Unsaturated Soils Behavior, Mechanics and Conditions PDF

ENVIRONMENTAL REMEDIATION TECHNOLOGIES,
REGULATIONS AND SAFETY
UNSATURATED SOILS
BEHAVIOR, MECHANICS
AND CONDITIONS
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ENVIRONMENTAL REMEDIATION
TECHNOLOGIES, REGULATIONS
AND SAFETY
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ENVIRONMENTAL REMEDIATION TECHNOLOGIES,
REGULATIONS AND SAFETY
UNSATURATED SOILS
BEHAVIOR, MECHANICS
AND CONDITIONS
MARTIN HERTZ
EDITOR
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Published by Nova Science Publishers, Inc. † New York

CONTENTS
Preface vii
Chapter 1 Unsaturated Soils:
Aspects That Control Moisture Content 1
Teresa M. Reyna, Santiago M. Reyna
and María Lábaque
Chapter 2 Some Aspects of Numerical Modelling of
Hydraulic Hysteresis of Unsaturated Soils 41
Javad Ghorbani and David W. Airey
Chapter 3 Temperature Distribution and Water
Migration in Unsaturated Soil 79
Bingxi Li, Yiran Hu, Fei Xu, Yaning Zhang,
Shuang Liang, Wenyu Song and Zhongbin Fu
Chapter 4 Chemical Potential in Soils and Complex Media 133
Jean-Claude Bénet
Index 193
Related Nova Publications 199
PREFACE
This compilation opens with an exploration of the vadose, or

unsaturated zone, which is of utmost importance as the nexus between
surface water and groundwater. It is the link between what happens on the
surface and what happens below, inside the aquifers. As such,
understanding this underground natural environment is essential for the
sustainable development of society.
Due to the complexities involved in considering the hysteretic response
of the Soil Water Characteristic Curve and its dependency on volume
changes, these two features are often ignored in numerical studies of
unsaturated soils. To facilitate their use in numerical modeling, a model for
the Soil Water Characteristic Curve equation based on the bounding
surface concept is proposed.
The authors go on to focus on the temperature distribution and water
migration in unsaturated soil, which is of significant importance because
these factors are related to the thermal-physical properties of soil. The
changes in these properties may cause disastrous engineering problems
such as the cracking of pavement, damage of structure foundation and
fracture of pipelines.
Lastly, Unsaturated Soils: Behavior, Mechanics and Conditions
addresses the measurement and expression of the mass chemical potential
in the presence of superficial layers induced by a complex structure. By
viii Martin Hertz
definition, the mass chemical potential of a constituent in a soil represents

the variation of the internal energy of the medium when a unit mass of the
constituent is transferred to a reference state with the entropy, volume and
mass of the other constituents remaining constant.
Chapter 1 - Humankind increasingly puts more pressure on natural
resources. The preservation of the underground natural environment is
becoming a necessity to guarantee the progress of humanity. The
evaluation of soil conditions in the field requires considerable time and
effort. This effort, time and equipment needed will depend on the range of
uses required for the data. The area and depth to be studied must be
carefully defined. The area to study will depend on the variability existing
in the place. In certain occasions the characteristics of the soil - water
interactions vary more with depth than with the area considered; some
cases are just the opposite. The study of the vadose, or unsaturated zone, is
of utmost importance because this zone is the nexus between surface water
and groundwater. It is the link between what happens on the surface and
what happens below, inside the aquifers. Improving the knowledge of this
underground natural environment is essential to guarantee the sustainable
development of society.
Chapter 2 - The Soil Water Characteristic Curve (SWCC) plays an
essential role in the response of unsaturated soils as it quantifies the ability
of soils to maintain or lose their available moisture. It is generally
understood that the SWCCs exhibit hysteresis when subjected to cycles of
wetting and drying, and more generally the relationship between suction,
volume changes, and the saturation degree for a given soil is not unique
and can be path-dependent. In particular, the SWCC may show strong
sensitivity to volume changes in cohesive soils. Due to the complexities
involved in considering the hysteretic response of the SWCC and its
dependency on volume changes, these two features are often ignored in
numerical studies of unsaturated soils. To facilitate their use in numerical
modeling, a model for the SWCC equation based on the bounding surface
concept is proposed. The resulting non-linear model is presented in an
incremental form relating the rate of saturation degree to the rate of suction
and volume changes. It is shown that the proposed model has the ability to
Preface ix
replicate the shape and the evolution of the scanning curves observed in the
experiments compared to currently available alternatives. The model has
benefits for numerical application as it improves the convergence
properties of the overall numerical analysis and includes a robust
integration scheme with automatic error control for updating the saturation
degree during the analyses. Results are presented to show the ability and
the robustness of the proposed scheme in modeling the unsaturated soil
response under various loading conditions including static and dynamic
analyses.
Chapter 3 - Temperature distribution and water migration in
unsaturated soil are of significant importance because they are related to
the thermal-physical properties of soil and the changes in these properties
may cause disastrous engineering problems including cracking of
pavement, damage of structure foundation, fracture of pipelines, etc. This
chapter focuses on the temperature distribution and water migration in
unsaturated soil. Temperature distribution and water migration in
unsaturated soil during the freezing and thawing processes are
experimentally investigated and the results are presented and discussed.
Based on the soil structure, multiphase flow, temperature distribution and
water potential, a mesoscopic lattice Boltzmann model (LBM) is
developed to simulate the temperature distribution and water migration in
unsaturated soil. Based on the soil structure, multiphase flow, temperature
distribution, water potential, melting film and interactive force, a modified
LBM model is also developed to simulate the temperature distribution and
water migration in unsaturated soil. Main conclusions and future outlook
are also briefly stated and summarized. The contents included in this
chapter not only detail the experimental procedures and the results of
temperature distribution and water migration in unsaturated soil, but also
introduce the models for estimating the temperature distribution and water
migration in unsaturated soil.
Chapter 4 - By definition, the mass chemical potential (CP) of a
constituent in a soil represents the variation of the internal energy of the
medium when a unit mass of the constituent is transferred to a reference
state with the entropy, volume and mass of the other constituents
x Martin Hertz
remaining constant. It quantifies the action of the rest of the environment

on the constituent considered. For water, it results from mechanical or
electrical actions generated by the superficial layers which are responsible
for this retention. CP is a fundamental quantity in the same way as
temperature or pressure This chapter addresses the measurement and
expression of the CP in the presence of superficial layers induced by a
complex structure. Measuring CP in soils, gels and various media of
biological origin, is based on one of its fundamental properties, namely
that, at equilibrium, the chemical potential of a component i has the same
value on either side of a membrane permeable to i, temperature being
uniform. The proposed analysis revisits conventional methods such as
tensiometry or the use of filter paper and exploitation of the desorption
isotherm. A mechanical method has been developed to measure the CP of
volatile organic compounds in soils. The combined effects of the interfaces
and a solute on the CP of constituents of an aqueous solution in the
capillary domain are analyzed. In the case of an ideal solution of large
molecules (e.g., polyethylene glycol) in a porous medium with a pore size
small enough to hinder diffusion, a solute gradient is established. The
Gibbs Duhem relationship induces a chemical potential gradient of water.
The phenomenon of osmotic dehydration appears and is accompanied by a
loss of water and stresses. The effect of gas phase pressure in the capillary
medium refers to tensiometric measurement methods, with an important
nuance: capillary potential and suction being empirical formulations of the
CP, these concepts can then benefit from the body of mechanics,
chemistry, thermodynamics, thus allowing a very broad approach to soil
function and the expression of state functions, i.e., chemical potential,
entropy and internal energy. The authors then examine the case of a
saturated medium (solid phase + water) subjected to deformations that may
result from external actions or internal water transfer. In the context of
elastic behavior of the whole medium, increments of CP and stresses can
be expressed as a function of thermomechanical coefficients. Soil is a very
special container generating charged surface layers, open on the outside,
capable of generating temporospatial CP variations and fluctuations of the
constituents of the aqueous solution. Passage of a solution from the free
Preface xi
state to that of a solution in soil opens perspectives on applications such as

plant nutrition, water transfer in hygroscopic environments, pollution/soil
remediation, geochemistry, analysis of water transfers in arid zones
(desertification) and prebiotic chemistry.
In: Unsaturated Soils ISBN: 978-1-53615-985-1
Editor: Martin Hertz © 2019 Nova Science Publishers, Inc.
Chapter 1
UNSATURATED SOILS: ASPECTS THAT

CONTROL MOISTURE CONTENT
Teresa M. Reyna*, PhD, Santiago M. Reyna, PhD

and María Lábaque, MS
Department of Production, Management and Enviroment,
Department of Hydraulics, National University of Cordoba,
Cordoba, Argentina
ABSTRACT
Humankind increasingly puts more pressure on natural resources.

The preservation of the underground natural environment is becoming a
necessity to guarantee the progress of humanity.
The evaluation of soil conditions in the field requires considerable
time and effort. This effort, time and equipment needed will depend on
the range of uses required for the data. The area and depth to be studied
must be carefully defined. The area to study will depend on the variability
existing in the place. In certain occasions the characteristics of the soil -
*
Corresponding Author’s E-mail: teresamaria.reyna@gmail.com.
2 Teresa M. Reyna, Santiago M. Reyna and Maria Labaque
water interactions vary more with depth than with the area considered;
some cases are just the opposite.
The study of the vadose, or unsaturated zone, is of utmost importance
because this zone is the nexus between surface water and groundwater. It
is the link between what happens on the surface and what happens below,
inside the aquifers. Improving the knowledge of this underground natural
environment is essential to guarantee the sustainable development of
society.
Keywords: unsaturated soils, moisture content, unsaturated media
INTRODUCTION
Along with air and water, soil is the basis of life on Earth. It has an
extremely important role in the production of food, and in the cycles of
water and nutrients as well. The formation of soils depends on a long and
complex process. It is sluggishly renewable since it continues to be
generated through natural processes, but very slowly, and it is not
renewable when its destruction is faster than its formation.
Humankind is exerting more pressure on natural resources, so the
preservation of the natural environment is becoming more and more a
necessity to guarantee the sustainable development of a community. In this
context, the protection of soil resources has become a priority.
When we talk about unsaturated soils, we refer to the portion of soil
that is above the groundwater table, which interacts with surface
hydrological processes and is very susceptible to be affected by the
anthropic activities carried out on the surface. The most outstanding
feature of unsaturated soils corresponds to the amount of water they have,
which generates a different behavior of them not only from the mechanical
point of view but also from the point of view of water, air and water flows,
and pollutants transport. This characteristic means that their study can be
carried out with different approaches for different problems. Agronomists,
geotechnicians, geologists, hydrogeologists, hydrologists, engineers,
sanitarists and environmentalists, among others, study unsaturated soils
Unsaturated Soils 3
where the selection of representative variables and hypotheses are adjusted

to the interaction phenomenon to be studied.
From the agronomical point of view, the amount of water in soil, as
well as the infiltration capacity, is a basic input for the calculation of crop
water needs and to determine the amount of irrigation water. Currently, the
basis for improvements in irrigation efficiency is based on improvements
in the calculation of soil moisture conditions and the application of models
that allow an efficient application given the costs of irrigation, especially
when they are the source as groundwater. From a hydrological point of
view, incorporating an infiltration model to determine the amount of water
retained in the soil, allowing continuous simulations, permits to obtain
hydrographs of surface floods and their flood areas. From a geotechnical
point of view, Dudley (1970) commented that Terzaghi had already called
attention to the tendency of unsaturated soils to experience volume changes
when they were flooded. Partially saturated soils are the most frequent in
many arid and semi-arid regions. Much of the behavior experienced by a
partially saturated soil is related to volumetric deformation. On the other
hand, there is a great diversity of partially saturated soils with particular
characteristics or behaviors under different moisture contents, such as very
plastic expansive clays (with swelling and shrinkage in wet and dry
cycles), alluvial deposits (collapsible soils when they present an open
structure), colluvial and aeolian soils, compacted soils, etc. Many of these
problems have been tried and solved separately as special ones (Alonso et
al., 1987).
From the environmental point of view, soil pollution affects the
transport of water in the unsaturated zone and contaminates the lower
layers, and also affects the surface waters that are linked to groundwater.
On the other hand, the effects of the transport of substances in soils affect
their quality and therefore their agronomic use. Solid waste landfills and
the use of land as the final destination of effluents produce soil
contamination. The transport of these pollutants has to be studied because
the remediation processes can be expensive and complex.
The problem and management of its protection and care by the
authorities requires, therefore, a complete vision of its environment and the
interactions that can generate contamination and deterioration. Pollution

and deterioration situations will directly impact on agricultural activities,
on surface and underground water resources, including civil infrastructure
and urbanization works.
This chapter presents a brief description of the water content
characteristics of unsaturated soils, the complicated issue of the
measurement of humidity, and introduces the issue of impacts produced in
the context of climate change.
UNSATURATED SOILS
To understand the processes that occur in the soil and how they
interact with surface processes, it is necessary to know the characteristics
of the soil, the ways to measure the amount of water they have, and the
hydraulic functions of the soil that will allow studying different areas.
The area from the water table to the floor surface is called the
“aeration” zone. In this area the pores contain air and water. It is
subdivided into zones (Bear, 1972), capillary, vadose and water - soil. The
“capillary” zone, where the water rises by capillarity from the water table,
the “vadose” or intermediate zone, where the water is motionless, governed
by hygroscopic and capillary forces, and the “ground water” zone, which is
the area adjacent to the soil surface and extends below it through the area
of plant roots. This area is affected by the conditions of the soil surface,
seasonal and diurnal fluctuations, irrigation, precipitation, humidity and air
temperature, etc. In cases where the phreatic level is at shallow depth, the
vadose zone disappears, since the water ascends by capillarity to the
surface.
Below the aeration zone, under the phreatic surface to the impermeable
mantle, there is the zone of “saturation”; in this area the pores are
completely filled with water.
On the other hand, three phases coexist in the soil: solid (50%), liquid
(20-30%) and gaseous (20-30%) and depending on the type of soil is the
percentage of the different phases. These components are interrelated, so
Unsaturated Soils 5
the organization of the solid components together determines the amount

of porous space allocated to air and water.
As stated, the amount of water and air in the ground is subjected to
great fluctuations, especially due to the influence of climatic conditions
and movements of the groundwater. In unsaturated soils we can observe
three phases:
 Solid Phase: The main constituents of the solid phase are mineral
or inorganic species and organic matter. The inorganic fraction
corresponds to a mixture of several primary components (quartz,
feldspars, etc.) and secondary (silicate clays), varying its size from
clay to rock fragments. They determine, in relation to other
components, the physical and physical chemical properties of soils.
In addition, they constitute a source of nutrients. The organic
fraction is composed of organic substances in varying degrees of
decomposition, including soil organisms, living and dead. The
humid colloidal fraction affects the physical and chemical
properties of soils, such as porosity, water retention and cation
exchange capacity among others. It is one of the sources of
nutrients such as nitrogen, phosphorus and sulfate.
 Liquid Phase: This phase is a solution containing dissolved salts in
small amounts in the form of ions, variable in quantity, and has the
ability to dissolve different solutes, in a dynamic relationship
between water and soil, producing chemical reactions. In some
cases, it is also possible to observe the presence of polluting
substances such as organic compounds and pesticides to which the
variation in temperature could also be added.
 Gas Phase: Corresponds to the product of the exchange between
numerous living organisms of the soil and the “atmosphere” of the
soil and, like the external atmosphereit is a mixture of gases such
as O2, N2, CO2 and minor gases. The soil has higher CO2 content
and a lower N2 and O2 content than the external air, due to the
biological activity of the soil. The relative humidity of this
atmosphere can reach 100% since part of the air is dissolved in the
soil solution. In addition, it provides the oxygen necessary for the

life of most soil organisms and plants (Honorato, 2000).
The knowledge of the existing interactions between the three phases of
the system constitutes the basic point for understanding the unsaturated soil
behavior. Two of the most important parameters for studying unsaturated
soils are their porosity (typical of the nature of the soil) and the
representative elementary volume (related to the appropriate scale to define
the average values of the properties).
Porosity
As it was presented in previous paragraphs, the soil is constituted by

three phases: Solid, Liquid and Gaseous (Air). The pores can be classified
into macropores and micropores according to their size. The porosity of a
material represents a percentage that relates the volume occupied by the
pores in a unit volume of soil; thus, if the porosity is 50%, it means that
half of the rock is made up of pores and the other half is solid particles.
Table 1. Porosity values for different soil types (Davis, 1969)
Material Porosity percentage

Clays 50-60
Fine sands 40-50
Medium sands 35-40
Thick sands 25-35
Gravel 20-30
Sand and gravel mixed 10-30
Glacial deposits 25-45
Solid rocks and dense rocks <1
Unequal fractured and weakened rocks 2-10
Recent permeable basalts 2-5
Vesicular lava 10-50
Volcanic rock 30
Sand conglomerate 5-30
Carbonate rock with original and secondary porosity 10-20
Unsaturated Soils 7
The porosity can be applied to granular material or fractured material;

there are even compact granular materials that are fractured and have what
is called double porosity.
Above is the range of observed porosity values for different types of
rocks and deposits (Table 1 - Davis, 1969).
Representative Elementary Volume
It should be mentioned that porosity cannot be defined as values

measured at a point, since a porous medium is a conglomeration of soil
grains and voids. Below a certain volume scale, porosity concepts have no
physical meaning. The representative elemental volume must be large
enough to contain a large number of pores that allow defining the average
global porosity.
STATE OF TENSIONS IN UNSATURATED SOILS
Effective stresses can be defined as those functions of the total stresses

and interstitial pressures that control all the stress-strain relationships of the
soil. According to the Terzaghi principle, the stress-strain relationships of
the soil depend exclusively on the excess of the total pressures on the
interstitial pressure. Two aspects of the Terzaghi principle are of great
importance:
1) The pore pressure of the water acts on the water and the solid in
each direction.
2) Only the changes in the effective tension explain the changes in the
state of the soil.
There are several expressions to determine the effective stresses for

unsaturated soils, a summary of the most common expressions that have
been proposed to determine the effective tension for unsaturated soils have
been given by Fredlund and Rahardjo (1993). The equations try to define a
unique effective tension that controls the tension-deformation behavior.
Jennings and Burland (1962) questioned the validity of Bishop’s
equation (1959). They argued that the equation defines a certain
intergranular tension that, by not controlling the behavior of the soil, one
cannot control the effective tension. Parameter χ depends on the type of
test and the tension path followed. The crucial problem lies in the
determination of parameter χ, which is highly dependent on the stress
trajectory and consequently on the drying and wetting cycles.
The most characteristic phenomena of unsaturated soil behavior are
related to their volumetric deformations when modifying the degree of
saturation. These deformations can be both positive, in which case a
collapse occurs, and negative, in which case a swelling occurs.
Table 2. Expressions of effective stresses for unsaturated soils

presented by various authors (Fredlund and Rahardjo, 1993)
Equation Variables Author

𝜎´ = 𝜎 − 𝑢𝑎 + 𝜒(𝑢𝑎 − 𝑢𝑤 ) 𝛸 parameter related to the Sc Bishop (1959)
u = gas pressure and vapor
phase
𝜎´ = 𝜎 − 𝛽´𝑢𝑤 β = binding factor Croney et al.
(1958)
𝜎´ = 𝜎𝑎𝑚 + 𝑢𝑎 𝑎𝑎 + 𝑢𝑤 𝑎𝑤 + 𝑅 aa = fraction of the total area Lambe (1960)
−𝐴 that is in contact with the air-air
𝜎´ = 𝜎 + Ψ𝑝´´ Ψ= parameter from zero to one Aitchison
p´´= negative pore-water (1961)
pressure
𝜎´ = 𝜎 + 𝛽𝑝´´ β= statistical factor Jennings (1961)
𝜎´ = 𝜎 − 𝑢𝑎 + 𝜒𝑚 (ℎ𝑚 + 𝑢𝑠 ) χm = parameter effective voltage Richards
+ 𝜒𝑠 (ℎ𝑠 + 𝑢𝑠 ) (matrix suction) (1966)
hm = matrix suction
χs = effective voltage parameter
(solute suction)
hs = solute suction
Unsaturated Soils 9
The deformation of partially saturated soils has been extensively

studied, mainly in the analysis of the behavior of potentially collapsible
and expansive soils.
WATER IN SATURATED AND UNSATURATED MEDIA
In a saturated medium it is possible to indicate different forces in water

particles depending on the distance they are from soil particles.
Adhesive Water: is the water adhered to the surface of the grains
through molecular attraction forces.
(1) First Absorption layer: of the order of ten molecules of thickness

