settlements in Africa
and the Pacific, this fund would unhesitatingly have been devoted,
wholly or in part, to the systematic exploration and study of these
colonies of ours. But this has not been done, or only in a very
uncertain and desultory manner—to the great grief of German
scientific circles, who, under these circumstances, were forced to
content themselves with the occasional reports of civil and military
officials supplemented by sporadic research expeditions, official or
private.
It was not till the first Colonial Congress in 1902 that a more
vigorous agitation took place for the application of the African Fund
on a large scale to the systematic investigation of our dependencies.
From specialists in all branches of knowledge—geography and
geology, anthropology and ethnography, zoology and botany,
linguistics, comparative law, and the new science of comparative
music—arose the same cry, with the result that, three years later, at
the second Colonial Congress (October, 1905), we were in a position
to state clearly the most pressing problems and mark out the
principal fields of research in
each subject. It might, however,
have taken years to put the work
in hand, but for the “Committee
for the Geographical
Exploration of the German
Colonies,” and its energetic
president, Dr. Hans Meyer, who
rescued the proceedings from
their normal condition of
endless discussions, and
translated them at one stroke
into action. Dr. Jäger, Herr
Eduard Oehler, and myself are
the living proofs of this (in our
COURTYARD AT DAR ES SALAM—Dolce far country) unwonted rapidity of
niente decision, being selected to carry
out the instructions of the
Committee (which is affiliated to the Colonial Office) and help to
realise the long-cherished dream of German science.
The task of the two gentlemen I have mentioned is purely
geographical, consisting in the examination of the interesting
volcanic area situated between Kilimanjaro and the Victoria Nyanza,
while I am commissioned to bring some order into the chaos of our
knowledge concerning the tribes who occupy approximately the
same region. It must be remembered that the country surrounding
Lakes Manyara and Eyasi, and extending to a considerable distance
south of them, swarms with tribes and peoples who, in spite of the
fact that our acquaintance with them dates more than twenty years
back, still present a variety of ethnological problems. Among these
tribes are the Wasandawi, whose language is known to contain clicks
like those of the Hottentots and Bushmen, and who are conjectured
to be the forgotten remnant of a primæval race going back to
prehistoric ages. The Wanege and Wakindiga, nomadic tribes in the
vicinity of Lake Eyasi, are said to be akin to them. In the whole mass
of African literature, a considerable part of which I have examined
during my twenty years’ study of this continent, the most amusing
thing I ever came across is the fact that our whole knowledge up to
date of these Wakindiga actually results from the accident that
Captain Werther had a field-glass in his hand at a given moment.
This brilliant traveller, who traversed the district in question twice
(in 1893 and 1896), heard of the existence of these people, but all
that he saw of them was a distant telescopic view of a few huts. As yet
we know no more of them than their bare name, conscientiously
entered in every colonial or ethnological publication that makes its
appearance.
Another group of as yet insufficiently-defined tribes is represented
by the Wafiomi, Wairaku, Wawasi, Wamburu and Waburunge. All
these are suspected of being Hamites, and some of them have
evolved remarkable culture-conditions of their own. But, under the
onrush of new developments, they are in danger of losing their
distinctive character still more rapidly than other African peoples,
and, if only for this reason, systematic observations are needed
before it is too late. The same may be said of the Wataturu or Tatoga,
who are undoubtedly to be looked on as the remnant of a formerly
numerous population. They are said to speak a language related to
Somali, but now live scattered over so wide a territory that the
danger of their being effaced by absorption in other races is, if
possible, still greater than in the case of the others. The last of the
tribes which specially concern me are the Wanyaturu, Wairangi and
Wambugwe. All of these belong to the great Bantu group, but have,
in consequence of their isolation, preserved certain peculiarities of
culture so faithfully that they too will be well worth a visit.
IN THE EUROPEAN QUARTER, DAR ES SALAM

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Liquid Vapor Phase Change

Phenomena An Introduction to the

Introduction to Transfer Phenomena in PEM Fuel Cells

Heat Transfer 4 : Convection, Two-Phase Flows and

Elements of Heat and Mass Transfer Second Edition Gupta

An introduction to the geography of tourism Third

Incropera s Principle of Heat and Mass Transfer

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Computational Fluid Dynamics and Heat Transfer, 2nd

Heat Transfer Evolution Design and Performance 1st

An Introduction to the Thermophysics of

© 2020 by Taylor & Francis Group, LLC

No claim to original U.S. Government works

Printed on acid-free paper

International Standard Book Number-13: 978-1-4987-1661-1 (Hardback)

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and the CRC Press Web site at

To Judith, Elizabeth and Sean.

Chapter 1 The Liquid-Vapor Interfacial Region: A Nanoscale Perspective..................................3

Chapter 2 The Liquid-Vapor Interface: A Macroscopic Treatment............................................. 39

Chapter 3 Wetting Phenomena and Contact Angles.................................................................... 69

Chapter 4 Transport Effects and Dynamic Behavior at Interfaces............................................ 109

Chapter 5 Phase Stability and Homogeneous Nucleation.......................................................... 153

Part II Boiling and Condensation Near Immersed Bodies

Chapter 6 Heterogeneous Nucleation and Bubble Growth in Liquids....................................... 203

Chapter 7 Pool Boiling............................................................................................................... 249

7.7 Transition Boiling........................................................................................... 316

Chapter 8 Other Aspects of Boiling and Evaporation in an Extensive Ambient....................... 331

Chapter 9 External Condensation.............................................................................................. 391

Part III Internal Flow Convective Boiling and Condensation

Chapter 10 Introduction to Two-Phase Flow............................................................................... 453

Chapter 11 Internal Convective Condensation............................................................................ 507

Chapter 12 Convective Boiling in Tubes and Channels.............................................................. 555

Rev Reynolds number for vapor phase flowing alone [= GxD /µ v ]

yi mass fraction of species i in vapor binary mixture

σ interfacial tension, or equivalently, the

International Journal of Heat and Mass Transfer, published by Elsevier.

Experimental Thermal and Fluid Science, published by Elsevier.

1.1 A MOLECULAR PERSPECTIVE ON LIQUID-VAPOR TRANSITIONS

φ LJ (r ) = 4ε[(r0 /r )12 − (r0 /r )6 ] (1.3)

FIGURE 1.1 The Lennard-Jones 6–12 potential.

3 N   2πMk B T (V − Nbv′ )2/3   (ξ − 5) 

bv′ = 1.350 ( π / 6 ) D 3 (1.6)

µ Nbv′ 3   2πMk B T (V − Nbv′ )2/3   (ξ − 5) 

b̂v = bv′ N A (1.14b)

µˆ bˆv 3   2πMk B T ( vˆ − bˆv )2/3   (ξ − 5) 

In reduced properties, these requirements become

Tr ,l = Tr ,v , Pr ,l = Pr ,v , µ r ,l = µˆ l / RTc = µ r ,v = µˆ v / RTc (1.22)

FIGURE 1.2 Reduced property van der Waals isotherms.

c = (2ε /m)1/2 (1.24)

Differentiating this relation yields

dc = (1/2m)1/2 ε −1/2 dε (1.25)

dN ε = 2πN (πk B T )−3/2 ε1/2e −ε / k BT dε (1.26)

Substituting into Eq. (1.28) yields

1.2 THE INTERFACIAL REGION - MOLECULAR THEORIES OF CAPILLARITY

In these relations, the earlier definitions of Pr and Tr apply and

Li = [ k B Tc /Pc ]1/3 (1.38)

In fact, the relation

In addition to providing a prediction of the interfacial tension, molecular theories of capillarity