(about 0.1 μm).
(2) Transition Zone: between 0.1 and 0.5 μm, it contains water
molecules that are still subjected to attractive forces that are not at
all negligible and remain immobile.
Free Water: the forces of attraction are negligible and water is said to
be free. It can be displaced due to gravity forces or pressure gradients.
The amount of water in the soil is determinant of the processes that
occur in it, so it is essential to know it.
In unsaturated soils, the liquid phase is not necessarily continuous and
the same occurs with the gas phase. When the degree of saturation of the
soil is low, the air can occupy its canaliculi that can be communicated with
each other and with the outside. From a geotechnical point of view, air is
considered compressible, in contrast to water that is always considered
incompressible.
Wroth and Houlsby (1985) proposed three different types of
unsaturated soils based on the continuity of the phase fluid.
Discontinuous air phase and continuous water phase. This type of
structure is found in unsaturated soils that have a high degree of saturation.
In these soils the air is in the form of discrete bubbles. This situation
probably occurs in a narrow transition zone in natural soils, over the

saturated zone and under an area with a low degree of saturation.
Continuous phases of air and water. This type of unsaturated soil is
found in soils with an intermediate degree of saturation; this range of
degree of saturation occurs: a) in a transition zone in a natural soil deposit;
b) in compacted fillers of fine grains (silt and clays).
Continuous air phase and discontinuous water phase. This type of
unsaturated soil is found in unsaturated soils with low degrees of
saturation. This occurs: a) in natural soils close to the surface and b) in
some compacted fillings such as breakwaters and rockfills.
CURVES OF MOISTURE - SUCTION OF SOILS
In soil moisture-suction curves, it is observed that granular soils for not

very high suctions have very low moisture contents. In the case of fine
soils for the same suction value, there are still high moisture content values
(Reyna, T., 2000). Typical Moisture-Soil Suction curves can be seen in
Figure 1.
Figure 1. Moisture-Soil Suction Curves (taken from Lu Ning and Likos, 2004).
Unsaturated Soils 11
Figure 2. Hysteresis diagram for the water content curve in a granular soil. Drying in
full line and wetting in a line of dashes (Klute, 1986).
In all curves, it is observed that the suction is very small for water
contents close to saturation and it increases as the moisture content
decreases, presenting, according to the type of soil, slopes or growth
functions that are quite different, basically depending on the granulometric
distribution and the structure of the soil. For the same suction value, the
soil moisture is greater during the drying process than during wetting. This
phenomenon is called hysteresis (which means that suction in the soil is
not a unique value function of soil moisture).
The main characteristic of the hysteresis of the retention function can
be seen in Figure 2. The drying curve that begins to complete saturation of
a porous medium is the curve (IDC). In some porous media, when water is
removed through a porous stone, the pressure loading matrix decreases (ie,
becomes more negative), and the water content approaches a limit called
residual water content, r.
The wetting curve (MWC) is obtained by moistening the soil from a
low water content. The initial water content of the sample that is used to
determine the MWC affects the relationship between, 0, and hm. In many
cases, the MWC is determined from the residual water content, θr.
Usually 0 is about 0.8s to 0.9s. The water content, 0, is called
natural saturation.
HYDRAULIC FUNCTIONS OF THE SOIL
The relationship between the water content in the soil and the suction
is a fundamental part of the characterization of the hydraulic properties of a
soil. For the determination of the hydraulic properties of soils, it is
necessary to make measurements either in the laboratory or in the field.
This relationship is identified in the literature in different ways, including
water retention function, characteristic humidity curve, and capillary
pressure - saturation curve. This function relates a capacity factor, water
content (humidity), with a factor of intensity, the state of energy of the soil
- water.
The study of curve adjustments of moisture data and hydraulic
conductivity in function of the suction allows knowing in greater depth the
hydraulic operation of soils.
A solution to the problem of measurements results in using
mathematical models (functions of conductivity - suction, water content -
suction) that allows representing the hydraulic properties of unsaturated
soils or generalizing existing experimental data to soils of similar hydraulic
behavior. The selection of the model is important because it must allow the
soil to be represented in all the moisture conditions it may have.
Various functions to describe the water retention curve as a function of
suction or humidity curves have been proposed. One of the most popular is
the Brooks - Corey moisture model (1964-1966). This model proposes the
function of moisture vs. suction using: θr and θs (residual and saturated
moisture contents, respectively) and two parameters: α, empirical
parameter whose inverse is often referred to as the value of the air inlet
pressure; and λ, index of distribution of pore sizes that affects the slope of
the humidity curve.
The Brooks - Corey equation produces relatively good results for
coarse gravels with large λ values. For the case of fine soils, the results
obtained were not as good (Van Genuchten et al., 1991).
The model of Brooks and Corey (1964, 1966) proposes:
( h )-  (  s -  r ) + r h > 1
=
h  1 (1)
s
where θr and θs, residual and saturated water content, , empirical

parameter, , pore distribution index, and h, indicates suction.
Van Genuchten (1980) presented a smooth function for moisture as a
function of suction with more attractive properties. This function depends,
in addition to θr and θs, on three empirical parameters α, m and n that affect
the shape of the humidity curve. This equation has as limit the expression
of Brooks and Corey for λ equal to m times n.
Van Genuchten (1980) presented an equation for calculating the
effective degree of saturation, which has advantages for its implementation
in flow calculation models in unsaturated porous media,
1 (1)
Se=
[1+ ( h )n ] m
where , n and m are empirical constants. Van Genuchten equation with

m = 1 was used by Ahuja and Swartzenruber (1972), Endelman and others
(1974) and Varallyay and Mironenko (1979).
To improve the description of water retention in the soil near
saturation, several continuously differentiable (smooth) equations have
been proposed. These include functions presented by King (1965), Visser
(1968), Laliberte (1969), Su and Brooks (1975), and Clapp and Hornberger
(1978). These functions were able to more accurately reproduce the
observed water retention data in the soil, but were mathematically too
complicated to be incorporated into models to determine hydraulic
conductivity, or they had other characteristics that made them less
attractive for the study of water infiltration in soils (such as the lack of a
simple inverse relationship). If constraints are imposed on parameters m
and n (e.g., m = 1-1/n, or m = 1-2/n), an expression of the relatively simple
hydraulic conductivity function can be reached. Conversely, considering
variables α and n leads to mathematical expressions for K and D (hydraulic
diffusivity, D = K dh/dq) that are very complicated to study the flow of

water in soils. Van Genuchten et al. (1991) concluded that the model
presented in 1980 fits very well the moisture data observed for most soils if
m and n variables are considered. The only exceptions are certain
structures or aggregates of soils characterized by a mainly bimodal pore
size distribution. Even so, these authors do not recommend the use of this
function for all observed moisture data sets, as in the case of field
measurements, where the available data correspond only to a narrow range
of humidity. Unless further measurements are made at relatively low water
contents (laboratory measurements), such data can lead to the definition of
an unsuitable retention curve in the dry range (Van Genuchten et al.,
1991). In the models presented by Brooks and Corey and Van Genuchten
we find the values of θr and θs defined in a traditional way, that is:
Parameter θr is the content of water in the soil that will not participate
in the flow of the liquid phase because its flow paths are blocked or
because the adsorption produced by the solid phase is very strong (Luckner
et al., 1989). Formally, θr, can be defined as the water content at which
dθ/dh and K tend to zero when h tends to large values. The residual water
content is an extrapolated parameter, and therefore, does not necessarily
represent the lowest water content that a soil can have. This is especially
true in arid regions where the transport of the gas phase can dry soils at
water contents much lower than θr.
The saturated water content, θs, denotes the maximum volumetric
water content of a soil. The saturated water content is not equal to the
porosity of the soil; θs in the field is generally between 5 to 10% less than
the porosity due to trapped or dissolved air.
In the water retention functions in the soil of these models, parameters,
θr and θs, are constants obtained essentially from statistical adjustments
made on measured values.
The Vogel and Cislerova model (1988) modifies Van Genuchten’s
(1980) equations to add flexibility in the description of hydraulic properties
near saturation. The proposed model replaces θs in the Van Genuchten
model by a fictitious parameter extrapolated θm, slightly larger than θs, for
a minimum capillary height, h, other than zero. Vogel and Cislerová (1988)
(presented by Simunek and others, 1996), modified Van Genuchten’s

equations (1980) adding flexibility in the description of hydraulic
properties near saturation.
The water retention function of the soil,  (h) is given by the equation:
 m - r
r+ m
h < hs
 (h)= (1 +| h |n ) (3)
s h  hs
where hs is the air input value and m, n are the same defined in van
Genuchten’s expression, m is a fictitious parameter a little larger than s.
Parr, Zou and Mc. Enroe (1998) use Van Genuchten’s model to
represent the hydraulic functions of soil in a study of the effects of
infiltration on the transport of pollutants in agriculture.
The model of Celia et al. (1987) proposes an exponential function of
conductivity that is a reasonable model for data obtained from the
laboratory.
Fredlund et al. (1994) developed equations to describe characteristic
water retention curves similar to those of Van Genuchten (1980) and
combine them with the hydraulic conductivity model of Childs and Collis
(1950). They showed that the proposed equation to describe retention
curves is effective in predicting the permeability coefficient in most soils.
In cases where there is no retention curve data for high suction values, this
equation can be used to estimate the behavior of the retention curve in
these ranges.
Mualem (1976a) presents a model in which hydraulic conductivity is
expressed as a function of saturated hydraulic conductivity, and a
parameter l estimated by Mualem as 0.5 being the average value for many
soils. In this model hydraulic conductivity decreases when n decreases,
parameters n and m are the same parameters that were defined in the Van
Genuchten model, and when n is equal to 1 relative hydraulic conductivity
is identical to zero. When n is less than 1, the conductivity function cannot
be predicted; this characteristic is an important limitation of the case of
variables m, n. For this reason, van Genuchten, Leij and Yates recommend
the use of variables m, n only for the case of having well-defined moisture
data, and the use of the restriction m = 1 - 1/n for all other cases.
The Mualem model (1976a) expresses hydraulic conductivity as:
f( S e ) 2
K( S e ) = K s S le [ ] (4)
f(1)
where
1
f( S e ) =  0S e dx (5)
h(x)
Ks is the hydraulic conductivity in saturation state and l is a parameter

of pore connectivity. Equation (4) can be solved using the complete
functions Beta ((p,q)) and incomplete Beta (I(p,q)).
The equations for conductivity and hydraulic diffusivity assume that
the value of hydraulic conductivity in a saturated state is well defined and
can be easily measured. This is true for granular soils, but for soils in the
natural state, this is not true. The inspection of the conductivity and
diffusivity curves shows that a small change in the moisture content
produces changes of several orders in K and D, which indicates that small
errors in the measurement of moisture content near saturation can produce
large errors in the estimation of the saturated hydraulic conductivity of the
soil.
Stankovich and Lockington (1995) propose the use of a method to
convert Van Genuchten’s model (1980). First used by Klenhard and others
(1989), this model presents results suitable for soils with a relatively small
pore distribution and less suitable for use in clay soils.
In the Burdine hydraulic conductivity model, parameter l has the value
of 2. One of the most important differences between the model proposed
by Burdine and the model of Mualem is that in the Burdine model the
value of n> 2 is maintained, while Mualem is only valid for all n> 1. Since
many soils have values less than 2, the Burdine model is less applicable
than the Mualem expression.
The model of Brooks and Corey (1964, 1966) poses the following
expression for the function of hydraulic conductivity as a function of
suction:
hb 2+( 5/2)
K s( ) h > hb
K ( h) = h (6)
Ks h  hb
where hb: suction, : pore distribution index.
Table 3. Parameters for water content

and hydraulic conductivity models
Moisture models Parameters for water Parameters for models of

content models hydraulic conductivity
Brooks and Corey r, s, ,  Ks, hb, 

(1964,1966)
Van Genuchten (1980) s, , n, m, r Ks, , n, m, l
Fredlund et al. (1994) s, a, p, q Ks, ha, 0, (h)
Vogel and Cislervá (1998) r, m, s, , n, m Ks, Kk, r, k, m, (h)
Mualem (1976a) Ks, l, 0, r, s, (h)
Burdine (1953) Ks, l, (h), s
Celia et al. (1987) K0/A,  K0, 
Boadu (2000) proposes the use of new regression models that take into
account the distribution of grain size in compacted soils for the
determination of saturated hydraulic conductivity. Table 3 shows the
necessary parameters for each model presented in this chapter.
The model by Celia et al., similar to the one proposed by Chen et al.
(2001), proposes a linear relationship between hydraulic conductivity of
unsaturated soils and moisture content, and a decreasing exponential
relation for the function of unsaturated hydraulic conductivity in function
of the suction and for the function of moisture depending on the suction. In
those soils where the relationship between hydraulic conductivity and
humidity is linear, the function proposed by Celia and others is adequate to
represent them (Reyna, 2000). For example, in Wyckoff and Botset sand
experiments (1936), and Irmay’s theoretical analysis (1955), shown by
Bear (1972), it was observed that for saturation values above 40%, the
linear adjustment is adequate, and therefore the functions of Celia and
others can be applied. This model or similar ones, such as that presented by
Chen et al. (2001), are used for theoretical studies because they allow
Richards equation to be linearized.
Hydraulic functions depend on some parameters they need for their
calibration of the hydraulic properties, determined by means of tests. There
are complications for measuring the hydraulic properties of soils due to
two important factors: non-linearity of conductivity and non-linearity of
moisture as a function of suction. A solution to the problem of hydraulic
properties in all suction values results in using mathematical models that
allow representing the hydraulic properties of unsaturated soils.
The data obtained from the measurements made in the field or in the
laboratory have the problem that they cannot cover the entire range of
moisture that the soil suffers. Mathematical models have the advantage of
representing in an approximate way the soil at the points where
measurements were made and, allow obtaining values in all the states of
the soil where no data were obtained through measurements. Within all the
mathematical models that can be used, semi-empirical models have the
great advantage that they represent the functions of hydraulic conductivity
and moisture in function of suction in an appropriate form and they need
less measurements for their definition. The choice of the best model to
represent the hydraulic properties of unsaturated soils will depend on the
subsequent use to be made with these functions.
It is also important to remember that soils undergo the hysteresis
phenomenon during wetting and drying processes and, on the other hand,
the non-uniformity of the pore distribution causes that there is always some
air and water left in the wetting and drainage processes. The lack of
definition of the curves for hysteresis cycles can generate some problems
in infiltration studies, especially when it is desired to try to couple the

equations of surface runoff and infiltration to perform hydrological
modeling.
PROCESSES UNDER WHICH THE SOLUTE

IS SUBJECTED DURING ITS TRANSPORT ON THE GROUND
The process of transporting a solute in the soil where volatilization,

which brings the solute into the atmosphere, runoff to water surfaces, and
leaching into groundwater (Cheng, 1990), will appear, are affected by
diffusion, convection and dispersion processes. In addition, there are other
processes that, added to the above, affect some solutes in their interaction
with the geological environment such as retention (adsorption or sorption),
and transformation. The processes of chemical transformation can be
catalyzed by the constituents of the soil or photochemically induced.
MEASUREMENT OF SOIL MOISTURE CONTENT
The evaluation of soil moisture content at different suction conditions

in the field requires considerable time and effort, as well as equipment. The
effort, time and equipment needed will depend on the range of interest
required for the data, be it between -15 to -20 x 102 kPa or only between 0
to -50 kPa. (Linares, 2012).
The area of the soil and the depth for which the determination of the
relationship is necessary must be carefully defined. The selection of the
size of the area where the studies will be carried out will depend on the
variability existing in the place whose characterization is the final objective
of the study. In certain occasions the characteristics of the soil - water vary
more with depth than with area.
The moisture in the soil depends mainly on texture or particle size
distribution. On the other hand, the content of organic matter and the
composition of the solution phase can play a determining role in soil

moisture function or retention function. Organic matter has a direct effect
on the retention function due to its hydrophilic nature, and an indirect
effect due to the modification of soil structure that can be affected by the
presence of organic matter (Reyna, 2000).
Currently, there are different equipment and techniques for
measurements among which neutron probe, tensiometers, sensors,
reflectometry and others can be mentioned.
Neutron Probe
A neutron probe is a sophisticated and accurate piece of equipment that

measures the moisture content in soil. It requires calibration and operation
by a licensed operator.
This technique is based on the theory that fast neutrons are thermalized
when they collide with a body of similar mass, such as hydrogen nuclei.
The energy of the neutrons is transmitted to the protons which causes the
neutron “bounce or shock” to be much lower.
The application of this technique consists of three steps: 1) emission of
fast neutrons from a radioactive source, 2) attenuation of the velocity of the
neutrons after successive collisions with the atoms at the point of emission
and 3) accounting for neutrons with attenuated velocity by a detector near
the source.
By means of electrical impulses, the neutrons captured by the detector
are translated into a digital reading.
To convert the reading of the neutron probe to volumetric moisture, a
calibration model is necessary, where the volumetric moisture of the soil is
the main factor. There are some factors that influence measurements such
as hydrogen from organic matter, chlorine, iron and boron present in the
soil, capable of attenuating neutrons and absorbing thermally neutron
nuclei (Díaz Trujillo, 2007).
Tensiometers
Tensiometers are widely used to measure the available water content of

the soil when the matrix potential is high (Reyna, T. 2000). These devices
are simple, they are not very expensive, and they are very practical in
agricultural systems.
They consist of a porous ceramic capsule permeable to water and
solutes, connected to a pressure gauge by means of a transparent plastic
tube that is filled with water, in such a way that the column of water in its
interior forms a continuous with the water of the solution of the soil in the
surrounding space through the porous capsule.
The values obtained reflect the soil tension; are negative, and the
operating range is from 0 to -80 kPa; below this value the water column
breaks, penetrating the air and invalidating the following measurements.
The tensiometers are insensitive to the osmotic potential of water in the
soil and therefore do not provide an adequate measurement of the water
potential in soils with significant salinity.
Tensiometers are often used in combination with the neutron sprayer,
resistance blocks or psychrometers to cover the full range of soil moisture.
They require relatively frequent maintenance, which consists of adding
water plus a solution for the control of algae (Diaz Trujillo, 2007).
Granular Matrix Sensors
They have been developed more recently (they were patented in 1985
and manufactured commercially since 1989). They measure the electrical
resistance between two electrodes inserted in a small cylinder composed of
a porous material. Each device is covered by a membrane consisting of a
stainless steel coupling, externally covered by a rubber that makes the
sensor more durable than the plaster block. However, the recorder is
calibrated to give the value in water tension, by means of an equation that
takes into account the temperature of the soil estimated or measured near
the sensor. The size of the pores in the matrix is greater than that of the
pores in the gypsum blocks, allowing greater sensitivity in the range of

more water content in the soil (Diaz Trujillo, 2007).
Dielectric Sensors
The TDR and FDR probes measure the dielectric constant of the
medium, which is an intrinsic property of the medium. The FDR system
calculates the moisture of a soil by responding to changes in the dielectric
constant of the medium, using a frequency domain reflectometry technique
known as capacitance, while the TDR uses time domain reflectometry
(Robinson, et al. 2008).
Time Domain Reflectometry (TDR)
The TDR system consists of an oscilloscope connected to two or three

metal rods that are inserted parallel to the ground. If a difference of
potential is applied to one end of the rods, the energy is transmitted along
the ends to the end, where they are reflected to the oscilloscope. In it, the
evolution of the potential over time is measured.
Some equipment consists of two main parts: the electronic unit, and
the waveguides. The electronic unit contains the oscilloscope and the
central processor, which controls all measurement, display, and storage
functions. The waveguides can be installed horizontally or vertically and
remain permanently on the ground to make periodic measurements in the
same location or be used in a portable way.
The TDR uses a series of conversion tables to convert the dielectric
constant to a percentage of moisture in the soil. There are different
conversion tables to be used with the different types of waveguides. It is
not necessary to have a different table for different soil types since the
dielectric constant depends more on the amount of water than on the other
soil components. The apparatus calculates the average value of humidity
over the total length of the waveguides. The apparatus allows manual
measurements or continuous measurements by connecting the fixed

sensors to a data-logger.
Reflectometry in the Frequency Domain (FDR)
The FDR method is also known as a capacitance probe. The electrodes

and the adjacent soil form a capacitor whose capacity is a function of the
dielectric constant of the soil. This is related empirically to the volumetric
content of water.
A capacitance sensor requires a probe calibration for each floor and
horizon to obtain an optimal measurement of volumetric moisture. The
volume of soil measured is not dependent on the type of soil or water
content and approaches a cylinder 10 cm high with a diameter of about 25
cm, assuming there are no spaces with air (Velez et al. 2007).
All capacitance sensors installed in soils, even with similar characte-
ristics, must be calibrated with the aim of improving their accuracy given
the influence on the measurement of other factors independent of the
moisture content such as pH variability or electrical conductivity inside the
porous matrix.
Capacitance sensors are the most economical and easy to install. In
addition, they allow a continuous recording of moisture values in the soil,
enabling direct information and in real time. They are very useful for the
planning of alert monitoring systems. They can be used as substitutes for
neutron probes.
CLIMATE CHANGE EFFECTS ON SATURATED

AND UNSATURATED SOILS
Global warming, environmental degradation, the loss of biodiversity,

the pollution of inland waters and the growth of conflict potential due to
competition for the use of natural resources are serious problems affecting
land. Climatic demands, such as drought, can lead to increased pumping of

groundwater or investment in new storage areas, which have long-term
effects. The increase in uncertainty, regarding climate outcomes and,
therefore, the supply of fresh water can change the directions of investment
and use in regional resources. Increasing the magnitude and frequency of
floods can result in changes in erosion and sedimentation processes and in
the mobility of biological and chemical pollutants in both surface water,
soil, and groundwater.
Population density and the use of resources per capita have increased
dramatically during the last century, and watersheds, aquifers and
associated ecosystems have undergone important modifications that affect
the vitality, quality, and availability of the resource (UNESCO, 2011).
The existence of reliable data sources and access to them are
fundamental for the evaluation, prediction and adaptation of global change.
A generalized decrease in the entry of water into the subsoil and the
storage of groundwater will also lead to a reduction in the natural
discharges of these, affecting, therefore, the ecosystems that depend on
groundwater.
It is expected that, in some regions of the planet, a greater
intensification of the risks associated with extreme climatic phenomena
such as floods and, especially, droughts will happen. In addition to
affecting the amount of water that reaches the surface of the land in the
form of rain or snow, the increase of greenhouse gases in the atmosphere
will also influence the concentration of CO2 that is dissolved in the
rainwater. Associated with this phenomenon, the type of vegetation cover
will be modified and the functioning of the ecosystems associated with
groundwater (wetlands, rivers, springs, etc.), could also be modified by the
decrease in water content in the soils.
The increase in temperature also causes the increase of wild fires and
therefore affects the soils. Meteorological conditions can cause ignition of
fires as well as rapid expansion of the fires as a consequence of strong
winds.
The heating of the surface of the earth and the atmosphere is mainly a
consequence of solar radiation from the Sun, however, on a smaller scale,
heat can be caused by a large fire.
In the environment of forest fires, direct sunlight and high
temperatures can preheat fuels, bringing them closer to their point of
ignition. The physical characteristics of the soil are affected by the heating
of the soil during forest fires. These characteristics include: texture, clay
content, structure, bulk density, and porosity (quantity and size). Physical
properties such as wettability and structure are affected at relatively low
temperatures, while the content of quartz sand that contributes to the
texture is less affected and only occurs at extreme temperatures. The
components of soil texture (sand, silt and clay) have high temperature
thresholds and are not affected by fire unless they are subject to high
temperatures on the soil surface.
Fires and associated soil warming can destroy the structure of the soil,
affecting both the total porosity and the pore size distribution in the surface
horizons of a soil.
Climate change represents a serious threat to world food security, in
large part due to its effects on soils. Changes in temperature and rainfall
patterns can have a great impact on organic matter and the processes that
take place in our soils, as well as on the plants and crops that grow in them.
In order to respond to the challenges related to global food security and
climate change, agriculture and land management practices must undergo
fundamental transformations. Improving agricultural practices and soil
management that increase soil organic carbon-such as agroecology,
organic farming, conservation agriculture, and agroforestry-bring multiple
benefits. They produce fertile soils that are rich in organic matter (carbon),
maintain soil surfaces with vegetation, require less chemical inputs, and
promote crop rotation and biodiversity. These soils are also less susceptible
to erosion and desertification, and will maintain vital ecosystem services
such as hydrological and nutrient cycles, which are essential to maintain
and increase food production. (FAO, 2015).
CONCLUSION
The concept of how we should use nature is evolving rapidly. The

resources provided by the planet are important for the development of life,
some of them are renewable and others non-renewable according to their
availability in time, their rate of generation (or regeneration), and their rate
of use or consumption.
In this chapter, concepts were developed that clarify and allow
establishing bases of these water-soil relationships and allow them to be
modeled. It is necessary to continue carrying out new studies, in particular
in the subject of obtaining data in order to characterize unsaturated soils in
greater depth, especially since they must be applied by different scientists
with different approaches.
Regarding the study of soils, this is fundamental since food production
activities are developed in them. Therefore, soils care depends on
knowledge, and to take care of something needs this knowledge basis first.
Soils must also be protected from both point and non-point contamination.
Unsaturated soils play an essential role in the care of soil and water
resources, so their nature and vulnerabilities must be studied and modeled
in order to anticipate the impacts that these resources could suffer.
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BIOGRAPHICAL SKETCHES
Teresa Maria Reyna
Affiliation: Department Production, Managament and Enviromental

and Department of Hydraulics, National University of Cordoba, Cordoba,
Argentina
Education: PhD in Engineering Sciences. National University of

Cordoba. Master’s in Engineering Sciences – Specialization in Water
Resources. National University of Cordoba. Civil Engineer. National
University of Cordoba
Research and Professional Experience:
 2017 to the present: Member of the Board of Directors of the High

Institute of Environmental Studies of the National University of
Cordoba.
 Professor in Charge of Technology, Environment and Society.
Department of Production, Management and Environment. School
of Exact, Physical and Natural Sciences. National University of
Cordoba. 2018-Present.
 2009 to the present: Director of Postgraduate Specialization in
Hydraulics.
 Director of the Department of Hydraulics, Faculty of Exact,
Physical and Natural Sciences. May 2016-December 2016.
 Sub-director of the Department of Hydraulics of the School of
Civil Engineering, Faculty of Exact, Physical and Natural
Sciences. August 2014 - May 2016.
 Adjunct Professor through competitive examination of the Chair of
“Hydrology and Hydraulic Processes”. Department of Hydraulics.
School of Exact, Physical and Natural Sciences. National
University of Cordoba. 2005-Present.
 Adjunct Professor of the Chair of “Hydrology and Hydraulic

Processes”. Department of Hydraulics. School of Exact, Physical
and Natural Sciences. National University of Cordoba. 1998 -
2005.
 Adjunct Professor of the Chair of “Hydraulics Works”.
Department of Hydraulics. School of Exact, Physical and Natural
Sciences. National University of Cordoba. 1998 - Present.
 Professor of the Master’s Program in Engineering Sciences (Water
Resources; Transportation; and Management). School of Exact,
Physical and Natural Sciences. National University of Cordoba.
2001 – Present.
Professional Appointments:
 Managing Partner of CEAS SA, consulting company dedicated to

studies and projects on hydraulics engineering, environmental
engineering and sanitation.
 Partner of GCIS, Consortium of Consulting Engineering
Companies, Cordoba, Argentina.
 Advisor of the Sub-Secretariat of Water Resources, National
Government, Argentina. March of 2006 to March 2010.
 Member of the Editorial Board of Pinnacle Journal Publication.
Pinnacle Agricultural Research and Management. Online Edition.
ISSN: 2360-9451.
 Associate Editor of the Journal Ambiente & Água - An
Interdisciplinary Journal of Applied Science/Institute of
Environmental Research in Bacias Hidrográficas. Taubaté
Taubaté: IPABHi. ISSN Quarterly Edition 1980-993X, 2014/2015.
Honors: She has been awarded numerous schollarships by prestigious

official institutions as: National Board of Scientific and Technological
Research (CONICET), and the Secretary of Science and Technology
(SECYT) of the National University of Córdoba. Besides, she has received
awards as first candidate in the selection of the Graduate Program of
Masters’ in Structural Engineering, Honor Diploma of the Engineering

Association of Córdoba and Special Mention (“Silver Medal”) for second
best GPA of her class of Civil Engineering, School of Exact, Physical and
Natural Sciences.
Publications from the Last 3 Years:
Editor of book
Garcia-Chevesich, Pablo A., Neary, Daniel G., Scott, David F.

Benyon, Richard G., Reyna, Teresa. Editors. Forest Management
and the Impact on Water Resource: A Review of 13 Nations. IHP -
VIII/Technical document Nº 37. Latin America and the Caribbean.
(2017). ISBN 978-92-3-100216-8. http://unesdoc.unesco.org/
images/0024/002479/247902E.pdf
Author of Book Chapters
Reyna, Teresa, Labaque, María; Reyna, Santiago; Funes, Fernanda. 2018.

Flow in unsaturated soils and transport of herbicides in agricultural
areas. In “Soil Contamination”, ISBN 978-953-51-6385-5.
Reyna, Teresa, Reyna, Santiago, Labaque Maria. 2017. Chapter 1. Forest
Management and Water in Argentina. Forest Management and the
Impact on Water Resource: A Review of 13 Nations. IHP -
ISBN 978-92-3-100216-8. http://unesdoc.unesco.org/images/0024/
002479/247902E.pdf.
Publications in Magazines with Reference
Reyna, Santiago; Teresa Reyna; Fabián Fulginiti; María Lábaque. 2018.

“Aplicación de Métodos Optimización para Hidrogeneración. Estudio
del Sistema de los Ríos Las Cañas - Gastona -Medina”. EPIO.
Investigacion Operativa - Año XXVI - Nº 43 – 24-36. [Application of
Optimization Methods for Hydrogeneration. Study of the Las Cañas

River System - Gastona -Medina. EPIO. Operative investigation]
Reyna, Teresa, Santiago Reyna, María Lábaque, César Riha, Carlos
Góngora. 2017. Desafíos ambientales para uso de la hidrogeneración.
Avances en Ciencias e Ingeniería (ISSN: 0718-8706). Vol. 8, N° 3.
Chile. [Environmental challenges for the use of hydrogeneration.
Advances in Science and Engineering]
Reyna, Teresa; Belén Irazusta, Maria Lábaque, Santiago Reyna, and Cesar
Riha. 2019. “Hydraulic Microturbines, Design, Adaptations for
Teaching of Microgeneration”. Modern Environmental Science and
Engineering. ISSN: 2333-2581.
Reyna, Teresa; Santiago Reyna, María Lábaque, César Riha, Belén
Irazusta, and Agustín Fragueiro. 2018. “Design of Microturbines
Kaplan and Turgo for Microgeneration Systems: Challenges and
Adaptations”. Modern Environmental Science and Engineering
Volume 4, Number 8. ISSN 2333-2581.
Reyna, Teresa; Santiago Reyna, María Lábaque, César Riha, Florencia
Grosso. 2016. Applications of Small Scale Renewable Energy. Journal
of Business and Economics ISSN 2155-7950, USA. Vol. 7, No. 2, pp.
250-258. DOI: 10.15341/jbe(2155-7950)/02.07.2015/008.
Santiago Ochoa,. Teresa Reyna, Carlos M. García, Horacio Herrero, José
Manuel Díaz, and Ana Heredia 2017. Análisis de la implementación de
un modelo hidrodinámico tridimensional al flujo de un cauce natural.
Revista Ingeniería del Agua. Universitat Politècnica de València.
Fundación para el Fomento de la Ingeniería del Agua. e-ISSN: 1886-
4996 - ISSN: 1134-2196. Vol. 21 N° 2. [Analysis of the
implementation of a three-dimensional hydrodynamic model to the
flow of a natural channel. Water Engineering Magazine.]
She has numerous refereed publications and has actively participated

in national and international congresses and conferences.
Santiago Maria Reyna

and Department of Hydraulics, National University of Cordoba, Córdoba,
Argentina
Education: PhD, MSCE, MSCE, Purdue University, USA. Civil

Engineer. National University of Córdoba

 Partner of GCIS, Consortium of Consulting Engineering
Companies, Cordoba, Argentina.
 Advisor of the Minister of Water, Environment and Public
Services, Province of Córdoba, Argentina. March of 2014 to
present.
 Advisor of the Sub-Secretary of Water Resources, National
Government, Argentina, (liaison with the ORSEP, INA,
ENOHSA; cooperation in the assessment and follow-up of Projects
of Hydraulic Works; in charge of Hydroelectric Projects; liaison
with the Secretariat of the Environment). March of 2006 to March
2014.
 He has represented the Republic of Argentina at the Plenary
Meeting in Nairobi of the United Nations Environment Program
(UNEP) and at the G5, in Geneva, on topics of the Environment
and Water Resources.
 He was, until Dec. 2013, Alternate Member of the Adaptation
Fund Board (Kyoto Protocol) representing GRULAC (Latin
America and the Caribbean Group).
 2008 to the present: Plenary Professor of the Chairs of

Environmental Engineering and Hydraulics Works. National
University of Córdoba.
 1997 to 2008: Full Professor through competitive examination of
the Chair of Hydraulics Works. Department of Hydraulics. School
of Exact, Physical and Natural Sciences. National University of
Cordoba.
 2000 to the present: Full Professor of the Chair of Environmental
Engineering. Department of Hydraulics. School of Exact, Physical
and Natural Sciences. National University of Córdoba. Resolution
24 - HCD-00.
 2001 to 2017: Head of the Graduate School of the School of Exact,
Physical and Natural Sciences, National University of Córdoba.
 2006 to the present: Director of two Masters’ Programs in
Engineering Sciences: Environmental Engineering and Water
Resources.
 2013 to the present: Coordinator of the Career of Environmental
Engineering, National University of Córdoba.
 2006 to 2008: Member of the Board of Directors of the High
Institute of Environmental Studies of the National University of
Córdoba.
 Consultant engineer for national and international organizations.

 President and Partner of CEAS SA, consulting company dedicated
to studies and projects on hydraulics engineering, environmental
engineering and sanitation, Córdoba, Argentina.
 CEO of GCIS, Consortium of Consulting Engineering Companies,
Córdoba, Argentina.
 Managing Partner of “Ambientes y Sistemas SRL” (until
December 2013), consulting company dedicated to the area of
environmental and sustainable development studies and the

application of their management, Córdoba, Argentina.
Honors:
 Full Academic of the Pan American Academy of Engineering

(2010).
 Full Academic of the “Academia del Plata”, Argentina (2013).
 Diplomate, Water Resources Engineer (DWRE), of the American
Academy of Water Resources Engineers (AAWRE), American
Society of Civil Engineers (2007).
 “Medalla de oro” (gold medal) for obtaining his degree in Civil
Engineering with highest honors (1984).
 University Award for Professors, National University of Córdoba
(1995).
Author of book chapters

areas. In Soil Contamination, ISBN 978-953-51-6385-5.
002479/247902E.pdf.


of Business and Economics. ISSN 2155-7950, USA. Vol. 7, No. 2, pp.
250-258. DOI: 10.15341/jbe(2155-7950)/02.07.2015/008.
He has numerous refereed publications and has actively participated in

national and international congresses and conferences.
Maria Labaque

and Department of Hydraulics, National University of Cordoba, Córdoba,
Argentina
Education: Master’s in Engineering Sciences – Specialization in

Water Resources. National University of Córdoba. Civil Engineer. Catolic
University of Córdoba
 Professor of Technology, Environment and Society. Department of

Production, Management and Environment. School of Exact,
2018-Present.
 2015 to the present: Technical Secretary of Postgraduate
Specialization in Hydraulics.
 Adjunct Professor of the Chair of “Hydraulics Works”.
Department of Hydraulics. School of Exact, Physical and Natural
Sciences. National University of Cordoba.
 Adjunct Professor to the Chairs of: Fluid Mechanics”. Department
of Hydraulics. School of Exact, Physical and Natural Sciences.
National University of Cordoba.
 Professor of the Master’s Program in Engineering Sciences (Water
Resources; Transportation; and Management). School of Exact,
2015 – Present.

Honors:
 She has been awarded scholarship by the Department of Science

and Technology (SECYT).
 She represented the Catholic University of Córdoba before the

Argentine Committee of Dams during 2003.
 She represented the National University of Córdoba before the
Committee of the Salí-Dulce Basin in the Workshop of
Contamination. El Mollar, Province of Tucumán. June 1998.
Author of book chapters

areas. In Soil Contamination, ISBN 978-953-51-6385-5.
002479/247902E.pdf.

of Business and Economics. ISSN 2155-7950, USA. Vol. 7, No. 2, pp.
250-258. DOI: 10.15341/jbe(2155-7950)/02.07.2015/008.
She has numerous refereed publications and has actively participated

in national and international congresses and conferences.
Chapter 2
SOME ASPECTS OF NUMERICAL

MODELLING OF HYDRAULIC HYSTERESIS
OF UNSATURATED SOILS
Javad Ghorbani and David W. Airey

School of Civil Engineering, The University of Sydney,
Camperdown, NSW, Australia
ABSTRACT
The Soil Water Characteristic Curve (SWCC) plays an essential role

in the response of unsaturated soils as it quantifies the ability of soils to
maintain or lose their available moisture. It is generally understood that
the SWCCs exhibit hysteresis when subjected to cycles of wetting and
drying, and more generally the relationship between suction, volume
changes, and the saturation degree for a given soil is not unique and can
be path-dependent. In particular, the SWCC may show strong sensitivity
to volume changes in cohesive soils.

Corresponding Author’s E-mail: javad.ghorbani@sydney.edu.au.
42 Javad Ghorbani and David W. Airey
Due to the complexities involved in considering the hysteretic

response of the SWCC and its dependency on volume changes, these two
features are often ignored in numerical studies of unsaturated soils. To
facilitate their use in numerical modeling, a model for the SWCC
equation based on the bounding surface concept is proposed. The
resulting non-linear model is presented in an incremental form relating
the rate of saturation degree to the rate of suction and volume changes. It
is shown that the proposed model has the ability to replicate the shape
and the evolution of the scanning curves observed in the experiments
compared to currently available alternatives. The model has benefits for
numerical application as it improves the convergence properties of the
overall numerical analysis and includes a robust integration scheme with
automatic error control for updating the saturation degree during the
analyses. Results are presented to show the ability and the robustness of
the proposed scheme in modeling the unsaturated soil response under
various loading conditions including static and dynamic analyses.
Keywords: unsaturated soils, hysteresis, finite element, multiphase flow,

porous media, plasticity
INTRODUCTION
Over the last twenty years, there has been a growing attempt to explain
and predict the response of unsaturated soils, which often exist in the upper
zone over much of the earth’s surface.
In unsaturated soils, solid, gas and liquid phases are simultaneously
present. Numerical equations governing solid and fluid interactions in a
porous medium were first developed by extending Biot’s theory to
unsaturated soils (Lewis and Schrefler, 1982; Li et al., 1989; Zienkiewicz
et al., 1990 and Li and Zienkiewicz, 1992). The authors assumed that
neither phase transfer nor any chemical reactions were possible during
fluid flow, which was referred to as “immiscible.”
In numerical analyses based on this approach, simplifying assumptions
have been made to ignore the effect of volume changes on variations of the
degree of saturation and to neglect the hysteretic behaviour of the SWCCs
during the analysis (Schrefler and Scotta, 2001; Khalili et al., 2008; Khoei
and Mohammadnejad, 2011; Ghorbani et al., 2016a and Ghorbani, 2016).
Some Aspects of Numerical Modelling of Hydraulic Hysteresis … 43
While the assumptions lead to simpler numerical implementation, they can

be in disagreement with experimental evidence, (Sheng and Zhou, 2011)
which shows that SWCCs can depend strongly on volume change (most
importantly for fine-grained soils) and exhibit hysteretic responses during
wetting and drying.
In this chapter, a dynamic fully coupled model which does not involve
the aforementioned simplifications will be presented and details of
important aspects of the modelling of hydraulic hysteresis in unsaturated
soils will be given.
MATHEMATICAL FRAMEWORK FOR

UNSATURATED SOIL DYNAMICS
The effective stress suggested by Bishop (1960) has been adopted

(Equation (1)) which provides the capability of smooth transitions between
saturated and unsaturated states.
𝛔′ = 𝛔 + 𝜒𝑝𝑤 𝐦 + (1 − 𝜒)𝑝𝑔 𝐦 (1)
In the above equation, 𝛔′ is the effective stress, 𝑝𝑔 denotes the air

pressure and 𝑝𝑤 is the pore water pressure. In addition, 𝜒 is the effective
stress or Bishop’s parameter, which ranges from 0 to 1 for dry to saturated
conditions, respectively. To maintain consistency with the authors’s earlier
publication (Ghorbani et al., 2014); Ghorbani et al., 2016a; Ghorbani et al.,
2016b; Ghorbani et al., 2016c and Ghorbani et al., 2017) the water and air
pressures are assumed positive in compression; whereas stress components
are assumed negative in compression. Moreover, 𝜒 is considered as
saturation degree, 𝑆𝑤 (e.g., Schrefler, 1984).
In addition, suction, 𝑝𝑐 , is defined as
𝑝𝑐 = 𝑝𝑔 − 𝑝𝑤 (2)
Solid (s), water (w) and gas (g) phases in unsaturated soils are assumed
to be continuously spread throughout space. The degree of saturation, 𝑆𝛽
(𝛽 = 𝑤, 𝑔), the density of each phase 𝜌𝛼 (𝛼 = 𝑠, 𝑤, 𝑔), and the volume
fraction of each phase in the soil 𝑛𝛼 are obtained from:
𝛺𝛽 𝑀𝛼 𝛺𝛼
𝑆𝛽 = , 𝜌𝛼 = , and 𝑛𝛼 = (3)
𝛺−𝛺𝑠 𝛺𝛼 𝛺
where 𝛺𝛼 and 𝛺 are the volume occupied by each phase and the total
volume of the unsaturated soil, respectively; and 𝑆𝑤 + 𝑆𝑔 = 1. 𝑀𝛼 is the
mass of each phase inside the soil.
Porosity of the unsaturated soil, 𝑛 is defined by
𝑛 = 𝑛w + 𝑛g = 1 − 𝑛s (4)
The average density of the soil, 𝜌, is defined as
𝜌 = (1 − 𝑛)𝜌𝑠 + 𝑛𝑆𝑤 𝜌𝑤 + 𝑛𝑆𝑔 𝜌𝑔 (5)
Conservation of Mass and Momentum Balance
Based on the principle of conservation of mass, inside an arbitrary

volume 𝛺, the flows of the soild, water, and gas phases through a surface,
d𝛤 can be described as 𝜌𝛼 𝑛𝛼 . 𝑽𝜶 . 𝐧∗ . d𝛤, where 𝐧∗ is the unit vector
normal to the surface, 𝜌𝛼 𝑛𝛼 is the partial mass density of each material,
and 𝑽𝜶 is the velocity of each phase.
The principle of mass conservation is defined by
𝑑
∫
𝑑𝑡 𝛺
𝜌𝛼 𝑛𝛼 𝑑𝛺 = − ∮𝛤 𝜌𝛼 𝑛𝛼 . 𝐕 𝜶 . n∗ . 𝑑𝛤 (6)
By applying the Gauss theorem, the conservation of mass can be

written in the form of a differential equation, as follows:
𝜕(𝜌𝛼 𝑛𝛼 )
𝜕𝑡
+ div(𝜌𝛼 𝑛𝛼 𝐕 𝜶 ) =0 (7)
By considering 𝐕 𝒔 = 𝐮̇ for the solid phase, ignoring the spatial

variations of the solid phase (𝛁𝜌𝑠 = 0, with 𝛁 as the gradient operator) and
neglecting the compressibility of solid particles, the following will be
obtained:
𝜕𝑛
−𝜌𝑠 𝜕𝑡 − 𝜌𝑠 𝐮̇ . 𝛁𝑛 + (1 − 𝑛)𝜌𝑠 div(𝐮̇ ) = 0 (8)
Dividing Equation (8) by 𝜌𝑠 and considering the concept of material

𝐷(∗) 𝜕(∗)
time derivative, 𝐷𝑡
= 𝜕𝑡
+ 𝐮̇ . 𝛁 ∗ results in the following equation:
𝐷𝑛
= (1 − 𝑛)div(𝐮̇ ) (9)
𝐷𝑡
Also, the conservation of mass for the fluid phases can be written as
Ghorbani et al., (2018c):
𝑛𝐷(𝜌𝑤 ) 𝑛𝐷(𝑆𝑤 ) 1 𝐰̇ 𝑤
+ + div(𝐮̇ ) + div(𝐰̇ 𝑤 ) + . 𝛁𝜌𝑤 =0 (10)
𝜌𝑤 𝐷𝑡 𝑆𝑤 𝐷𝑡 𝑆𝑤 S𝑤 𝜌𝑤
and
𝑛𝐷(𝜌𝑔 ) 𝑛𝐷(𝑆𝑔 ) 1 𝐰̇ 𝑔
𝜌𝑔 𝐷𝑡
+ 𝑆𝑔 𝐷𝑡
+ div(𝐮̇ ) + 𝑆 div(𝐰̇𝑔 ) + 𝑆 . 𝛁𝜌𝑔 =0 (11)
𝑔 𝑔 𝜌𝑔
In an isothermal environment, the rate of change in the fluid density is:
1 𝐷𝜌𝛽 1 𝐷𝑝𝛽
𝜌𝛽 𝐷𝑡
=𝐾 , (𝛽 = 𝑤, 𝑔) (12)
𝛽 𝐷𝑡
where 𝐾𝛽 is the bulk modulus of the fluid phases.

Substituting Equations (12) into (10) and (11) leads to the following:
𝑛 𝐷𝑝𝑤 𝑛𝐷𝑆w 1 𝐰̇ 𝑤
𝐾𝑤 𝐷𝑡
+ 𝑆𝑤 𝐷𝑡
+ div(𝐮̇ ) + 𝑆 div(𝐰̇ 𝑤 ) + S . 𝛁𝜌𝑤 =0 (13)
𝑤 𝑤 𝜌𝑤
and
𝑛 𝐷𝑝𝑔 𝑛𝐷𝑆𝑔 1 𝐰̇ 𝑔
𝐾𝑔 𝐷𝑡
+𝑆 + div(𝐮̇ ) + 𝑆 div(𝐰̇𝑔 ) + 𝑆 . 𝛁𝜌𝑔 =0 (14)
𝑔 𝐷𝑡 𝑔 𝑔 𝜌𝑔
To consider the dependency of saturation degree on suction and

porosity (or void ratio), we can describe the rate of saturation change by
𝐷𝑆𝑤 𝜕𝑆𝑤 𝐷𝑝𝑐 𝜕𝑆𝑤

= + (1 − 𝑛)div(𝐮̇ ) (15)
𝐷𝑡 𝜕𝑝𝑐 𝐷𝑡 𝜕𝑛
By adding Equation (15) to (13) and (14) and multiplication of (13)

and (14) by 𝑆𝑤 and 𝑆𝑔 and defining
𝑛𝑆𝑤
𝐶1 = 𝐾𝑤
(16)
𝜕𝑆
𝐶2 = 𝑛 𝜕𝑝𝑤 (17)
𝑐
𝑛𝑆𝑔
𝐶3 = 𝐾𝑔
(18)
𝑛 𝜕𝑆w
𝐶4 = 𝑆 −𝑛 (19)
𝐾𝑔 𝑔 𝜕𝑝𝑐
𝜕𝑆𝑤
𝐶5 = (1 − 𝑛) + 𝑆𝑤 (20)
𝜕𝑛
𝜕𝑆𝑤
𝐶6 = 𝑆𝑔 − (1 − 𝑛) (21)
𝜕𝑛
the following governing equations will be obtained:

𝐰̇ 𝑤
𝐶1 𝑝̇𝑤 + 𝐶2 𝑝̇𝑐 + 𝐶5 div(𝐮̇ ) + div(𝐰̇ 𝑤 ) + 𝜌 . 𝛁𝜌𝑤 = 0 (22)
𝑤
and
𝐰̇ 𝑔
𝐶3 𝑝̇𝑤 + 𝐶4 𝑝̇𝑐 + 𝐶6 div(𝐮̇ ) + div(𝐰̇𝑔 ) + . 𝛁𝜌𝑔 =0 (23)
𝜌𝑔
where the super-imposed dot represents the time derivative of a variable.

For the non-solid phases, the linear momentum balance equation is
following Li and Zienkiewicz (1992) as
𝐷 𝐰̇ 𝛽
𝐰̇𝛽 = 𝐤𝛽 [−𝛁𝑝𝛽 + 𝜌𝛽 (𝐛 − 𝐮̈ ) − ( )] , (𝛽 = 𝑤, 𝑔) (24)
𝐷𝑡 𝑛𝑆𝛽
where 𝐤 𝑤 and 𝐤𝑔 are the permeability matrices of unsaturated soils,

defined by
𝑘𝑟𝛽
𝐤𝛽 = 𝐤 𝑖𝑛𝑡 . 𝜂𝛽
(25)
with 𝑘𝑟𝑤 and 𝑘𝑟𝑔 being the relative permeability of the water phase and
the air phase, respectively; 𝐤 𝑖𝑛𝑡 is the intrinsic or absolute permeability
matrix of the soil, 𝜂𝛽 denotes the viscosity of non-solid phases.
The linear momentum balance equation for the unsaturated soil can be
obtained by
𝐷 𝐰̇ 𝑔 𝐷 𝐰̇ 𝑤
𝐋𝑇 𝛔 + 𝜌𝐛 − 𝜌𝐮̈ − 𝑛 [(1 − 𝑆𝑤 )𝜌𝑔 𝐷𝑡 (𝑛(1−𝑆 )) + S𝑤 𝜌𝑤 𝐷𝑡 (𝑛𝑆 )] = 0
𝑤 𝑤
(26)
where
𝜕 𝜕 𝜕
𝜕𝑥
0 0 𝜕𝑦
0 𝜕𝑧
𝜕 𝜕 𝜕
𝐋𝑇 = 0 𝜕𝑦
0 𝜕𝑥 𝜕𝑧
0 (27)
𝜕 𝜕 𝜕
[0 0 𝜕𝑧
0 𝜕𝑦 𝜕𝑥 ]
According to Lewis and Schrefler (1999) and Zienkiewicz et al.,

(1999), the relative acceleration of the fluids can be assumed to be
negligible, so that:
𝐷
𝐷𝑡
(𝐰̇𝛽 ) = 0, (𝛽 = 𝑤, 𝑔) (28)
The imposed Dirichlet boundary conditions for the primary variables

on the boundaries are:
̅ on 𝛤𝑢
𝐮=𝐮 (29)
𝑝𝑤 = 𝑝̅𝑤 on 𝛤𝑝𝑤 (30)
𝑝𝑤 = 𝑝̅𝑐 on 𝛤𝑝𝑐 (31)
whereas the Neumann boundary conditions on the prescribed tractions and

fluxes are:
𝐈𝜎𝑇 𝛔 = 𝐭̅ on 𝛤𝑡 (32)
̅̇ 𝑤 on 𝛤𝑞
𝐤 𝑤 [−𝛁𝑝𝑤 + 𝜌𝑤 (𝐛 − 𝐮̈ )]. 𝐧∗ = 𝑤 (33)
𝑤
̅̇ 𝑔 on 𝛤𝑞
𝐤𝑔 [−𝛁𝑝𝑔 + 𝜌𝑔 (𝐛 − 𝐮̈ )]. 𝐧∗ = 𝑤 (34)
𝑔
̅̇ 𝛽 (𝛽 = 𝑤, 𝑔) are the prescribed values of the outflow rate of non-

where 𝑤
solid phase on the permeable boundaries 𝛤𝑞𝛽 (𝛽 = 𝑤, 𝑔).
Moreover, we define,
𝑛𝑥 0 0 𝑛𝑦 0 𝑛𝑧
𝐈𝜎𝑇 =[0 𝑛𝑦 0 𝑛𝑥 𝑛𝑧 0] (35)
0 0 𝑛𝑧 0 𝑛𝑦 𝑛𝑥
and
𝑛𝑥
𝐧∗ = [ 𝑛 𝑦 ] (36)
𝑛𝑧
with 𝑛𝛼 (𝛼 = 𝑥, 𝑦, 𝑧) as unit outward normal vector to the boundaries in x,

y and z directions.
Note that 𝛤𝑢 ∪ 𝛤𝑡 = 𝛤 , 𝛤𝑞𝑤 ∪ 𝛤𝑝𝑤 = 𝛤 and 𝛤𝑞𝑔 ∪ 𝛤𝑝𝑐 = 𝛤 .
The weak form of the governing equation for the unsaturated soils can
then be written as:
∫𝛺 𝛿𝑝𝑤 (𝐶1 𝑝̇𝑤 + 𝐶2 𝑝̇𝑐 + 𝐶5 div(𝐮̇ ) + div(𝐤 𝑤 [−𝛁𝑝𝑤 + 𝜌𝑤 (𝐛 −

1
𝐮̈ )]) + 𝜌 𝐤 𝑤 [−𝛁𝑝𝑤 + 𝜌𝑤 (𝐛 − 𝐮̈ )]. 𝛁𝜌𝑤 ) 𝑑𝛺 + ∫𝛺 (𝛿𝑝𝑐 +
𝑤
𝛿𝑝𝑤 ) (𝐶3 𝑝̇𝑤 + 𝐶4 𝑝̇𝑐 + 𝐶6 div(𝐮̇ ) + div(𝐤𝑔 [−𝛁𝑝𝑔 + 𝜌𝑔 (𝐛 − 𝐮̈ )]) +

1
𝐤 [−𝛁𝑝𝑔
𝜌𝑔 𝑔
+ 𝜌𝑔 (𝐛 − 𝐮̈ )]. 𝛁𝜌𝑔 ) 𝑑𝛺 + ∫𝛤 𝛿𝑝𝑤 [𝐤 𝑤 [−𝛁𝑝𝑤 +
𝑞𝑤
∗
𝜌𝑤 (𝐛 − 𝐮̈ )]. 𝐧 − 𝑤̇ ̅ 𝑤] 𝑑Г − ∫𝛤 (𝛿𝑝𝑐 + 𝛿𝑝𝑤 )[𝐤𝑔 [−𝛁𝑝𝑔 + 𝜌𝑔 (𝐛 −
q𝑔
∗ ̅̇ 𝑔 ] 𝑑Г = 0
𝐮̈ )]. 𝐧 − 𝑤 (37)
∫𝛺 𝛿𝑢(𝐋𝑇 𝛔 + 𝜌𝐛 − 𝜌𝐮̈ )𝑑𝛺 + ∫𝛤 𝛿𝑢(𝐭̅ − 𝐈𝜎𝑇 𝛔)𝑑Г = 0 (38)

𝑡
Spatial and Time Discretisations by Finite Element Approach
The finite element discretisation interpolates the unknown

displacements, pore water pressures and suctions, respectively shown by 𝐮,
𝑝𝑤 and 𝑝𝑐 , per:
𝐮 = 𝐍𝐮 𝐔, 𝑝𝑤 = 𝐍𝐩𝐰 𝐏𝐰 and 𝑝𝑐 = 𝐍𝐩𝐜 𝐏𝐜 (39)
where 𝐍𝐮 , 𝐍𝐩𝐰 and 𝐍𝐩𝐜 are the shape functions for the displacement, pore
water pressure and suction, respectively. Based on the above interpolation
functions, and considering pore water pressure as positive in compression,
the following system of fully-coupled algebraic equations can be derived in
matrix form as:
𝐌𝐮 𝐔̈ + 𝐂𝐔̇ + ∫𝛺 𝐁𝑇 𝛔′ d𝛺 − 𝐐𝐰 𝐏𝐰 − 𝐐c 𝐏𝐜 = 𝐅𝐮 (40)
𝐌𝐰 𝐔̈ + 𝐐𝑇𝐰 𝐔̇ + 𝐂𝐰𝐰 𝐏̇𝐰 + 𝐂𝐰𝐜 𝐏̇𝐜 + 𝐇𝐰𝐰 𝐏𝐰 + 𝐇𝐰𝐜 𝐏𝐜 = 𝐅𝐰 (41)
𝐌𝐜 𝐔̈ + 𝐑𝐓𝐜 𝐔̇ + 𝐂𝐜𝐰 𝐏̇𝐰 + 𝐂𝐜𝐜 𝐏̇𝐜 + 𝐇𝐰𝐜

𝑇
𝐏𝐰 + 𝐇𝐜𝐜 𝐏𝐜 = 𝐅𝐜 (42)
where 𝐁 is the strain-displacement matrix and 𝐂 is the damping matrix.

The definitions of the various matrices and vectors are given below:
𝐌𝐮 = ∫𝛺 𝐍𝐮𝑇 𝜌𝐍𝐮 𝑑𝛺 (43)
𝑇
𝐌𝐰 = ∫𝛺 (𝛁𝐍𝐩𝐰 ) ( 𝐤𝑔 𝜌𝑔 + 𝐤 𝑤 ρ𝑤 )𝐍𝐮 𝑑𝛺 (44)
𝐐𝐜 = ∫𝛺 𝐁𝑇 (1 − 𝑆𝑤 )𝐦𝐍𝐩𝐜 𝑑𝛺 (45)
𝐐𝐰 = ∫𝛺 𝐁𝑇 𝐦𝐍𝐩𝐰 𝑑𝛺 (46)
𝐌𝐂 = ∫𝛺 (𝛁𝐍𝐩𝐜 )𝑇 𝐤𝑔 𝜌𝑔 𝐍𝐮 𝑑𝛺 (47)
𝑇
𝐇𝐰𝐰 = ∫𝛺 (𝛁𝐍𝐩𝐰 ) ( 𝐤𝑔 + 𝐤 𝑤 )(𝛁𝐍𝐩𝐰 )d𝛺 (48)
𝑇
𝐇𝐜𝐜 = ∫𝛺 (𝛁𝐍𝐩𝐜 ) ( 𝐤𝑔 )(𝛁𝐍𝐩𝐜 )𝑑𝛺 (49)
𝑇
𝐇𝐰𝐜 = ∫𝛺 (𝛁𝐍𝐩𝐰 ) ( 𝐤𝑔 )(𝛁𝐍𝐩𝐜 )𝑑𝛺 (50)
𝑇
𝐂𝐰𝐰 = ∫𝛺 𝐍𝐩𝐰 𝐶1∗ 𝐍𝐩𝐰 𝑑𝛺 (51)
𝑇 ∗
𝐂𝐜𝐜 = ∫𝛺 𝐍𝐩𝐜 𝐶2 𝐍𝐩𝐜 𝑑𝛺 (52)
𝑇
𝐂𝐰𝐜 = ∫𝛺 𝐍𝐩𝐰 𝐶3∗ 𝐍𝐩𝐜 𝑑𝛺 (53)
𝑇 ∗
𝐂𝐜𝐰 = ∫𝛺 𝐍𝐩𝐜 𝐶3 𝐍𝐩𝐰 𝑑𝛺 (54)
𝐑 𝐜 = ∫𝛺 𝐁𝑇 𝐶6 𝐦𝐍𝐩𝐜 𝑑𝛺 (55)
It is assumed that
𝑛𝑆𝑤 𝑛𝑆𝑔
𝐶1∗ = 𝐶1 + 𝐶3 = + (56)
𝐾𝑤 𝐾𝑔
𝑛 𝜕𝑆
𝐶2∗ = 𝐶4 = 𝑆𝑔 𝐾 − 𝑛 𝜕𝑝𝑤 (57)
𝑔 𝑐
𝑛
𝐶3∗ = 𝐶4 + 𝐶2 = 𝑆𝑔 𝐾 (58)
𝑔
The load and the flow vectors are defined by:
𝐅𝐮 = ∫𝛺 𝐍𝐮T 𝜌𝐛𝑑𝛺 + ∫𝛤 𝐍𝐮𝑇 𝐭𝑑

̅ 𝛤 (59)
𝑡
𝑇 𝑇 ̅
𝐅𝐰 = ∫𝛺 (𝛁𝐍𝐩𝐰 ) ( 𝐤𝑔 𝜌𝑔 + 𝐤 𝑤 𝜌𝑤 )𝐛 𝑑𝛺 − ∫𝛤 𝐍𝐩𝐰 𝑤̇𝑤 𝑑𝛤 −
𝑞𝑤
𝑇 ̅ 𝑇 𝐰̇ 𝑇
∫𝛤 𝐍𝐩𝐰 𝑤̇𝑔 𝑑𝛤 − ∫𝛤 𝐍𝐩𝐰 𝐰̇𝑔𝑇 𝐧∗ 𝑑𝛤 − ∫𝛺 𝐍𝐩𝐰
𝑇
( 𝜌 𝑤 𝛁𝜌𝑤 +
𝑞𝑤 ∩ 𝛤𝑞𝑔 𝑃𝑐 ∩ 𝛤𝑞𝑤 𝑤
𝐰̇𝑔𝑇
𝛁𝜌𝑔 ) 𝑑𝛺 (60)
𝜌𝑔
𝑇 𝑇 ̅ 𝑇 𝑔 𝐰̇ 𝑇
𝐅𝐜 = ∫𝛺 (𝛁𝐍𝐩𝐜 ) 𝐤𝑔 𝜌𝑔 𝐛 𝑑𝛺 − ∫𝛤 𝐍𝐩𝐜 𝑤̇𝑔 𝑑𝛤 − ∫𝛺 𝐍𝐩𝐜 𝜌
𝛁𝜌𝑔 𝑑𝛺
𝑞𝑔 𝑔
(61)
where 𝐛 represents the vector of body force. Also by using Voigt notation
in this paper, we define matrix 𝐦 in three-dimensional space as follows
𝐦𝑇 = [1 1 1 0 0 0] (62)
The generalised-α method (originally introduced by Chung and

Hulbert (1993) for structural dynamics and later modified for the case of
partially saturated soils by Ghorbani et al., (2014) and Ghorbani et al.,
(2016)) is chosen. The integration parameters in this method satisfy the
following relations:
2𝜌∞ −1 𝜌∞ 1
𝛼𝑚 = 𝜌∞ +1
, 𝛼𝑓 = 𝜌 and 𝛽𝑡 = 4 (1 − 𝛼𝑚 + 𝛼𝑓 )2
∞ +1
and the following condition yields second order accuracy
1
𝛾𝑡 = 2 − 𝛼𝑚 + 𝛼𝑓 (63)
where 𝜌∞ is the desired value of the spectral radius at infinity, and 𝛽𝑡 and
𝛾𝑡 are Newmark’s parameters. The unconditional stability of the method is
guaranteed if
1 1
𝜃𝑡 ≥ 0.5, 𝛼𝑚 ≤ 𝛼𝑓 ≤ 0.5 and 𝛽𝑡 ≥ 4 + 2 (𝛼𝑓 − 𝛼𝑚 )
where 𝜃𝑡 is an integration parameter.

Coupling the generalized–α method with a Newton-Raphson iteration
gives the following equations for Jacobian matrix, 𝐉
1 𝛾
(1 − 𝛼𝑚 )𝐌𝐮 + 𝑡 (1 − 𝛼𝑓 )𝐂 + (1 − 𝛼𝑓 )𝐊 −𝐐𝐰 (1 − 𝛼𝑓 ) −𝐐𝐜 (1 − 𝛼𝑓 )
𝛽𝑡 Δ𝑡 2 𝛽𝑡 Δ𝑡
1 𝛾 1 1
𝐉= (1 − 𝛼𝑚 )𝐌𝐰 + 𝑡 (1 − 𝛼𝑓 )𝐐𝑇𝐖 (1 − 𝛼𝑓 )𝐂𝐰𝐰 + (1 − 𝛼𝑓 )𝐇𝐰𝐰 (1 − 𝛼𝑓 )𝐂𝐰𝐜 + (1 − 𝛼𝑓 )𝐇𝐰𝐜
𝛽𝑡 Δ𝑡 2 𝛽𝑡 Δ𝑡 𝜃𝑡 Δ𝑡 𝜃𝑡 Δ𝑡
1 𝛾 1 1
(1 − 𝛼𝑚 )𝐌𝐜 + 𝑡 (1 − 𝛼𝑓 )𝐑𝑇𝐜 𝑇
(1 − 𝛼𝑓 )𝐂𝐜𝐰 + (1 − 𝛼𝑓 )𝐇𝐰𝐜 (1 − 𝛼𝑓 )𝐂𝐜𝐜 + (1 − 𝛼𝑓 )𝐇𝐜𝐜
[ 𝛽𝑡 Δ𝑡 2 𝛽𝑡 Δ𝑡 𝜃𝑡 Δ𝑡 𝜃𝑡 Δ𝑡 ]
MODELING HYSTERETIC BEHAVIUOR OF THE SWCC
It is well known that the Soil Water Characteristic curves (SWCCs)

show hysteresis during wetting and drying. For instance, experimental data
of hysteretic behaviour of the SWCC have been presented by researchers
such as Fredlund and Rahardjo (1993). This gives a non-unique and path-
dependent relationship between the saturation degree 𝑆𝑤 , porosity 𝑛 and
suction 𝑝𝑐 , for a soil. There are various approaches for modelling the
SWCC that will be explained in coming sections.
Approach 1: Assumption of Elasticity for Scanning Curves
In this method, the hysteretic SWCC equation is described by the main

wetting and drying relations playing a role similar to the yield surface in
elasto-plastic mechanical constitutive models. The hydraulic state cannot
exceed the two yield surfaces in the space defined by the logarithm of
suction and the saturation degree. A schematic representation of the
intermediate paths between the yield surfaces, known as “scanning
curves,” are shown in Figure 1. In this figure, the wetting and drying lines
have been generated using the empirical equation proposed by Brooks and
Corey (1964) which can be approximated as follows
𝑏−𝛼
𝑃𝛼 𝜈
( ) (𝛼 = 𝑤, 𝑑) 𝑝𝑐 > 𝑃𝑑
𝑆𝑒 = { 𝑝𝑐∗ (64)
𝑑
1 𝑝𝑐 ≤ 𝑃
where 𝑃𝛼 (with 𝛼 = 𝑤 and 𝑑 for the wetting and drying lines, respectively)
is known as the air-entry value and 𝜈 𝑏−𝛼 is a fitting parameter. 𝑆𝑒 is the
effective degree of saturation defined by
𝑆 −𝑆
𝑆𝑒 = 𝑆 𝑤 −𝑆𝑟𝑎 (65)
𝑟𝑤 𝑟𝑎
where 𝑆𝑟𝑎 is the residual degree of saturation at extremely dry conditions,

and 𝑆𝑟𝑤 is the residual degree of saturation (normally =1.0) when fully
saturated (Ghorbani et al., (2018a)).
In addition, Equation (64) incorporates a modified suction, 𝑝𝑐∗ defined
by
′
𝑝𝑐∗ = 𝑒 𝛺 𝑝𝑐 (66)
where 𝛺′ is an additional fitting parameter quantifying the role of volume

changes in altering the saturation degree. This definition of 𝑝𝑐∗ was also
used by Ghorbani et al., (2018c) for modification of the SWCC equation
by Van Genuchten (1980).
For the scanning curve shown in Figure 1, it has been assumed that a
relationship can be established between any two arbitrary initial and final
𝑝∗ 𝑖 𝑝∗ 𝑖 + 𝛥𝑝∗
points along this line, located at | 𝑐𝑖 and | 𝑐 𝑓 𝑐 , respectively. The
𝑆𝑒 𝑆𝑒
transition between these two points can be approximated by the following
relationship
𝑖
𝑓 𝑝𝑐∗ +𝛥𝑝𝑐∗
𝑆𝑒 = 𝑆𝑒𝑖 + 𝑐 ℎ ln ( ) (67)
𝑝𝑐𝑖
where 𝑐 ℎ is the slope of the scanning curve.

The main advantage of using this method is the simplicity of
implementation. However, the approach has the following shortcomings:
1) An inability to model arbitrary paths of scanning curves as noted

by Li (2005).
2) The presence of critical points at the intersections of the scanning
curves and the main wetting and drying line which leads to a
numerical problem as outlined below.
1.2
1
Saturation Degree
0.8 Scanning
curves
0.6
Drying
line
0.4
0.2 Wetting line
0
1 10 100 1000
Ln (p*c)
Figure 1. A typical SWCC considering the effect of hysteresis.
The latter is identified by Ghorbani et al., (2018c). To elaborate this

further, it should be realized that in the preceding sections, a fully implicit
time integration scheme was presented for solving the equations of
unsaturated soil dynamics, by combining the generalised-α method and
Newton-Raphson iteration. Because the derivatives of saturation degree
𝜕𝑆𝑤 𝜕𝑆𝑤
with respect to suction and porosity, 𝜕𝑝𝑐
and 𝜕𝑛
, are present in the fully
coupled equations, it can be expected that the Newton-Raphson iteration,
may fail to converge in the neighbourhood of the critical points. This can
occur if the initial guess for the solution (required at the initiation of the
Newton-Raphson algorithm) is far from the correct solution.
Approach 2: Arbitrary Evolution of Scanning Curves
This approach was originally proposed by Li (2005) where the main

wetting and drying lines were considered as two bounding lines
determining the area (in the space defined by the saturation degree, and the
modified suction) within which the material state can be located. A simpler
version of this approach was presented by Zhou et al., (2012) where the
evolution of the scanning curves was defined based on the distance from
the bounding lines. Unlike the elastic approach, this method yields an
incremental relationship relating the changes of the saturation degree to the
changes of volume and suction. The rate of change of the effective
saturation degree, 𝑆𝑒 (or the saturation degree 𝑆𝑤 ) can be described by
𝑑𝑆𝑒 = 𝑀∗ . 𝑑𝑝𝑐∗ (68)
where
𝜕𝑝𝑐∗ 𝜕𝑝𝑐∗
𝑑𝑝𝑐∗ = 𝑑𝑝𝑐 + 𝑑𝑛 (69)
𝜕𝑝𝑐 𝜕𝑛
To define the equation of 𝑀∗, we can suppose that, for a certain value
of 𝑝𝑐∗ , the slope of the SWCC in 𝑆𝑒 − 𝑝𝑐∗ space should approach the slope
𝜕𝑆 𝑤 𝜕𝑆𝑒𝑑
of the main wetting, (𝜕𝑝∗𝑒𝑤), and the slope of the main drying, ( 𝑑 ),
𝑐 𝜕𝑝𝑐∗
curves once we get close to these two lines. Then, an interpolation function
can be employed by which the slope of the SWCC at any arbitrary points
between these two lines is obtained as follows
𝑝∗ 𝑏𝛼 𝜕𝑆 𝛼
𝑀∗ = (𝑝∗𝑐𝛼 ) 𝑒
𝜕𝑝𝑐∗
, (𝛼 = 𝑤, 𝑑) (70)
𝑐
with
𝑝𝑐∗ 𝛼 = 𝑆𝑒𝛼 −1 , (𝛼 = 𝑤, 𝑑) (71)

and 𝑏𝑤 and 𝑏𝑑 are model parameters with negative and positive values in
the wetting and the drying processes, respectively.
𝜕𝑆 𝛼
Note that once 𝑝𝑐∗ reaches 𝑝𝑐∗ 𝛼 , we get 𝑀∗ = 𝜕𝑝∗𝑒𝛼.
𝑐
Finding a closed-from solutions for Equation (69) and (70) is generally
not possible, and therefore, a numerical integration scheme may be
required to solve them. One such scheme is given by Ghorbani et al.,
(2018c) who suggested to use an adaptive explicit integration method with
automatic error control. The scheme breaks the suction and void ratio
increments, in the time step 𝑡, into several subincrements in pseudo time
steps. The method evaluates the error in calculating the saturation degree
using the Modified Euler method and uses the obtained errors to set the
size of the subincrements during the integration process.
Eventually, the effective saturation degree will be updated in each time
step of the analysis as follows
Δ𝑝𝑐∗
𝑆𝑒𝑡+Δ𝑡 = 𝑆𝑒𝑡 + ∫0 𝑀∗ . 𝑑𝑝𝑐∗ (72)
In the initial step of the algorithm, we identify the current position in

𝑆𝑒 − 𝑝𝑐∗ space. In this space, we assume that the main wetting and drying
lines are two bounding lines. Hence, at any time of the analysis, the state
can only be located within (on a scanning curve) or on the main wetting
and drying lines. If the state is situated outside the area enclosed by the
wetting and drying lines it should be discarded and the analysis should be
ended. Then, there is a need to check if the previous wetting/drying process
is reversed in the current time step as follows
Δ𝑝𝑐∗ 𝑡−∆𝑡 . Δ𝑝𝑐∗ 𝑡 < 0 (73)
where Δ𝑝𝑐∗ 𝑡−∆𝑡 and Δ𝑝𝑐∗ 𝑡 are the change of the scaled suction, 𝑝𝑐∗ , in the
previous and the current time steps, respectively. The algorithm is
described hereinafter.
1. Initial input: 𝑛𝑡 , Δ𝑛𝑡 , Δ𝑛𝑡−Δ𝑡 , 𝑆𝑒𝑡 , 𝑝𝑐𝑡 , Δ𝑝𝑐𝑡 , Δ𝑝𝑐𝑡−Δ𝑡 , 𝑝𝑐𝑟 , 𝑛𝑟 and
𝑆𝑊𝑇𝑜𝑙.
2. Find the location of the material in 𝑆𝑒 − 𝑝𝑐∗ space; stop the analysis
if it is outside the region encompassed by the main wetting and
drying curves.
Else:
3. Check if a reverse process happens
4. Set 𝑡̃ = 0 and Δ𝑡̃ = 1
5. While 𝑡̃ < 1 perform the following:
Compute Δ𝑆𝑒𝑖 , for 𝑖 = 1,2, using:
Δ𝑆𝑒𝑖 = Δ𝑡̃. 𝑀𝑝𝑐 𝑖 . Δ𝑝𝑐𝑡 + Δ𝑡̃. 𝑀𝑛 𝑖 Δ𝑛𝑡 (74)
with
𝜕𝑝𝑐∗ 𝑖
𝑀𝑝𝑐 𝑖 (𝑆𝑒𝑖 , 𝑝𝑐𝑖 , 𝑛𝑖 , 𝑝𝑐𝑟 , 𝑛𝑟 ) = 𝑀∗ 𝑖 ( )
𝜕𝑝𝑐
and
𝜕𝑝∗ 𝑖
𝑀𝑛 𝑖 (𝑆𝑒𝑖 , 𝑝𝑐𝑖 , 𝑛𝑖 , 𝑝𝑐𝑟 , 𝑛𝑟 ) = 𝑀∗ 𝑖 ( 𝜕𝑛𝑐 )
Also,
𝑆𝑒1 = 𝑆𝑒𝑡̃ , 𝑝𝑐1 = 𝑝𝑐𝑡 + 𝑡̃. Δ𝑝𝑐𝑡 , 𝑛1 = 𝑛𝑡 + 𝑡̃. Δ𝑛𝑡
𝑆𝑒2 = 𝑆𝑒𝑡̃ + Δ𝑆𝑒1 , 𝑝𝑐2 = 𝑝𝑐𝑡 + (𝑡̃ + Δ𝑡̃). Δ𝑝𝑐𝑡 , 𝑛2 = 𝑛𝑡 + (𝑡̃ + Δ𝑡̃).
Δ𝑛𝑡
and lastly
1
𝑆𝑒𝑡̃+Δ𝑡̃ = 𝑆𝑒𝑡̃ + 2 (Δ𝑆𝑒1 + Δ𝑆𝑒2 ) (75)
𝑝𝑐𝑡̃+Δ𝑡̃ = 𝑝𝑐2
𝑛𝑡̃+Δ𝑡̃ = 𝑛2
6. Calculate the relative error for the current substep:
|Δ𝑆𝑒2 −Δ𝑆𝑒1 |
𝐸 = 𝑚𝑎𝑥 { ̃ ̃ , 𝐸𝑃𝑆} (76)
|𝑆𝑒𝑡+Δ𝑡 |
where EPS is a machine constant denoting the smallest relative error

that can be calculated.
7. If 𝐸 > 𝑆𝑊𝑇𝑜𝑙 the substep has failed. First calculate:
𝑆𝑊𝑇𝑜𝑙
𝒜 = 𝑚𝑎𝑥 {0.9√ 𝐸
, 0.1} (77)
then set:
∆𝑡̃ ← 𝑚𝑎𝑥{𝒜∆𝑡̃, 𝛥𝑡̃𝑚𝑖𝑛 },
8. and go to step 5.
9. The substep is accepted, update porosity, suction and the effective
saturation degree.
10. Extrapolate to get the size of next subincremenet as follows:
𝑆𝑊𝑇𝑜𝑙
𝒜 = 𝑚𝑖𝑛 {0.9√ , 1.1}
𝐸
then set
∆𝑡̃ ← 𝒜∆𝑡̃,
𝑡̃ ← 𝑡̃ + ∆𝑡̃.
11. Do not let the next step size drop below the minimum step size and
ensure that the pseudo-time does not proceed beyond 𝑡̃= 1 by
setting:
∆𝑡̃ ← 𝑚𝑎𝑥{∆𝑡̃, Δ𝑡̃𝑚𝑖𝑛 }
and then
∆𝑡̃ ← 𝑚𝑎𝑥{∆𝑡̃, 1 − 𝑡̃}.
12. Exit with the updated effective saturation degree once 𝑡̃ = 1.
A desirable integration tolerance is considered in the integration

algorithm by 𝑆𝑊𝑇𝑜𝑙 which can be used as a tool to control the integration
error in the analysis. In the following algorithm 𝑡̃ is the pseudo-time (used
for substepping) and should not be confused with the actual time 𝑡 in the
analysis. A recommendation for the minimum substep size (Δ𝑡̃𝑚𝑖𝑛 ), based
on the authors’ experience, is of the order of 10−4 and is considered in this
paper. Throughout this chapter 𝑆𝑊𝑇𝑜𝑙 is of the order of 10−5 unless stated
otherwise.
To demonstrate the performance of this approach, the following
equation is chosen as the equation of the main wetting and drying curves:
𝛼
𝛼 −𝑚
𝑝𝑐∗ 𝑛
𝑆𝑒 = (1 + (𝑃𝑑 ) ) (𝛼 = 𝑤, 𝑑) (78)
where 𝑛𝛼 and 𝑚𝛼 (𝛼 = 𝑤, 𝑑) are two fitting parameters and 𝑃𝛼 (𝛼 = 𝑤, 𝑑)

are the air-entry values of the main wetting and drying curves. Also, the
parameters given in Table 1 are selected to simulate a multi-stage
wetting/drying process as follows.
Table 1. The SWCC parameters
𝒏𝒅 𝒎𝒅 𝑷𝒅 (kPa) 𝒃𝒅 𝒏𝒘 𝒎𝒘 𝑷𝒘 (kPa) 𝒃𝒘
20 0.1 100 5.0 20 0.1 50.0 -5.0
Figure 2. Simulation of a four-stage process of wetting and drying with the approach
proposed by Zhou et al., (2012).
The starting values of 𝑆𝑒 and 𝑝𝑐∗ are 0.4 and 150.00 kPa, respectively.
The following four-stage process has been modelled:
 Wetting with Δ𝑝𝑐∗ = −72.0 kPa

 Drying with Δ𝑝𝑐∗ = 37.0 kPa
 Wetting with Δ𝑝𝑐∗ = −51.0 kPa
 Drying with Δ𝑝𝑐∗ = 60.0 kPa
The result of the simulation is presented in Figure 2. It is noticed that

the chosen procedure can allow arbitrary paths for scanning curves in
simulating a multi-step wetting and drying process.
Nevertheless, the approach fails to avoid the generation of critical
points at the wetting/drying reversals. The points are circled in the figure.
Approach 3: Smooth Evolution of Scanning Curves
This approach was introduced by Ghorbani et al., (2018c) with the

motivation to eliminate the critical points in Approach 2. Ghorbani et al.,
(2018c) showed that this can be achieved by storing the values of 𝑝𝑐∗ and
𝑆𝑒 at the initiations of reversals, referred to by 𝑝𝑐∗ 𝑟 and 𝑆𝑒𝑟 , respectively.
Moreover, the slope of the SWCC at the beginning of a reverse process, is
needed and is given by 𝑀∗ 𝑟 . This allows the definition of 𝑀∗ in Equation
(70) to be altered such that at the start of a reverse process 𝑀∗ 𝑟 is obtained
𝑝𝑐∗ 𝑏𝛼 𝜕𝑆𝑒𝛼
and at the end of the process ( 𝛼) is acquired. Here, an interpolation
𝑝𝑐∗ 𝜕𝑝𝑐∗
function is introduced to gradually damp 𝑀∗ 𝑟 as 𝑝𝑐∗ changes from 𝑝𝑐∗ 𝑟 to
𝑝𝑐∗ 𝛼 as follows
𝛼 𝑏𝑠𝑐
𝑝∗ −𝑝∗
𝑀∗ 𝑠𝑐 = 𝑀∗ 𝑟 (𝑝∗𝑐𝑟 −𝑝𝑐∗ 𝛼) (79)
𝑐 𝑐
Note that Equation (79) ensures that once 𝑝𝑐∗ → 𝑝𝑐∗ 𝑟 , we get 𝑀∗ 𝑠𝑐 →
𝑀∗ 𝑟 ; and once 𝑝𝑐∗ → 𝑝𝑐∗ 𝛼 , we get 𝑀∗ 𝑠𝑐 → 0.0. Another parameter (𝑏𝑠𝑐 ) is
added, which is a positive quantity, to have extra control on the shape of
scanning curves near the start of a reverse process. By having this
definition, the updated form of Equation (70) becomes
𝑝∗ 𝑏𝛼 𝜕𝑆 𝛼
𝑀∗ = (𝑝∗𝑐𝛼 ) 𝑒
𝜕𝑝𝑐∗
+ 𝑀∗ 𝑠𝑐 (80)
𝑐
The result of the simulation of the four-stage process (demonstrated in

Figure 2, previously) with the modified approach is presented in Figure 3.
The material parameters and the initial conditions are the same and 𝑏𝑠𝑐 =
20.0. It is clear that the approach has succeeded in making smooth
variations of the SWCC slopes upon the initiation of reverse processes
(circled in Figure 2) which was the main motivation of the presented
modifications.
Figure 3. Simulation of the four-stage process by the modified approach.
From Equation (79), it can be seen that as 𝑏 𝑠𝑐 → ∞, we get 𝑀∗ 𝑠𝑐 → 0.

In this case, the model by Zhou et al., (2012) will be recovered. This is
shown in Figure 4 where three analyses were performed with 𝑏 𝑠𝑐 being set
to 10, 20 and 50. Other parameters are set to be the same as those provided
in Table 1. The initial saturation degree and suction are set to 0.53 and 74
kPa, respectively. It is demonstrated that all the studied cases follow the
same initial wetting path (∆𝑝𝑐∗ = −10 kPa) since 𝑏 𝑠𝑐 does not change the
shape of the scanning curves in this situation. It is also shown that as 𝑏 𝑠𝑐
increases, a sharper change of the slope of SWCC at the transition point is
obtained.
Figure 4. The effect of 𝑏 𝑠𝑐 on the shape of scanning curve.
Figure 5. Simulation of the test reported by Kwa et al., (2018).
Table 2. The SWCC parameters for the test performed

by Kwa et al., (2018)
𝒏𝒅 𝒎𝒅 𝑷𝒅 𝒃𝒅 𝒏𝒘 𝒎𝒘 𝑷𝒘 (kPa) 𝒃𝒘 𝒃𝒔𝒄 𝜴′ 𝑺𝒓𝒂 𝑺𝒓𝒘

(kPa)
2.1 0.0105 2.0 5 2.3 0.08 0.1 -5 20 0 0 1
Applied pressure
Drainage boundary
smooth / impermeable
smooth / impermeable
H=10 m
rough / impermeable
displacement nodes
displacement, pore pressure and suction nodes
Figure 6. Soil column and boundary conditions.
The performance of the model in reproducing the evolution of the

scanning curve during a wetting/drying cycles has been evaluated against
the data provided by Kwa et al., (2018) of a soil containing basalt
aggregates with particle sizes from 9.5mm to 2 𝜇m and 18% of feldspar
fines. As mentioned by the authors, the dependency of the SWCC equation
on void ratio is small; therefore, it has been ignored in the presented

simulations. The results of simulations together with the data are presented
in Figure 5 corresponding to a wetting/drying process. The main wetting
and drying curves are approximated by taking the equation proposed by
Van Genuchten (1980). The parameters of the model are shown in Table 3.
In obtaining the curves, it is assumed that the initial saturation degree
and suction are 0.336 and 189.1 kPa, respectively as done in the test. It is
seen that good agreement with the experimental data can be achieved with
the selected approach, in particular in the way the scanning curves evolve
during cycles of wetting and drying.
APPLICATION TO BOUNDARY-VALUE PROBLEMS
Two example problems are selected to demonstrate the performance of

the proposed model and the accompanying integration scheme in solving
boundary value problems.
The first studies the response of an elastic one-dimensional soil
column to a loading/unloading process and the subsequent wetting/drying
cycle. An unsaturated soil column with a height of 10 m is considered. The
boundary conditions and the geometry of the column are shown in Figure
6. The initial saturation degree, 𝑆𝑤 is set to 0.3 everywhere. The material
properties and SWCC parameters are given in Table 3 and Table 4,
respectively.
A preesure ramp is applied on the top boundary so that the pressure
increases from 0 to 10 MPa over 1000 seconds and then reduced to zero
over further 1000 seconds as shown in Figure 7. Two analyses have been
carried out with this pressure, time history. In the first, the SWCC
formulation is assumed to not have any hysteresis, whereas in the second
analysis the hysteresis is considered. In both analyses, the initial material
state is considered to be on the main drying curve (𝑆𝑤 = 0.3).
Table 3. Material parameters
Parameter type Symbol Value Unit

Porosity 𝑛 0.375 -
Density of the solid skeleton 𝜌𝑠 2650 kg m−3
Density of the water 𝜌𝑤 997 kg m−3
Density of the air 𝜌𝑎 1.01 kg m−3
Elastic modulus of the mixture 𝐸 40.0 MPa
Poisson’s ratio 𝜈 0.02 Pa
Bulk modulus of the water 𝐾𝑤 2.25 × 109 Pa
Bulk modulus of the air 𝐾𝑎 1.10 × 105 Pa
Intrinsic permeability 𝑘 2.5 × 10−12 m2
Viscosity of the water 𝜂𝑤 1.0 × 10−3 Ns m−2
Viscosity of the air 𝜂𝑎 1.8 × 10−5 Ns m−2
There are two mechanisms associated with the response of the column.
During the loading, the column shows compression. As the column settles,
the saturation degree increases. Thus, the suction decreases and
consequently water pressure increases. On the other hand, throughout the
unloading, the column expands and saturation degree decreases. In this
condition, the suction increases, and the water pressure decreases.
The variations of the saturation degree against the suction at the
bottom of the column in both analyses are plotted in Figure 8 along with
the main drying and wetting lines. It is demonstrated that in the absence of
hysteresis) the wetting and the drying paths will be the same and the 𝑆𝑤 −
𝑝𝑐 state moves up and down the drying line.
However, in the presence of hysteresis (second analysis), as
compression begins the material gradually moves away from its initial
position on the main drying curve. In such a condition, the material is
located on a scanning curve and tends to reach the bounding line shown by
the main wetting curves. In the second step of the analysis where
unloading begins, the material moves back toward the drying curves. The
hysteresis loop is clearly seen in the graph. Also, both transitions from the
main wetting and drying curves to the scanning curves have occurred
smoothly.
Table 4. The SWCC parameter

(kPa)
25.0 0.4 500.0 5.0 4.0 0.7 250.0 -5 20 0 0 1
Figure 7. The pressure applied on the top of the unsaturated column.
Figure 8. Comparison of the saturation degree variation in the bottom of the

unsaturated column in the analyses with and without hysteretic SWCC.
Table 5. Comparison of the relative error, 𝑬𝑺𝒆 , and computational

time for the simulations with different integration tolerances
𝑺𝑾𝑻𝒐𝒍 𝑬𝑺𝒆 CPU time

10e-1 3.55e-3 0.94
10e-2 2.91e-3 0.95
10e-3 8.45e-4 0.95
10e-4 4.10e-4 0.95
10e-5 5.69e-5 0.95
10e-12 - 1
To evaluate the integration process, a tight tolerance of 10−12 for

𝑆𝑊𝑇𝑜𝑙 is selected as a benchmark by which the relationships of 𝑆𝑊𝑇𝑜𝑙
with the accuracy of the intergration scheme and the computational times
are investigated. The relative error, 𝐸𝑆𝑒 , in the analysis is given by
𝑟𝑒𝑓
∑𝑙𝑖=1|𝑆𝑒 −𝑆𝑒 |
𝐸𝑆𝑒 = 𝑟𝑒𝑓
𝑖
(81)
∑𝑙𝑖=1 𝑆𝑒
𝑖
𝑟𝑒𝑓
where 𝑆𝑒 is the effective saturation degree calculated by taking
−12
𝑆𝑊𝑇𝑜𝑙 = 10 ; and the subscript 𝑖 denotes the ith integration point in the
mesh and 𝑙 is the total number of integration points. Five tolerances of
10−1, 10−2, 10−3, 10−4 and 10−5 were chosen for 𝑆𝑊𝑇𝑜𝑙. The relative
error (𝐸𝑆𝑒 ) and CPU time for these analyses are compared in Table 5. The
results indicate that tighter integration tolerance can decrease the relative
error 𝐸𝑆𝑒 without significant changes of the speed of the analysis as the
corresponding values of CPU time suggest in the table.
Coupling the hysteretic SWCC model with elasto-plasticity
For the final example, the capability of the proposed approach in

modelling the elasto-plastic response of unsaturated soils during an impact
load is demonstrated.
Table 6. The SWCC parameter for the impact problem

(kPa)
20.0 0.14 200.0 5 20 0.14 100 -5 20 0.05 0 1.0
Figure 9. The schematic finite element model for the problem of a rigid footing.
The geometry of the plane strain model is presented in Figure 8. In this

example, a rigid strip footing is placed on top of the soil. The top boundary
is permeable; and the side boundaries are restrained so that no lateral
displacements are possible. The overall width of the footing is 2 m. The
Updated Lagrangian framework (Ghorbani et al., 2016b and Ghorbani et
al., 2018b) is selected to consider the occurrence of large deformations in

this example. The SWCC parameters for this analysis are listed in Table 6.
The selected constitutive model is the same as that used by Ghorbani et al.,
(2018c) (given in Appendix A) and its parameters are shown in Table 7.
In this example, the saturation degree of 0.5 and suction value 180 kPa
were prescribed initially on the domain. A triangular dynamic pressure
with the maximum of 90 kPa is applied on the footing (Figure 9.a).
For the given load, a settlement of 33.4 cm is predicted by the model
(Figure 9.b) during the impact. During the loading, the saturation degree
below the impact area rises because of the compression of the soil. The
process is inverted once the unloading step is begun.
Table 7. Constitutive model and material parameters
Parameter type Symbol Value Unit

Slope of critical state line 𝑀𝑚𝑎𝑥 0.9833 -
The slope of loading line in fully saturated 𝜆0 0.2 -
state
Poisson’s ratio of the mixture 𝜇 0.3 -
The slope of unloading/reloading line in 𝜅 0.04 -
fully saturated state
Specific volume at 𝑝′ = 1 𝛤∗ 2.5 -
Over Consolidation Ratio (OCR) - 1.0 -
Initial yield surface size 𝛼 10 kPa
Unsaturated material parameter 𝑏 5.4 1/(kPa)
Unsaturated material parameter 𝑟 0.75 -
Density of the solid skeleton 𝜌𝑠 2700 kg m−3
Density of the water 𝜌𝑤 997 kg m−3
Density of the air 𝜌𝑎 1.1 kg m−3
Bulk modulus of the water 𝐾𝑤 2.25 × 109 Pa
Bulk modulus of the air 𝐾𝑎 1.01 × 105 Pa
Intrinsic permeability 𝑘 2.5 × 10−12 m2
Viscosity of the water 𝜂𝑤 1.0 × 10−3 Ns m−2
Viscosity of the air 𝜂𝑎 1.8 × 10−5 Ns m−2
(a) (b)
(c) (d)
Figure 10. The dynamic applied load and the model response during the impact. a)
Applied pressure. b) Settlement of the ground during the impact. c) Saturation degree
changes at 25 cm below the centre of the footing. d) Suction changes at 25 cm below
the centre of the footing.
This is illustrated in Figure 9.c at a point located at 25 cm under the

centre of the footing. Saturation degree and suction have an inverse
relationship. This is illustrated in Figure 9.d where, at the same point,
suction initially decreases and then increases.
The variations of the scaled suction with respect to the saturation
degree is given in Figure 10. The figure clearly illustrates the hysteretic
behavior predicted by the model during the impact with a smooth transition
at the wetting/drying reversals.
Wetting
Initial point
Figure 11. Hysteretic response of SWCC at 25 cm below the centre of the footing.
CONCLUSION
This chapter initially has provided the finite element formulations for
modelling dynamic response of unsaturated soils. Then, three approaches
for modelling the hysteretic response of the SWCCs have been presented
and the numerical problems associated with each method along with their
capabilities have been demonstrated. It has been shown that the approach
presented by Ghorbani et al., (2018c) can provide robust solutions in
solving complex boundary-value problems in unsaturated soil mechanics
involving large deformations, elasto-plasticity and dynamic loadings.
APPENDIX A. ELASTO-PLASTIC CONSTITUTIVE MODEL
An extension of the Modified Cam Clay (MCC) model first proposed

by Roscoe (1968) for unsaturated soils is selected. The yield surface, 𝑓,
and the plastic potential surface, 𝑔, are described by
2 2
1 (1+𝛽 ′ )𝑝′ (1+𝛽 ′ )𝑞
𝑓 = 𝑔 = 𝛽2 ( 𝛼∗
− 1) + ( 𝑀(𝜃)𝛼∗ ) − 1 (82)
where 𝛼 ∗ determines the size of the yield surface for unsaturated

conditions, 𝑝′ represents the effective mean stress and 𝑞 is the deviatoric
stress. 𝛽 ′ and 𝛽 as two parameters adjusting the shape of the yield surface.
𝑀 is the slope of the critical state line in 𝑝′ − 𝑞 stress space and can
change with the Lode angle, 𝜃 according to the rule suggested by Sheng et
al., (2000) where
4 1/4
2𝛼′
𝑀 = 𝑀𝑚𝑎𝑥 ( 4 4 ) (83)
1+𝛼 ′ −(1−𝛼′ ) sin 3𝜃
where 𝑀𝑚𝑎𝑥 is the slope of the CSL under triaxial compression when Lode
angle equals to 30°; and 𝛼 ′ can have the following relationship with
friction angle, 𝜙
3−sin 𝜙
𝛼 ′ = 3+sin 𝜙 (84)
The elastic s bulk modulus 𝐾 is defined as follows
−(1+𝑒)𝑝′
𝐾= 𝜅
(85)
where 𝑒 is the void ratio, 𝜅 is a model parameter.

The evolution of the yield surface is expressed by an equation
suggested by Zhou et al., (2012) where the hardening parameter for
unsaturated soil, 𝛼 ∗ is expressed by
𝛼∗ 𝛼 (𝜆0 −𝜅)/(𝜆−𝜅)
𝑝𝑟
= (𝑝 ) (86)
𝑟
where 𝛼 is the yield surface size at the fully saturated condition, 𝑝𝑟 is a

reference mean effective stress, 𝜅 represents the slope of the compression-
recompression line, and 𝜆 and 𝜆0 are the slopes of the normal compression
lines for the unsaturated and saturated conditions, respectively. The
variation of 𝜆 with respect to the effective saturation degree, 𝑆𝑒 , is
described by:
𝜆 = 𝜆0 (1 − (1 − 𝑆e )𝑏1 (1 − 𝑟)) (87)
APPENDIX B. ADDITIONAL DETAILS

ON THE EQUATIONS OF SWCC
The equation of the SWCC is
𝛼
𝛼 −𝑚
𝑝𝑐∗ 𝑛
𝑆𝑒𝛼 = (1 + (𝑃𝛼 ) ) (𝛼 = 𝑤, 𝑑) (88)
which yields
1
−1 𝑛𝛼
𝑆𝑒𝛼 −1 = 𝑝𝑐∗ 𝛼 (𝑆𝑒 ) 𝛼
= 𝑃 ((𝑆𝑒 ) 𝑚𝛼 − 1) (𝛼 = 𝑤, 𝑑) (89)
In addition,
𝛼
𝑝𝑐 ∗ 𝑛
𝜕𝑆𝑒𝛼 −𝑚𝛼 𝑛𝛼 𝑆𝑒𝛼 ( 𝛼 )
𝑃
𝜕𝑝𝑐∗
= ∗ 𝑛𝛼
(𝛼 = 𝑤, 𝑑) (90)
𝑝 𝑐)
𝑝𝑐∗ (1+( 𝛼 )
𝑃
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Chapter 3
TEMPERATURE DISTRIBUTION AND WATER

MIGRATION IN UNSATURATED SOIL
Bingxi Li, Yiran Hu, Fei Xu, Yaning Zhang*,

Shuang Liang, Wenyu Song and Zhongbin Fu
School of Energy Science and Engineering, Harbin Institute of
Technology (HIT), Harbin, Heilongjiang, China
ABSTRACT
Temperature distribution and water migration in unsaturated soil are

of significant importance because they are related to the thermal-physical
properties of soil and the changes in these properties may cause
disastrous engineering problems including cracking of pavement, damage
of structure foundation, fracture of pipelines, etc. This chapter focuses on
the temperature distribution and water migration in unsaturated soil.
Temperature distribution and water migration in unsaturated soil during
the freezing and thawing processes are experimentally investigated and
the results are presented and discussed. Based on the soil structure,
multiphase flow, temperature distribution and water potential, a
*
Corresponding Author’s E-mail: ynzhang@hit.edu.cn.
80 Bingxi Li, Yiran Hu, Fei Xu et al.
mesoscopic lattice Boltzmann model (LBM) is developed to simulate the

temperature distribution and water migration in unsaturated soil. Based
on the soil structure, multiphase flow, temperature distribution, water
potential, melting film and interactive force, a modified LBM model is
also developed to simulate the temperature distribution and water
migration in unsaturated soil. Main conclusions and future outlook are
also briefly stated and summarized. The contents included in this chapter
not only detail the experimental procedures and the results of temperature
distribution and water migration in unsaturated soil, but also introduce the
models for estimating the temperature distribution and water migration in
unsaturated soil.
Keywords: unsaturated soil, temperature distribution, water migration,

freezing, thawing, lattice Boltzmann model
1. INTRODUCTION
Frozen grounds (permafrost and seasonally frozen grounds) occupy

approximately 54 million km2 of the exposed land areas of the northern
hemisphere [1], and these grounds (especially the seasonally frozen
grounds) freeze and thaw in response to the temperature change and water
variation, causing many serious engineering problems including pavement
cracking, building foundation damage, pipelines fracture, etc. [2, 3].
During the soil freezing and thawing processes, heat transfer and water
migration coexist and they occur in a coupled manner. Due to the
temperature difference between different soil zones, especially between the
ground surface and the interior, a temperature gradient forms, driving the
heat to flow from the higher temperature zone towards the lower one.
Meanwhile, pore water migrates from the unfrozen zone to the freezing
fringe and builds the frozen front, influencing the heat conduction process
due to the effect of convection and latent heat of phase change [4]. Thus,
systematic experiments and simulations of temperature distribution and
water migration during the freezing and thawing processes are of
significant importance.
Temperature Distribution and Water Migration… 81
2. TEMPERATURE DISTRIBUTION
AND WATER MIGRATION IN UNSATURATED SOIL
For unsaturated soil, it initially contains a certain amount of water

which then will redistribute along the temperature gradient during the
freezing and thawing processes. When the soil starts to freeze, temperature
gradient forms from the surface to the deeper soil which leads the water to
freeze from the surface, and then the soil water potential gradient causes
the migration of water from the unfrozen region to the frozen region.
During the soil thawing process, water is obstructed by the middle frozen
layer while the ice layer starts to melt from both upper and lower sides. To
study the basic properties of temperature distribution and water migration
in unsaturated soil, experiments are considered in this section. The
temperature distribution and water migration in unsaturated soil can be
studied based on experimental device which is mainly composed of soil
storage system, water supply system, temperature control system,
parameter measurement system and so on. The soil storage system is used
to put the soil sample, the water supply system is used to supply water to
the bottom of the soil sample as groundwater, the temperature control
system is used to control the freezing and thawing temperature of the soil
sample, and the parameter measurement system is used to measure the
temperature and the other parameters of the soil sample along the depth
during freezing and thawing processes.
2.1. Experiment Devices Used
The experimental devices are usually divided into two types based on
the scales: the small-scale experimental device and the feet-scale
experimental device. In small-scale experiment device, the depth and cross
section diameter of soil sample is smaller than 1 feet due to experimental
operability, but to some extent it's different from the actual situation due to
the scale. In feet-scale experimental device, the depth and cross section
diameter of soil sample is larger than 1 feet.
Figure 1 shows a small-scale experiment device established by Bai et
al. [5]. The small-scale experimental apparatus is composed of temperature
control system, water supply system and data acquisition system. The
temperature control system includes a top plate, a bottom plate, a test box
and a visualization software. The water supply system is a Mariotte flask
connected with the bottom plate via a plastic tube. The data acquisition
system is a DT80 data logger, the apparatus is instrumented along the
vertical direction to measure the soil temperatures at different depths and
one displacement sensor at the top of the sample to measure the amount of
frost heave in vertical direction.
Figure 2 shows a feet-scale soil freezing and thawing system (SFTS)
constructed by Xu et al. [6] in Harbin Institute of Technology (HIT),
China. The SFTS consists of two subsystems: (a) the soil test system and
(b) the temperature control system. The soil test system comprises several
parts: a sample loading barrel (inner diameter of 1 m, height of 2.5 m),
eight temperature-humidity sensors (placed along the axis of the
container), and two temperature walls at the top and the bottom separately.
The temperature control system is a hydraulic refrigeration cycle system
which supplies cold and warm fluid flows to the top and bottom walls to
control the temperatures, respectively.
Figure 1. Small-scale freezing and thawing test chamber [5].

Figure 2. Feet-scale unsaturated soil freezing–thawing experimental device [6].
2.2. Temperature Distribution during Freezing Process
During the freezing process, the temperatures of the soil at different

depths generally decrease with varying degrees. The top soil is the first one
to freeze, so the temperature there decreases initially and it is reduced with
a rapid rate. Along the depth, the deeper the soil is, the lower the
temperature decreasing rate shows. After freezing or declining to a certain
extent, the temperature of soil at different depths may stay stable and
change slightly.
Figure 3. Temperature distribution at different times during freezing process [6].
Figure 3 shows the temperature distribution at different times during

freezing process, layer 1-8 distribute from the shallow to the deep. Initially,
the temperature distribution along the depth was uniform and the
temperature walls at the top and bottom were set at -20 C and 10 C to
start the freezing process respectively. The whole freezing process lasted
for 20 days. It is observed that the temperature at the shallowest layer 1
decreased sharply in the first 7 days and then kept almost unchanged in the
rest of the freezing process. The temperature at the deepest layer 8
decreased more slowly and after about 14 days it reached 10 C. During
the freezing process, all the temperatures at layers of different depths
decreased in varying degrees, from the shallow to the deep, the
temperature decline rate slows down gradually. On the other hand, the
temperature distribution also shows differences along the depth at different
days. On the 7th day, the difference in temperature in the shallower depth is
much larger than that in the deeper depth, and the temperature at layer 2 is
close to the bulk water freezing point while the temperatures at layers 3-8
are higher than that. Then on the 14th and 20th days, the soil temperatures
along layers 1-8 go up almost linearly in the range of -25 C to 10 C, the
temperatures at layers 1-3 are lower than the freezing point which means
the freezing may reach and stop at around layer 3.
Figure 4. Temperature variations at different depths [5].
Figure 4 shows the temperature variations at different depths during

the freezing process [5]. It is observed that the temperature changes with
time at different depths, and the changes can be divided into a cooling
stage and a steady stage. The cooling stage is from 0 h to about 10 h and
the steady stage is from 10 h to the end of the measurement (96 h). In the
cooling stage, the temperatures in the top decrease first from 12 C and
then keep steady at -3 C. The temperatures at deeper depths also reduce
with the temperatures decreasing in different degrees, and the closer to the
top the soil is, the larger the cooling rate shows. In the steady stage, the
temperatures at different depths show slight increases and they then keep
steady while the frozen front also keeps steady in this stage.
2.3. Water Migration during Freezing Process
During the freezing process, the initial water contents at different soil
depths may show differences due to the scale of the experiment. Figure 5
shows the initial water contents at different soil depths in a feet-scale
experiment [6], it is almost linear from the shallow to the deep.
Researchers [7-9] explained that the pore water evaporation and gravity
force lead to the decrease of water content in upper soil, meanwhile the
capillary force among upper soil particles sucks the pore water from the
lower soil. The dynamic equilibrium between the decrease of water content
in upper soil and migration from the lower results in the linear water
content gradient as shown in Figure 5. Figure 6 shows the total volumetric
water content change during freezing process in a small-scale experiment
[10]. At 0 h, the initial water contents at different soil depths are generally
uniform, which is different from the initial water content distribution in the
feet-scale experiments. This is mainly because in small-scale device, the
evaporation, gravity force and capillary force are not so obvious to show
differences in depths at the beginning of freezing.
Figure 5. Initial water contents at different soil depths [6].
When the freezing process starts, water in the top soil freezes, and
water in the deeper soils flows toward freezing fronts where it changes
from liquid to solid. This will result in a sharp increase in the water content
in the freezing area, then water changes into ice and is fixed in the top area,
due to the evaporation, sometimes water content in the surface may show a
little decrease. As the freezing front moves to the deeper soil, the precipice
of the water content caused by the freezing fringe will also move to the
deeper place and stop at the end of the freezing process.
Figure 6. The total volumetric water content 0, 12, 24, and 50 h after freezing [10].
Figure 7. Water contents at different times during freezing process [6].
Figure 6 shows the measured values of the total volumetric water

contents at 0, 12, 24, and 50 h after freezing started [10]. At the beginning
of the freezing, the water content is almost uniform along the depth as
mentioned above, then as the freezing starts, the water content of soil in 0
cm-5 cm shows significant increase, and a precipice of the water content
forms around the depth of -5 cm that indicates where the freezing front is.
When the freezing moves deeper, the freezing front moves from -5 cm to -
19 cm as the freezing time changes from 12 h to 50 h. When freezing
stops, water content in the frozen region is significantly higher than the
unfrozen region.
Figure 7 shows the water contents along the depth at different times
during the freezing process [6]. When freezing began, the water contents in
the shallow showed a rise at first and then fell back (layer 1 and 2), and the
water contents in the deep soils changed a little. On 7th day, water content
decreased initially and then increased again. On 14th day, the water content
increased initially, then decreased slightly and increased again. The general
water content distribution on the 20 day is similar to that on 14 day. From
0 day to 20 day, the peak of the water content moved from layer 1 to layer
3 which shows the frozen front moving from surface to the deeper soil. The
water content peak is mainly caused by cryo-suction in the frozen front. As
a result, there is no water content decrease in frozen front while there is a
slight increase in contrary, meanwhile the water contents in the deeper
soils (layer 6-8) show a decrease with the water supply from the bottom.
2.4. Temperature Distribution during Thawing Process
Generally, the temperature in the unsaturated frozen soil distributes

almost linearly in the beginning of thawing process. When the environment
temperature at the top rises from the bulk water freezing point below and
the freezing state of the top soil can no longer be maintained, thawing
starts at the top and the temperature of the top soil rises with a rate. Then
heat travels to the deep with ice in the upper soil melting, resulting in the
temperature rise of the deeper soil. Due to the heat attenuation, the
temperature rise rate is usually lower than the upper one. Thus, during the
thawing process, the temperature curve appears a concave peak along the
depth and the concave peak gradually diminishes with the temperature
curve usually becoming a stable straight line at the end of the thawing
process. Generally, the temperature of the deeper soil keeps almost

unchanged owing to the groundwater with basic constant temperature.
Figure 8. Temperature distribution at different times during thawing process [6].
Figure 9. Soil temperatures at Valletta site during the freeze-thaw period of autumn
1998 [11].
Figure 8 shows the temperature distributions along soil depth at

different times of the experiments [6]. At the beginning of the thawing
process, the top layer was around -10 C while the deepest layer was about
10 C, then the temperatures of top and bottom walls were fixed at about
15 C to start the thawing. It can be easily seen that during the thawing
process, a downward temperature curve peak is shown along the depth.
Figure 9 shows the soil temperatures at Valletta site during the freeze-thaw
period of autumn 1998 given by Matsuoka et al. [11] and Figure 10 shows
the rock temperature during pre-macrocracking given by Murton et al.
[12]. During the thawing period of the temperature curve, the temperature
of shallow soil rises notably faster than the deeper. The difference is that at
the end of the thawing period, the temperatures of the surface and upper
soils are much higher than the deeper, which may be because the
experiments carried out by Matsuoka et al. and Murton et al. were in the
outside and the measured depths were less than 50 cm.
Figure 10. Rock temperature during pre-macrocracking. Freezing periods are

numbered ‘1F’ and ‘2F’. Thawing periods are numbered ‘1T’ and ‘2F’ [12].
2.5. Water Migration during Thawing Process
At the end of the freezing process, the frozen region has gone into the
soil at a certain depth, and water in the upper frozen soil has turned into
ice. In the freezing front area, water is sucked upward due to the capillary
force which results in water content at a certain level in the freezing front.
When the thawing process begins, ice in the top soil starts to melt and then
the melting will go downward to the deep region of the frozen soil. Ice in
the frozen area changes into water after melting, and then the melting
water will be affected by the evaporation and gravity. Water content in the
top soil may rise initially due to the melting and then fall back because of
the evaporation and gravity. Water contents in the middle and lower
regions of the frozen area are hard to predict because water in this area is
not only converted from ice, but also supplied by the melting water from
the upper area. Meanwhile, water in this area will migrate downward under
the effect of the gravity. Water in the unfrozen deeper soil normally shows
insignificant change, there may be little rise of the water content in this
area due to the melting water from above. Migration of water in the frozen
soil is coupled with the temperature in the upper frozen soil especially
around the bulk water freezing point, when temperature rises from below
to above the freezing point, usually the water content may fluctuate
meanwhile.
Figure 11. Water content variations at different times during thawing process [6].
Figure 11 shows the water content variations at different times along

the depth during thawing process and Figure 12 shows the volumetric
water content variation with temperature during the soil thawing process
for soils at layer 1 and 2 [6]. In Figure 11, the top layer 1 of the frozen
region shows a rise after the thawing and then falls back, the water
contents of layer 2-4 all fall to the linear moisture distribution of all depth,
water contents of layer 5-8 all change with a little rise. In Figure 12, water
contents in layer 1 and 2 show obvious fluctuations around the freezing
point 0 C.
Figure 12. Volumetric water content variation with temperature during the soil thawing
process for soils at layer 1 and layer 2 [6].
Figure 13. Unfrozen water content dynamics during freezing and thawing [13].
Figure 13 shows the unfrozen water content dynamics during the

freezing and thawing [13]. During soil thawing, both the unfrozen water
contents at depths of 7 cm and 11 cm increase rapidly and after the thawing
water content at the depth of 7 cm is much higher than that at the depth of
11 cm because of the moisture migration from warm area to cold area.
3. LBM MODEL FOR TEMPERATURE DISTRIBUTION

AND WATER MIGRATION IN UNSATURATED SOIL
Water migration and heat transfer in soil are coupled processes. During
the freezing and thawing processes, the temperature, ice content and liquid
water content show highly nonlinear relationships [14]. Fundamentally,
soil is particulate porous material, and researches show that the heat and
mass transport in porous material is strongly affected by its pore structure
[15, 16]. Lattice Boltzmann methods (LBM) which is originated from the
lattice gas automata (LGA) method, is a simplified fictitious molecular
dynamics model in which space, time, and particle velocities are all
discrete [17]. In LBM, the macroscopic dynamics of fluids are the
statistical average results of the microscopic thermal behavior of fluids
molecules and the macroscopic dynamics behaviors are insensitive to the
movement details of each specific molecule. Thus, the LBM can be
considered as a mesoscopic numerical methodology between microscopic
molecular dynamics and macroscopic fluid dynamics. Therefore, the LBM
shows capability of simulating transport phenomena which involves
complex boundaries and interfacial dynamics. Song et al. [18] presented a
mesoscopic numerical model based on LBM for simulating the heat and
mass transfer phenomena with phase transformation in frozen soil during
freezing process. Then, Xu et al. [4, 19] developed a modified LBM model
to simulate the temperature distribution and water migration during
unsaturated soil freezing.
3.1. Reconstruction of Soil Structure
Typically, unsaturated soil is consisted of solids (mineral and organic

matter) and voids (or pores) of which a part is occupied by water and the
other part by gas [20]. To simulate the coupled complex heat and mass
transport process in the soil, the first thing is to reconstruct the soil
structure. Because soil consists of particles of various sizes and these
particles are in completely random distribution, stochastic approaches are
considered reliable [21, 22]. The physical properties of soils usually
considered are structure, bulk density, porosity, temperature, resistivity and
so on [23]. To rebuild the soil structure, porosity is usually the first
essential element to be considered. Based on the given certain porosity and
some other properties, the pore structure is created randomly and the rest
parameters are determined.
To reflect the stochastic phase distribution characteristics of most
porous media, Wang et al. [24] proposed a random internal morphology
and structure generation-growth method, which was termed the quartet
structure generation set (QSGS) based on the stochastic cluster growth
theory for generating more realistic microstructures of porous media. The
flowchart of QSGS process is shown in Figure 14. Based on the QSGS
method, Li et al. [25] rebuilt a two-dimensional soil structure occupied by
single-phase fluid and Figure 15 gives the random two-dimensional pore
structure with different porosities  in which the black part is the solid
skeleton and the white part is the pore. Song et al. [18] adopted the QSGS
method to reconstruct soil structure based on a given porosity.
Figure 16 gives the soil structure generated by stochastic generation-
growth method and connectivity of pores under different porosities  and
core distribution probabilities d . In the figure, black represents solid
elements and white represents fluid elements in the first row and black
represents impermeable region and white represents permeable region in
the second row. Porosity  determines the final void spaces in the soil and
core distribution probability d determines the quantity of particles.
Figure 14. Flowchart of the QSGS process [24].
(a)   0.43 (b)   0.52
Figure 15. Schematics of generated porous media using QSGS method [25].
(a) (b) (c)
Figure 16. Soil structure generated by stochastic generation-growth method and

connectivity of pores. (a)   0.55 , d  0.5 ; (b)   0.40 , d  0.3 ; (c)   0.40 ,
d  0.35 [18].
3.2. Multiphase LBM Model
Flows in unsaturated soil are usually consisted of multiphases

including water, air and so on. Shan el al. [26-29] proposed and modified a
pseudopotential LBM model to describe the multiphase flow in porous
media. Due to its simplicity and versatility, the pseudopotential model is
considered as the most widely used multiphase LBM model [30]. Based on
the simple and popular Bhatnagar-Gross-Krook (BGK) collision operator
[31], the single relaxation time LB equation can be expressed as follows
1
f ,i (x, t  t )  f ,i (x, t )  ( f ,i (x, t )  feq,i (x, t )) (1)
  ,v
f ,i (x  ei t , t  t )  f ,i (x, t  t ) (2)
where f ,i (x, t ) is the density distribution function of the ith direction at
the lattice site x and time t (see Figure 17); f eq is the equilibrium
distribution function; c  x / t is the lattice speed, in which
x  t  1 represents the lattice spacing and time step respectively;  v is
the dimensionless relaxation time. Eq. (2) represents the streaming step in
which fluid particles are streamed from one lattice to a neighboring lattice
according to the discrete velocity ei in the lattice. For a D2Q9 lattice,
 0, 0
 
i0

 
ei   cos   1  / 2  ,sin   1  / 2  i  1, 2,3, 4


 2 cos   5   / 2   / 4  ,sin   5   / 2   / 4   i  5, 6, 7,8
(3)
eq
The equilibrium distribution function f is given by
 2
feq,i  i  1  2  ei  ueq   4  ei  ueq   2  ueq  
3 9 2 3
(4)
 c 2c 2c 
where the weight factor  i in Eq. (4) is given by
4 / 9 i  0

i  1/ 9 i  1, 2,3, 4 (5)
1/ 36 i  5, 6, 7,8

The viscosity in lattice unit is given by
   cs2   ,  0.5  t (6)

where cs is the lattice sound speed. The macroscopic density and

momentum at each lattice node are given by
   f ,i (7)
i
 u   f ,iei (8)
i
The mass fraction  of phase  is calculated by

  (9)
  
In the soil, different bulk forces exist such as fluid–fluid interaction

force, fluid–solid interaction force, gravitational force and others. Velocity
shift scheme provided by Shan et al. [26] is used to describe the force term,
the parameter u eq in Eq. (4) in the scheme is given by
  , F
ueq  u  (10)

where u  is the common velocity of the fluid mixture which is
 u
   ,
u  (11)

  
 ,
In Eq. (10), F is the sum of all interactive forces between fluid

particles. In this model, F  Fcoh  Fads  Fb  Ftmp , Fcoh is the cohesive
force between particles from the same phase; Fads is the adhesive force
between fluid particles and solid boundary; Fb is the sum of bulk forces
such as gravitational force and buoyancy force; Ftmp is the bulk force
caused by temperature potential change.
To simplify the question, vapor in soil is neglected and then the fluid
system only consists of water and air. Therefore, only repulsion is needed
to consider for different components, and the interactive force applied on
the particles of one component is given by
Fcoh  x      x, t  Gcoh    x  ei ei (12)

i
where  represents the other component of the fluid mixture; Gcoh is an

adjuster to tune the surface tension between two components. The cohesive
force between fluid particles and solid boundary is given by
Fads  x      x, t  Gads i si  x  ei ei (13)

i
where si works as a tag, and the value of si is
0 node x+ei is fluid lattice node

si  x  ei    (14)
1 node x+ei is solid boundary
Gads adjusts the interaction force between the particles of component

 and solid boundary, and it is positive for wetting fluid while negative
for non-wetting fluid. The effect mass is
   
  0 1  exp     (15)
  0  
The gravitational force of component  is given by
Fb   g (16)
Figure 17. The layout of velocity directions of a D2Q9 lattice.
3.3. LBM Model for Temperature Distribution
In LBM model, another layer of thermal lattice is used to describe the

heat conduction process. A D2Q9 thermal lattice is adopted and the LB
equation for thermal diffusion can be expressed as
gi  x  ei t , t  t   gi  x, t  
1

 g  x, t   g  x, t 
i
eq
i (17)
The discrete velocity ei in the lattice is expressed in Eq. (3). The

equilibrium distribution function g ieq is given by
g ieq  iT (18)

The weight factor  i is given in Eq. (5). The thermal diffusivity  is

given by
  cs2    0.5 t (19)
The macroscopic temperature can be calculated from
T   gi (20)
i
In order to solve the heat conduction problem with phase change,

Jiaung et al. [32] added a source term to Eq. (17) and proposed a new LB
equation, which is given by
gi  x  ei t , t  t   gi  x, t  
1

 g  x, t   g  x, t  
i
eq
i
(21)
 i  fl ,i  t  t   f l ,i  t  
L
C
3.4. LBM Model for Water Potential
In soil, water migrates under the influence of different forces such as

gravity, pressure and capillary force. Water potential  is used to quantify
the tendency of water movement and the total water potential  Tot is
given by
 Tot   P   Z   S   A   tmp (22)
where  P ,  Z ,  S ,  A and  tmp are pressure, gravitational, solute

(osmotic), air pressure and temperature potentials, respectively.  S and
 A can be neglected for low salinity soil under standard atmospheric

pressure, then Eq. (22) is simplified to
 Tot   P   Z   tmp (23)
In the LBM model,  P is represented by Fcoh and Fads (caused by

capillary action),  Z is represented by Fb and  tmp is represented by
Ftmp .
The movement of water in soil can be quantified by the gradient of
water potential  caused by temperature change and it can be derived
from Clapeyron’s equation when the soil temperature is above freezing
point which can be written as
Ll
  T (24)
T Vl
where Ll and Vl represent the latent heat of condensation and specific
volume change during vapor condensation, respectively. When the soil
temperature reaches the freezing point, the gradient of water potential
caused by temperature is given by
Ls
  T (25)
T Vs
where Ls and Vs represent the latent heat of fusion and specific volume
change during freezing, respectively. Ls and Vs in Eq. (25) are the
property of water and T  273K is the freezing point of water in Kelvin.
Therefore, Eq. (25) becomes
  13.48 106 T (26)

The temperature water potential has the same value with the suction
pressure caused by freezing process which is given by
Ls  u2
Pr   r r (27)
T Vs 2
In lattice unit the suction pressure is given by
u 2
P (28)
2
Then the suction pressure in lattice unit becomes
u 2
P P (29)
 r ur2 r
It is known that
ur csr
 (30)
u cs
where csr is the real speed of sound,  r is the real density of water.
However, Eq. (26) needs to be revised for real soil. The correction
factor depends on the type of soil [33]. Song et al. [18] proposed a relation
to implement  in lattices which is given by
Ftmp  G tmpx (31)
tmp
where G is determined by the type of soil.
3.5. Validation of the LBM Model
In 1990, Mizoguchi [34] performed a classic laboratory experiment,

the experiment results have been adopted to validate numerical models in
various studies [10, 35]. Though the previous models are not based on
lattice Boltzmann method, it does not hinder the experiment results being
appropriate to validate the LBM model. In Mizoguchi’s experiment, he
packed four identical cylinders with Kanagawa sandy loam, and each
cylinder was 20 cm long and had an internal diameter of 8 cm. The
samples were prepared with the same initial conditions involving a uniform
temperature of 6.7 C and a close to uniform volumetric water content of
0.33. Three samples were prepared for the freezing test while the fourth
was prepared to measure the initial condition. The sides and bottoms of the
cylinders were thermally insulated. The temperature of the top was
controlled at -6 C by circulating fluid. Thus the samples were frozen from
the top down. Thermal couples were installed in the cylinders at different
depths to obtain the temperature distributions. The samples were taken
from the freezing apparatus after different hours. When being removed
from the cylinders, the samples were divided into 1 cm thick slices and
dried in an oven to obtain total water content (liquid water plus ice)
distributions.
Figure 18 shows the comparisons of temperature distribution in
experimental results and simulation results after 12, 24 and 45 h freezing.
It can be observed that the temperature of simulation in frozen soil is lower
than those of experiment at 12 h, and the simulation results show good
agreements with the experimental results at 24 and 45 h. The reason for the
difference between simulation data and experimental results is that the heat
flux caused by water flux is neglected due to the considerably low water
flow speed in this model while the water flow flux is relatively high during
the first hours of freezing.
Figures 19-21 show the comparisons of experimental results and
simulation results after 12, 24 and 50 h freezing, respectively. All the
simulation results show good agreements with the experimental results.
Figure 18. Comparison between experimental and numerical results of temperature

distribution after 12, 24 and 45 h freezing [18].
Figure 19. Comparison between experimental and numerical results of water content
distribution after 12 h freezing [18].
The freezing front is clearly visible in Figures 19-21 where the water
content decreases rapidly along the depth, and with the freezing time
increases the freezing front moves to a deeper position. Thus in the model
the rapid decrease of water content in frozen fringe and slow recovery in
deeper position are well predicted. However, the size of the frozen fringe
in simulation is smaller than that in the experiment which is because that
the water in simulation freezes instantly in frozen fringe while it is not the
same in reality.
4. MODIFIED LBM MODEL FOR TEMPERATURE

DISTRIBUTION AND WATER MIGRATION IN
UNSATURATED SOIL
4.1. Physical Model
The physical model of the modified LBM model is schematically

given in Figure 22 [4]. When the soil freezing starts, temperature gradient
forms in the soil due to the difference of temperature along the depth, and
heat transfers to low temperature region from the higher one while water
moves to frozen region from the unfrozen one. According to the freezing
situation, the soil region is divided into frozen zone, freezing fringe and
unfrozen zone. In frozen zone, Wettlaufer et al. [36, 37] pointed out that
pre-melted films exist between the ice lens and soil particles which is
caused by certain amount of unfrozen water fixed due to the intermolecular
forces. Style et al. [38] pointed out that these pre-melted films provide
channels for water from unfrozen region moving to freezing front to supply
the growth of ice lenses. In freezing fringe, ice cores form due to the
temperature there which is lower than freezing point Tm , on the other hand,
the temperature there is also higher than the ice entering point Tie which
stops the ice invasion from frozen zone. Due to the Gibbs-Thomson effect
[39, 40], a certain amount of unfrozen water exists between the soil
particles and ice grains. In the unfrozen zone, water exits in the voids
among soil particles where the adhesion force and water-air interface
tension keep balance with gravity.
In section 3.1, it’s mentioned that soil consists of particles of various
sizes which are in completely random distribution and Wang et al. [24]
proposed a QSGS method to reflect the stochastic phase distribution
characteristics of most porous media. Because the QSGS method is simple,
it is also used in the modified LBM model to generate the stochastic pore
structure.
In the modified LBM model, attempts are made to find functional

correlations between the particle size distribution and some macroscopic
properties of the porous medium. Koponen et al. [41] pointed that the
porosity  and the specific surface area S are two important macroscopic
properties of the porous medium, which give the ratios of the total void
volume and the total interstitial surface area to the bulk volume,
respectively. Xu et al. [4] related the porosity  and the specific surface
area S to the average volume fraction of obstacles f v . The value of
porosity is equal to the probability that a given point in volume V is not
overlapped by any of the obstacles, the porosity  is given by
  1  f v 
K
(32)
Figure 22. Diagram of physical model for unsaturated soil freezing [4].
where K is the number of obstacles, f v  V0 / V is the average volume

fraction of obstacles, V0 is the average volume of obstacles.
The specific surface area is S  A / V while A is the value of the
total surface area of all obstacles, A is given by
A  KA0 1  f v 
K 1
(33)
where A0 is the average surface area of obstacles.

Then the porosity  and the specific surface area S are related to the
average volume fraction of obstacles f v . Moreover, the average volume
fraction of obstacles f vl and the average number of obstacles in a single
lattice N are related to f v , where f vl  Nf v .
4.2. Governing Equations
In 1992, a series of DdQm models (d-dimensional space, m-discrete

velocities) are proposed by Qian et al. [42], and they constitute the basic
models of LB method. Due to its common for solving fluid flow problems,
the D2Q9 lattice model is also used in modified LBM model and the layout
is shown in Figure 23. The streaming velocity for the D2Q9 model is given
by
 0, 0  i 1

ei   1, 0  ,  0, 1 i  2  5 (34)
 1, 1 i  69

The associated lattice weights wi are

Figure 23. D2Q9 lattice model for modified LBM model.
4
9 i  1

1
wi   i  25 (35)
9
1
 36 i  6  9

The sound speed ( cs ) is equal to 1 / 3 .

The mass conservations for each of two fluids and the solid fraction
are given by
 g
     g ug   0 (36a)
t
s
 m (36b)
t
l
    l ul    m (36c)
t
where  m is the melting rate, u g and ul are the local fluid velocities of
liquid and gas, respectively.
The momentum equations for the fluid mixture are treated as a single
one which is given by
 u 
   u   u   p      v  u  u    g (37)
 t 
where     is the total density of the mixture. The total momentum

of the fluid mixture is
u   fi vi  1 2  F (38)
 i 
The initial conditions are given by
u g  ul  0
  0
 s
 (39)
g  g0

 l  l 0
Figure 24 shows the fluid flow boundary conditions. Bounce back

boundaries are applied on the top, the down and the ice-fluid interfaces to
maintain the mass conservation. Periodic boundaries are applied on the
sides to maintain the continuity of flow.
Figure 24. Fluid flow boundary conditions [4].
The enthalpy conservation of the three phases is
   s CsTs 
 ks Ts (40a)
t
  l ClTl 
 l ClTl  kl Tl (40b)
t
   g Cg Tg 
  g Cg Tg  k g Tg (40c)
t
where ki and Ti are respectively the thermal conductivity and temperature

of phase i, Ci is the specific heat,  s ,  l and  g are the local density of
solid, liquid and gas, respectively.
The initial condition is
T  Tcold (41)
The boundary conditions are given by

Tup  Tcold at t  0 (42)
Tdown  Thot at t  0 (43)
The side boundary conditions are periodic as shown in Figure 25.

The usual Lattice Boltzmann equation is applicable for the thermal
diffusion during soil freezing process which is given by
Figure 25. Temperature boundary conditions [4].
t
gi  X  ei t , t  t   gi  X , t    g  X , t   gi
eq
 X , t  (44)
h  i
where g i is the temperature distribution function in the i-th velocity

direction, and  h is the relaxation time related to the thermal diffusion by
  cs2  h  0.5 . The equilibrium distribution function for g ieq can be
obtained by: gi
eq
 X , t   wi g .
4.3. Multiphase Fluid
Due to its simplicity and versatility, the Shan-Chen pseudopotential

model is also used in the modified LBM model to describe the multiphase
fluid. In Shan-Chen model, the usual Lattice Boltzmann equation is used as

the distribution function of all components during soil freezing which is
given by
t
fi  X  ei t , t  t   fi  X , t    fi  X , t   f i ,eq  X , t 

(45)
where f i  is the density distribution function of the  -th component in

the i-th velocity direction, and   is the relaxation time related to the
kinematic viscosity for the component  by v  cs    0.5 . The
2
equilibrium distribution function for fi

 ,eq
 x, t  can be obtained by
  ei  ueq  ueq 
2

2
eq
e u
fi  , eq
 X , t   i   1  2 
i 
 2 (46)
 cs 2cs4 2cs 
 
where the density and momentum of the  fluid component are given by
  i fi and  u  i Vi fi (47)
u eq in equation (46) is determined by
  F
ueq  u  (48)

where u  is the common velocity of the fluid mixture, and it is given by

 u
  
u  
(49)

And F  Fcoh  Fads  Fb is the sum of the interactive force
between fluid particles, Fcoh stands for cohesion force between solid
boundary and fluid particles, Fads stands for adhesion forces and Fb
stands for external body forces such as gravity and buoyancy forces.
The interactive force which acts on the particles of species  located
at position x can be obtained by
Fcoh  X , t      X , t  G coh i   X  ei t  ei (50)

i
where  and  are the first and second components of the fluid mixture
coh
respectively, G is the adjustment parameter of surface tension between
the two modeled fluids.
The cohesion force between particles of fluid  and the solid
boundary can be obtained by
Fads  X , t      X , t  Gads i si  X  ei t  ei (51)

i
where si  1 if the lattice node i belongs to the solid boundary and si  0

if i belongs to a fluid lattice node.
The body force to mimic the effect of a buoyancy force can be
obtained by
Fb  X , t    g (52)

where g is the gravity and  is the difference in density between the two
components.
4.4. Melting Problem
Bulk water freezes in the soil porous medium, this Neumann-Stefan

problem including half space conduction melting with thermal diffusivity
has been solved analytically by Neumann [43]. Jiaung et al. [32, 44]
proposed an enthalpy-based lattice Boltzmann method and it has been
successfully used for solid-liquid phase change problem in Huo’s work
[45]. In the modified LBM model, Jiaung’s enthalpy-based method is used
for melt-solid moving boundary in porous media that has not been
considered in section 3.
The melting term is treated as a source for crystallization or sink term
for melting. At the time-step n and iteration kn, the macroscopic
temperature is obtained by
T n,k   gin,k (53)

i
where Tn,kn  Tkn  t  n  .

The local enthalpy is obtained by
Enn,kn  cT n,kn  L f fl n,kn1 (54)
The enthalpy is used to linearly interpolate the melt fraction
0 En n ,kn  Ens  cTm 0

 n ,kn
 En  Ens
fl n ,kn  Ens  En n ,kn  Ens  L f (55)
 Enl  Ens
1 En n ,kn  Ens  L f

where Ens and Enl are the enthalpies of the solid and liquid at the
melting temperature Tm .
Saruya et al. [46] pointed out that the particle size distribution shows
important relationship with the Gibbs-Thomson effect in the freezing
fringe. Saruya et al. [46] also pointed out that T f which describes the
difference between the warmest temperature and the normal bulk melting
temperature Tm 0  273.15 K can be obtained by
T f  Tm 0  Tm  2 slTm 0 /   L f R p  , where R p is the characteristic
radius of a pore throat,  L f  3.110 J/m is the latent heat of fusion

8 3
per unit volume and  sl  29  103 J/m 2 is the ice-liquid surface energy.
So, the actual water melting temperature in porous media is
2 slTm 0
Tm  Tm 0  (56)
 L f Rp
R p is given by R p   p R where R is the particle radius and  p is a

correlation coefficient given by  p  0.7 . The average characteristic
radius of a single lattice is given by
1
 3 f 3
Rp   p  v  (57)
 4 
In the frozen zone, Engemann et al. [47] pointed out that pre-melted
film exists between ice and soil particle surface below bulk melting point
due to the intermolecular forces between components (particles, liquid, and
ice), and the thickness follows a logarithmic growth law when approaching
the melting point
Tm  T0
L T   a  0  ln (58)
Tm  T
where T0  Tm  17 K . The constant a  0  0.84 nm corresponds to the

decay length of the non-ordering (average) density.
Figure 26 shows the schematic of pre-melted film, the average
thickness of the pre-melted film in a single lattice is given by
Figure 26. Schematic of pre-melted film [4].
1
 3 3
L   1  fl  fl f v  (59)
 4 
The relationship between the average obstacle volume fraction f v and

pre-melted film melting temperature is given by
T T
Tmi  Tm  
m 0
1 
(60)
  3 1 f  f f  3 
  4  l l v 
 
 
 a 0 
 
 
 
e
In the modified LBM model, the bulk melting temperature Tm in

equation (55) is substituted by the variable melting temperature Tmi to
make the formation of pre-melted possible.
The collision is given by
 gi  X   gieq  X    ti f  f l n,k  X   f l n1  X  

1 L
gin,k 1  X  ei   gi  X  
h c
(61)
where  h is the relaxation time related to the thermal diffusion of the

component  by k  cs  h  0.5 .
2
The macroscopic temperature is given by
T   Ti (62)
i
4.5. Interactive Force
During soil freezing, water moves towards the frozen front through the
freezing fringe from the unfrozen zone, overcoming the resistance along
the path at the same time. In the modified LBM model, two more
interactive forces are considered based on the formula
F  Fcoh  Fads  Fb given in section 4.3. One is Ffre which describes
the suction in frozen front by treating as a kind of interactive force between
ice and water particles, and it is similar to the adhesion force between fluid
particles and solid boundaries in the Shan-Chen model. The other is a body
force Fblo which describes the resistance along the path in unfrozen
region, and it is related to the distance from freezing fringe according to
Darcy’s law. Thus, the sum of the interactive forces for mixture fluid flow
during soil freezing is given by
F  Fcoh  Fads  Ffre  Fblo  Fb (63)
The adhesion force Fads in soil is related to the soil particle

distribution which is obtained by
Fads  X , t      X , t  Gads  i fi  X  ei t  ei (64)

i
where f is a flag variable equal to the soil particle volume fraction of the
lattice node i.
The suction force Ffre is caused by the pore water pressure difference
among frozen zone, freezing fringe and unfrozen zone. Water moves from
unfrozen zone towards the freezing fringe due to the pore water pressure
decrease between ice grain surfaces and soil particle surfaces and then
from the freezing fringe towards the frozen front due to water pressure
deep decrease of pre-melted film in frozen front. This suction behavior
only forms in the freezing fringe and pre-melted film near the ice particles
and it is reasonable to be treated as an adhesion force between ice particles
and fluid particles. The suction force Ffre can be obtained by
Ffre  X , t      X , t  G fre ili  X  ei t  ei (65)

i
where l is a flag variable that equals to fl for the particles of fluid  with
phase change happening near the phase change boundary, and it is equal to
0 for the particles of fluid  without phase change happening. G is the

fre
parameter that describes the magnitude of suction force which is related to

the pore water pressure drop in freezing fringe and pre-melted film.
The generalized Clapeyron equation can be described by
Tm  T
Pcl  P   L f (66)
Tm
where Pcl is the pore water pressure in the freezing fringe and pre-melted
film at temperature T, P is the soil particle pressure in warm region, Tm is
the bulk water freezing point, L f is the latent heat of ice melting,  is the
ice density. When ground water supplies at pressure PR , the pore water
pressure difference between ground water and pore water near ice particles
is
Tm  T
P  PR  P   L f (67)
Tm
fre
The parameter G is related to the maximum pressure difference that
locates in the frozen front where the temperature is equal to the ice
entering temperature Tie while Tie is given by
Tm sl
Tie  Tm  (68)
 L f Rp
Consequently, the suction force can be obtained by
 sl
PR  P 
Rp
Ffre  (69)
Ac
where Ac is the cross-sectional area of flow.

fre
Thus, G can be considered as a parameter relating to the surface
tension at ice-water interface and the pore structure of soil particles.
According to the kinetics of ice growth in porous media described by
Style et al. [33], two kinds of resistance exist along the path way for water
moving from unfrozen zone to the freezing fringe then to the frozen front:
(a) the hydraulic resistance due to the flow in the porous medium and (b)
the resistance due to the flow in the thin films around the particles.
The hydraulic resistance is given by
h
Fh  (70)
kp
where k p is the permeability from Carman-Kozeny equation
R 2 1   
3
kp  (71)
100 2
The resistance in the thin films is given by
3k p R 2
F 
f
(72)
2 L3
where  p is the viscosity of water in thin films.

Then the whole resistance along the path is given by
Fblo  Fh  Ff (73)
Figure 27 shows the stress of fluid particles in unfrozen zone. In Figure

27 (a), the adhesion force and surface tension at the water-air interface
keep balance with gravity as Ft   ghA while there is no pressure
gradient between pore water and ground water before soil freezing. In
Figure 27 (b), pressure gradient forms in the pore water by which the
tension force is gradually replaced to keep the balance with gravity during
soil freezing and water flow begins after the pressure gradient overcomes
the gravity. Thus the body force Fb is thought as a block force by this
varying force which is given by
0    ,initisl  3 gh
Fb   (74)
  gh    ,initisl  3 gh
(a) (b)
Figure 27. The stress of fluid particles in unfrozen zone [4].
4.6. Validation of the Modified LBM Model
Mizoguchi’s experiment is also used to validate the modified LBM

model, and the details of the experiment are described in section 3.5. The
comparisons of experimental and numerical results of water contents after
12, 24, 50 h freezing are shown in Figure 28-30 [19]. From Figures 28-30,
it is observed that all the simulation results are in good agreements with the
experimental results.
In Figure 28 (a), after soil freezing for 12 hours, along the depth of soil
sample from 0 to 20 cm, the water content decreases slightly from 0.425 to
0.39, then decreases sharply from 0.39 to 0.29 and increases from 0.29 to
initial water content 0.33. The soil freezing front locates nearly at the depth
of 6.5 cm where the water content shows sharp decrease in Figure 28 (a).
In Figure 29 (a), after the soil freezing for 24 hours, water content varies in
the range from 0.42 to 0.39 in the shallow depths, then decreases sharply
from 0.4 to 0.27 and increases from 0.27 to 0.32. The water content sharp
decrease at around the depth of 9 cm in Figure 29 (a) indicates the freezing
front locates here. In Figure 30 (a), after the soil freezing for 50 hours, the
water content decreases slightly from 0.41 to 0.37, then decreases sharply
from 0.37 to 0.25 and increases from 0.25 to the initial water content of
0.30. The freezing front locates at around the depth of 14 cm in Figure 30
(a). In these three figures, water contents along the depth of experiments
and simulations are generally close, the freezing front moving trend and
the freezing front location of experiments and simulations during the
freezing process are similar. Besides, in Figures 28 (b), 29 (b) and 30 (b),
the correlation coefficients between the simulated values and experimental
data after 12, 24 and 50 hours freezing are 0.92, 0.83 and 0.92 respectively.
The high correlation coefficients also indicate the reliability and
availability of the modified LBM model.
(a) Volumetric water content distribution (b) Correlation coefficient
Figure 28. Experimental and numerical results of water contents after 12 h freezing
[19].
[19].
[19].
CONCLUSION AND FUTURE OUTLOOK
Temperature distribution and water transfer in the unsaturated soil are

mainly related to the soil movement phenomenon which may be harmful to
the road and building ground safety. Experiment researches on temperature
distribution and water migration in unsaturated soil during the freezing and
thawing processes, LBM model establishment and validation, modified
LBM model establishment and validation are presented and discussed.
Experiment devices in small-scale and feet-scale are briefly
introduced, the constituent parts of the two scales are generally similar
while the most obvious difference is the size of the soil sample size. The
temperature decreases faster in the lower depths as compared with the
interior during the freezing process, and it increases initially and then the
temperature curve appears a concave peak along the depth with the peak
gradually diminishing during the thawing process. The water content is
generally uniform along the depth in small-scale while it is almost linear in
feet-scale at the beginning of the freezing process. Water content in the top
soil may rise initially while in the unfrozen deeper soil it normally shows
insignificant change during the thawing process.
A D2Q9 mesoscopic lattice Boltzmann model (LBM) is established,
and it includes: (a) soil structure reconstruction, (b) multiphase flow
calculation, (c) temperature distribution calculation and (d) water potential
calculation. (a)~(c) are based on the quartet structure generation set
(QSGS) method, Shan-Chen pseudopotential model, double distribution
function model respectively, while (d) considers cohesive force between
particles from the same phase, adhesive force between fluid particles and
solid boundary, external bulk forces and buoyancy force and temperature
potential change bulk force.
A modified D2Q9 LBM model is developed, and it includes: (a) soil
structure reconstruction, (b) multiphase flow calculation, (c) temperature
distribution calculation, (d) water potential calculation, (e) melting film
consideration and (f) interactive force reconstruction. As compared with
the LBM model, the modified model adopts Jiaung’s enthalpy-based
method for melt-solid moving boundary in porous media, moreover it
considers the suction in frozen front and the resistance along the path in
unfrozen region for the interactive force reconstruction.
Currently, experiments and simulation works have yielded some good
results. However, the temperature distribution and water transfer in
unsaturated soil are complex phenomena, more work is needed to put
forward in the future: (a) more elaborate experiments to explore the water
migration in the freezing fringe, (b) further experiment researches on the
interaction between temperature distribution and water transfer, (c) new
models to predict temperature distribution and water transfer in unsaturated
soil, etc.
ACKNOWLEDGMENTS
This study is supported by Natural Science Foundation of China (Grant

No. 51776049) and Special Foundation for Major Program of Civil
Aviation Administration of China (Grant No. MB20140066).
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Chapter 4
CHEMICAL POTENTIAL
IN SOILS AND COMPLEX MEDIA
Jean-Claude Bénet*, PhD

Laboratoire de Mécanique et Génie Civil,
Université de Montpellier, Montpellier, France
ABSTRACT
By definition, the mass chemical potential (CP) of a constituent in a

soil represents the variation of the internal energy of the medium when a
unit mass of the constituent is transferred to a reference state with the
entropy, volume and mass of the other constituents remaining constant. It
quantifies the action of the rest of the environment on the constituent
considered. For water, it results from mechanical or electrical actions
generated by the superficial layers which are responsible for this
retention. CP is a fundamental quantity in the same way as temperature or
pressure
*
Corresponding Author’s E-mail: Jean-Claude.benet@umontpellier.fr.
134 Jean-Claude Bénet
This chapter addresses the measurement and expression of the CP in

the presence of superficial layers induced by a complex structure.
Measuring CP in soils, gels and various media of biological origin, is
based on one of its fundamental properties, namely that, at equilibrium,
the chemical potential of a component i has the same value on either side
of a membrane permeable to i, temperature being uniform. The proposed
analysis revisits conventional methods such as tensiometry or the use of
filter paper and exploitation of the desorption isotherm. A mechanical
method has been developed to measure the CP of volatile organic
compounds in soils.
The combined effects of the interfaces and a solute on the CP of
constituents of an aqueous solution in the capillary domain are analyzed.
In the case of an ideal solution of large molecules (e.g., polyethylene
glycol) in a porous medium with a pore size small enough to hinder
diffusion, a solute gradient is established. The Gibbs Duhem relationship
induces a chemical potential gradient of water. The phenomenon of
osmotic dehydration appears and is accompanied by a loss of water and
stresses.
The effect of gas phase pressure in the capillary medium refers to
tensiometric measurement methods, with an important nuance: capillary
potential and suction being empirical formulations of the CP, these
concepts can then benefit from the body of mechanics, chemistry,
thermodynamics, thus allowing a very broad approach to soil function
and the expression of state functions, i.e., chemical potential, entropy and
internal energy.
We then examine the case of a saturated medium (solid phase +
water) subjected to deformations that may result from external actions or
internal water transfer. In the context of elastic behavior of the whole
medium, increments of CP and stresses can be expressed as a function of
thermomechanical coefficients
Soil is a very special container generating charged surface layers,
open on the outside, capable of generating temporospatial CP variations
and fluctuations of the constituents of the aqueous solution. Passage of a
solution from the free state to that of a solution in soil opens perspectives
on applications such as plant nutrition, water transfer in hygroscopic
environments, pollution/soil remediation, geochemistry, analysis of water
transfers in arid zones (desertification) and prebiotic chemistry.
INTRODUCTION
So-called complex media consist of three phases (solid, liquid and

gas), finely divided and nested, and separated by large extension interfaces
Chemical Potential in Soils and Complex Media 135
that influence the thermal, mechanical and thermodynamic behavior of the

medium as a whole. The solid phase confers a shape specific to the
building; the superficial phases induce self-stressing forces that contribute
to maintaining the shape of the object. The pores of the solid phase host
solutions and gas mixtures in communication with the outside. A complex
medium is an open reactor that can be the seat of chemical reactions. These
media are highly represented in our environment and constitute everything
that cannot be described as a continuous environment, including soils,
rocks, porous materials, gels and biological media.
Complicated calculation is not needed to find that it is easier to extract
a kilogram of water from a bottle than the same mass of water contained in
a cubic meter of clay with little moisture. In the first case, the binding
forces of the water with the container are low and tilting the bottle is
enough to remove the water. In clay, the binding forces involved between
atoms, ions and molecules are all the stronger as the surface layers
sequester much of the water. It is then necessary to supply energy to the
system in order to obtain a kilogram of water of quality equivalent to that
contained in the bottle. The surface layers determine the availability of
water. This can be extended to any chemical species in the medium. In
order to live and grow, plants must extract water from the soil. Water in the
soil is translated by a value of its chemical potential. If this very low, roots
cannot extract moisture and we must water the plants. To subsist and
develop, micro-organisms must be able to extract water from food, the
preservation of which exploits an ancient technique, namely drying.
These situations can be approached in a rigorous way using the idea of
chemical potential [1]. After presenting the theoretical bases that lead to
the concept of chemical potential, currently available chemical potential
measurement techniques are presented.
Water, in three states, is the most abundant substance on the surface of
the globe; it is the preferred solvent for many organic and inorganic
substances. The main measurement techniques for water in soils are
discussed and are extended to volatile organic compounds (VOCs) in soils.
Various solid phases are also considered, including gels, food products and
plant tissues
After this experimental approach, the calculation of the chemical

potential will be extended to more complex case
 the combined effect of a solute and superficial liquid-gas layers,

 the case of the impeded diffusion of large molecules in solution,
osmotic potential,
 the effect of gas phase pressure,
 the effect of a stress tensor.
THEORETICAL BASES
Gibbs and Gibbs-Duhem’s Relationship
We consider a complex system (SC) contained in a volume V

subjected to exchanges of heat, work, and material with the outside (Figure
1). There are two scales to describe how the SC changes. The so-called
micro scale corresponds to the characteristic dimensions of the
singularities of the medium: size of the grains, thickness of the liquid
pockets and size of the gas bubbles. The macro scale contains a large
number of singularities. To define the macro scale, average extensive
quantities—mass, internal energy, entropy, etc.—are calculated on a sphere
centered at a point M (Figure 1). The representative elementary volume
(VER) is the quantity from which the mean values vary little. Continuous
displacement of the point M generates continuous fields of mass or volume
quantities assigned to the point M. The size of the VER—given by
measurement of the radius of the sphere—defines the macro scale.
Subsequently it is assumed that the medium is macroscopically
homogeneous meaning that the size of the VER is independent of the
position of the point M on the geometric space occupied by the SC. In
addition, the fields of variables and macroscopic functions are uniform
over this space.
Complex medium
WORK 
MASS
Chemical Chemical
Pressure P
reactions potential  i
Stress  M
VER
HEAT
Temperature T
Figure 1. Open complex system.
If U, V, S, mi are the internal energy, volume, entropy and mass of the

constituent i in the SC, the principles of thermodynamics make it possible
to write the Gibbs relation [2, p.23]:
m
dU  TdS  PdV   i dmi (1)
i 1
The increment of U is an exact total differential of the variables V, S,

mi which results in:
U
T ( )V , mi (2)
S
U
P( ) S , mi (3)
V
U
i  ( ) S ,V ,m j , j i (4)
mi
T and P are temperature and pressure evaluated with constant

composition. It is possible to introduce strain and stress tensors to express
work as will be done later.
The intensive variable, evaluated at constant S and V since only
constituent i is exchanged with the outside, is the chemical potential of
component i in the complex system. Relationship (4) defines the chemical
potential. It represents the action of the whole of the medium on the
constituent i.
The variables U, V, S, mi being extensive and the system
homogeneous, by modifying its size in the parameter  :
U (  S ,  V ,  m j )   ( S , V , mi ) (5)
Euler’s theorem implies [3, p.59]:
m
U  TS  PV    i mi (6)
i 1
This relationship combined with (1) gives the relation of Gibbs Duhem
[3,p.60]:
m
SdT  VdP    i dmi (7)
i 1
Knowing the state function of a pure phase, this relationship will yield
an expression of the chemical potential in simple cases, at constant
temperature.
Thermodynamic Equilibrium Relative to the Transport of

a Constituent
An isolated system consisting of two subsystems 1 and 2 separated by

a rigid wall, diathermy, permeable to a single chemical species i; mi1 and
mi2 are the numbers of moles of species i in systems 1 and 2. A reversible
transformation during which dmi1 the mass of i which passes from 1 to 2, is
considered:
dmi 2   dmi1 (8)
dU1  dU i 2  0 (9)
Any infinitesimal transformation from a state of equilibrium being

reversible:
dS = 0 (10)
By expressing dS from (1):
S1 S2 S S
dS  (  )dU1  ( 1  2 )dmi1  0 (11)
U1 U 2 mi1 mi 2
What is written with (2) and (3):
1 1  
dS  (  )dU1  ( i1  i 2 )dmi1  0
T1 T2 T1 T2 (12)
Since this relationship is true for all infinitesimal variations of dU and

dmi1 [2. p.34]:
T1  T2 and 1   2 (13)
If both systems are at the same temperature, the equilibrium between

two phases separated by a membrane that is semi permeable to a given
species results in equal chemical potentials of said species on either side of
the membrane.
Chemical Equilibrium in a Phase
A reactive system is considered in a reactor whose walls are rigid and

adiabatic. The reaction involving chemical species is written in symbolic
form:
r
 i Ri  0 (14)
1
Where Ri are the chemical species involved in the reaction and  i are
the stoichiometric coefficients counted negatively for the species that are
consumed and positively in the opposite case.
Given the constraints imposed (dU = 0 and dV = 0), T being the
temperature at equilibrium, the entropy variation (1) is of the form:
r
i m
dS   dmi
1 T (15)
The mass variation dmi is proportional to the stoichiometric

coefficient of i in the reaction and the coefficient of proportionality is the
degree of progress of the reaction:
dmi   i d (16)
The entropy variation dS takes the form:

d r
dS  
T

1

im i
(17)
At equilibrium [2, p. 167]:

1
 0
im i (18)
This relationship is at the origin of the introduction of chemical

potential by Gibbs (1985). It is only applicable if the reactor is rigid and
adiabatic.
Expressions of Chemical Potential Simple Cases
We limit ourselves to the case of a perfect gas whose equation of state

is of the form:
PVm  RT (19)
Vm is the molar volume and R is the perfect gas constant (R = 8,314 J

mole-1 K-1). According to the Gibbs-Duhem relationship (7) along an
isothermal transformation, the change in molar chemical potential is
written:
dP
dm  Vm dP  RT (20)
P
By integrating this relationship between a reference pressure P  and

the pressure P, the temperature being assumed constant:
P
m (T , P)  m  (T )  RT ln( ) (21)
P
Table 1. Expression of molar chemical potential

for pure phases or ideal mixtures
System State function Molar chemical potential

Perfect gas PVm  RT P
 m (T , P)   m  (T )  RT ln( )
[2, p. 106] R: perfect gas constant P
(22)
Van der PVm  RT  B' ( T )P  C' ( T )P 2 P ( P )
 m   m  ( T )  RT (ln )
Waals gas P
B' and C ' functions of Van der (23)
[4., p.155]
Waals coefficients
 (P) expressed in terms of B' and
C'
Perfect gas PVm  RT ; Pi   Pi im  im

(T )  RT ln
Pi (24)
mixture P
[2, p. 207] Pi : partial pressure of i
Ideal solution
Gi m im  im

(T )  RT ln xi (25)
G   mi (  RT ln i )
[2,p.220]
i Ni  mi i
xi : molar fraction of i
G : free enthalpy of the mixture

Pure, slightly Vm (T , P)  Vm (T , P  )(1  T ( P  P  )  im   im  (T )  P /  (T ) (26)
compressible  T : Isothermal compressibility  (T ) : density of the liquid
liquid
[2,p.122]
m (T ) is the reference chemical potential at temperature T and pressure

reference. Table 1 summarizes the main cases for which the chemical
potential can be calculated using Gibbs-Duhem relation..
Laplace and Kelvin’s Relations
The Laplace model applies to the liquid gas interface. On the

mechanical level, it is modelled by a curved surface of small thickness
which separates the two fluids at different pressures. The mechanical
equilibrium of the interface is translated by Laplace’s relation [2, p. 44]:
1 1
pG  pL   LG (  ) (27)
R1 R2
pG and pL are the pressures in the gaseous and liquid phases,  LG is
the surface tension of the liquid-gas interface (0.072 N/ m 2 for water at
20°C), R1 and R2 the main radii of curvature at a point on the surface. This
relation applied to a spherical gas bubble of radius R gives:
1
pG  pL  2 LG (28)
R
It is found experimentally that curved liquid-gas surface phenomena

directed towards the gas phase have the effect of lowering the equilibrium
vapor pressure of the liquid. To analyze the effect of curvature of the
interface, three surface geometries are considered: a flat surface, the bubble
and the droplet (Figure 2).
P' , v' , '

Pvs( T )
P " , v" ,  " P " , v" ,  "
Figure 2. Vapor-liquid equilibrium in bubbles and droplets.
In the first case, the vapor pressure is equal to the saturation vapor
pressure at the temperature T: We note P, v,   the pressure, mass
volume, chemical potential on the side of the concavity and P,v,   the
same quantities on the outside of the bubble or droplet. The radius of the
bubble or droplet is r .
In an infinitesimal variation, the mechanical equilibrium obeys the
Laplace relationship:
2 LG
dP"  dP'  d ( ) (29)
r
At a fixed temperature, the equilibrium with respect to the transfer of

matter obeys (13):
d m"  d m' (30)
At constant temperature, the Gibbs-Duhem relationship applied to the

liquid and gaseous phases gives:
d m'  v ' dP' (31)
d m"  v" dP" (32)
So:
v' dP'  v" dP" (33)
Substituting into (29)
( dP' ( v " v )  d ( 2 LG )
' "
(34)
v r
v'  v" 2
dP" ( )  d ( LG ) (35)
v' r
For the droplet, v  is the molar volume of the liquid phase which is
negligible compared to the molar volume of its vapour. By adopting the
law of perfect gases:
RT
v'  (36)
P'
Relationship (34) gives:
RT 2
dP' ( ' "
)  d ( LG ) (37)
Pv r
Assuming constant surface tension and integrating between an infinite

radius: 1/r = 0 for which P'= Pvs (T)) and any radius r corresponding to an
equilibrium pressure P drop , we obtain the Kelvin formula:
P drop) 2 v m
ln( )  LG (38)
Pvs(T ) RrT
Soil geometry is of the bubble type and, in the same way:
P bulle 2 v m
ln( )   LG (39)
Pvs( T ) RrT
It can be seen that the curvature of the interface increases the

equilibrium pressure of the vapor in the case of a droplet and decreases it
in the case of a bubble.
MEASURING CHEMICAL POTENTIAL IN COMPLEX MEDIA
Table 2 gives some characteristics of a loamy clay soil (SLA is the

reference medium for this study).
Table 2. Some characteristics of silty clay soil (SLA)
Real Density Apparent Porosity Granulometry Mineralogical

of the solid density of D = diameter of composition
phase solid phase grains
2650 kg/m3 1500 kg/m3 43% 0.001 mm < D Quartz : 40%
<0.3 mm Clay : 10%
Calcite : 50%
Principle of Measurement Method
A pure liquid is considered in a complex medium and in the free state,

both systems being at the same temperature (Figure 3). A membrane semi-
permeable to the chemical species in the liquid is available. For the free
liquid, the equilibrium vapor pressure is given by the saturated vapor
pressure Pvs (T ) which is known for many liquids. The semi-permeable
membrane makes it possible to isolate the pure constituent whether in
liquid or gaseous form. The equilibrium partial pressure in the measuring
apparatus is different from Pvs (T ) because of actions of the interfaces and
other constituents; this is Pveq (T ) .
Regulated temperature enclosure

Semi permeable
Menbrane to i
Saturated vapor
pressure pvs (T )
Liquid i in
Pure i free sta te
Complex media
contenig i Measuring device
Figure 3. Schematic diagram of the measurement of the chemical potential of a

constituent of a complex medium.
At equilibrium, there is equality of the chemical potentials of i in the

complex medium and in the reservoir of the measuring apparatus.
Activity
Assuming that the constituent in the reservoir behaves like a perfect

gas, according to (22), Table 1, being the molar mass of i, the mass
chemical potential is written:
RT pveq
i (T , P)  i  (T )  ln(  ) (40)
Mi P
The same reasoning applies to pure free-state liquid whose chemical

potential is i
0
(T , P) with:
RT pvs (T )
i0 (T , P)    (T )  ln(  ) (41)
Mi P
With (40) and (41), the chemical potential in the medium is expressed
in the form:
RT pveq
i (T , P)  i0 (T , P)  ln( ) (42)
Mi pvs (T )
The activity of constituent i is defined by:
pveq
ai (T )  (43)
pvs (T )
The saturating vapor pressure is insensitive to total pressure [2] so

relationship (42) becomes:
RT
i (T , P)  i0 (T , P)  ln( ai (T )) (44)
Mi
The relationship (43) shows that ai varies between 0 and 1; when the
reference state corresponding to the pure liquid is adopted with i0 (T , P) =
0, the chemical potential is negative and varies between 0 and   .
Energy must be provided to bring the mass unit of the constituent of the
medium to the reference state.
Table 3. Value of water activity for various

saturated salt solutions at T = 30°C
Sel KOH CH3CO MgCl Cr2Na207,2H NaCl K2SO4

OK 20
aw (/) 0,07 0,22 0,33 0,52 0,75 0,96
In the case of water, the activity of liquid water and its equilibrium
vapor can be regulated by saturated salt solutions (Table 3).
These solutions are used to control the relative humidity of water vapor
in a closed isothermal chamber and for relative humidity sensor
calibration.
The foregoing developments have been carried out in the case in which
the material in the tank of the measuring apparatus is a perfect gas. This
reasoning can be extended to other behaviors; the appropriate relationship
from Table 1 must be taken into account. In particular, if the material
isolated by the measuring apparatus is in the form of a pure, slightly
compressible liquid, relationship ((26) Table 1) gives the mass chemical
potential:
P
i (T , P)  i0 (T , P)  ; P0 (45)
 (T )
Capillary and Hygroscopic Media
Relationships (22) to (26) can only be applied in very special cases.

Given the complex structure of complex natural and artificial media,
physical measurement is almost mandatory. Table 4 gives some values for
chemical potential calculated using the laws of Laplace (28) and Kelvin
(39). The calculated chemical potentials are of very different orders of
magnitude.
Table 4. Variation of liquid pressure (Laplace) and activity,

for a bubble, depending on the radius
(Case of water  LG = 73 10-3J/m2, T = 291 K)
Laplace
Radius (m) Liquid pressure – gaz pressure Mass chemical potential (J/kg)
(kPa)
10-4 -1.440 -1.44
10-5 -14.400 -14.4
10-6 -144 -144
10-7 1440 -1440
Kelvin
Radius m(m) Activity aw = Pvbulle/pvs Chemical potential (J/kg)

infinite 1 0
10-6 0,999 -1360
10-7 0,989 -1496
K2SO4/0,96 -5524
10-8 0,897 -14710
10-9 0,337 -147198
Measured pressures are less than 500 kPa in absolute value,

corresponding to a chemical potential of the order of -500 J/kg for water.
With a solution of K2SO4, water activity is 0.96 which gives a chemical
potential of -5000 J/kg. Two domains characterized by different physical
phenomena appear: above -500 J/kg and below -5000 J/kg. Distinction is
made between the domain where the equilibrium is managed by the
capillarity (this state is called capillary) and the domain where there is a
direct connection between the liquid and the solid and Van de Waals
forces, hydrogen bonding, etc. predominate (qualified as a hygroscopic
state). On the experimental level, the distinction between capillary and
hygroscopic states results in two different measurement techniques
 For capillary media, the semi-permeable water membrane is a

porous stone that lets the supposedly pure liquid water pass
between the medium and a reservoir. Measurement of the pressure
in the reservoir gives the chemical potential of the liquid phase in
this reservoir and in the medium,
 For hygroscopic media, the surface of the medium, possibly
supported by a coarse mesh grid is the semi-permeable membrane.
Chemical potential is determined by measuring the vapor activity
of the constituent in the gas phase. A radius of 109 m is 10 times
the size of a water molecule, i.e., outside of macroscopic physics.
Below this order of magnitude, water molecules are in the form of
layers, fixed on the surface of the solid and in equilibrium with a
vapour.
Measuring Chemical Potential Using a Tensiometer
In a capillary field, the pressure of the liquid phase is measured using a

tensiometer (Figure 4). A porous stone makes the junction between the
water in the unsaturated medium and a pressure sensor. This device
homogenizes the distribution of water on the side of the porous medium so
that its pressure can be considered uniform. The existence of a concave
interface facing the gas phase implies, according to Laplace’s law, that the
pressure of the liquid phase is lower than the pressure of the gas phase.
Pressurized air
Water content
Sample
Gas pressure- Water pressure

Porous plate
Pressure transducer
(a) (b)
Figure 4. Measuring the chemical potential of pure water in a capillary medium using a
tensiometer
*
In the case of a pure, relatively incompressible liquid at pressure p l at
*
the scale of the pores, according to (45) with p g being the reference
pressure, the mass chemical potential of the liquid can be written:
pl* ( w)  p*g
l (T , p ( w)   (T , p ) 
* 0 *
(46)
l (T )
l l g
The water content w is defined by:
e
w (47)
s
e and  s being the apparent densities of water and solid phase. The
*
relationship pl ( w ) gives the chemical potential of water. A tensiometer’s
measurement range is limited by the capacity for fluid contact through the
porous stone and by temperature-activated cavitation but it can be
increased by raising the gas phase pressure in the pores of the capillary
*
medium ( pg ) to reduce cavitation.
Measurements performed in imbibition and drainage show major
hysteresis phenomena. These phenomena can be attributed to the
heterogeneity and roughness of the grain surface inducing hysteresis of the
wetting angle. It follows on from this phenomenon that the capillary
potential water content relationship is not unique and depends on the
medium’s water history. This phenomenon is currently poorly modeled but
it can be ignored if, in the transformations envisaged, the variation of water
content is monotonous: imbibition or drainage.
Nothing prevents using a tensiometer for pure liquids other than water.
The essential difficulty is the choice of a porous stone capable of
establishing the connection between the liquid phase of the porous medium
and that of the reservoir. This technique will be used in the case of pure
ethanol in SLA.
Calibrated Filter Paper
This method has been approved by the American Society for Testing
and Materials (ASTM) as a standard method for measuring soil pressure
[5]. It consists of inserting a triple-thick filter paper between two
compacted soil slabs with the same liquid content (Figure 5). The two slabs
are secured by adhesive tape; the whole is enclosed in a hermetically
sealed container to prevent evaporation during balancing (that can take
about twenty days). At equilibrium, the water content of the central filter
paper, free of soil traces, is weighed at 1/10,000.
Here, the semi-permeable membrane is constituted by the contact
surfaces between the paper and the soil. If the filter paper is saturated, the
water moves towards the soil; if it is dry, the paper will absorb water from
the soil.
Figure 5. Placing the filter paper on a soil sample.
At equilibrium the chemical potential of the water is the same in the

soil and the filter paper. Prior to calibration, the relationship between the
chemical potential and the paper’s water content is established. The
calibration curve of the filter paper suggests a possibility of measuring the
chemical potential between -1 and -100,000 J/kg for a change in water
content of the paper of between 0 and 180%. Various authors have
suggested that Whatman No. 42 filter paper is the most suitable for soils.
The chemical potential of the water is derived from measurement of the
water content of the central filter paper.
Macroscopic Approach to Adsorption Phenomena

Desorption Isotherm
The desorption isotherm describes the relationship between water

activity and the equilibrium water content of a medium at a fixed
temperature and gas phase pressure. To establish this relationship, the wet
medium sample is placed in a temperature-controlled, closed chamber
(Figure 6a). The activity of water vapor in the enclosure is regulated by
saturated saline solutions (Table 3). The surface of the sample acts as a
semi-permeable membrane. Continuous weighing makes it possible to
judge the equilibrium and determine the equilibrium water content. This
operation is repeated for saturated saline solutions with different activities

in order to establish the desorption isotherm (Figure 6 b).
Balance
Sample
Water content
1
Salt solution aw Water activity aw
(a) (b)
Figure 6. Schematic diagram of a desorption experiment.
Water can be trapped in different microstructures such as clay sheets or

adsorbed in layers on grains. These microstructures are supposed to be
open and can exchange the water component. When the measured weight
becomes constant, the equilibrium of the medium as a whole is reached
accompanied by local balances of water within microstructures and
between them. The chemical potential of the water and therefore the
activity is the same in all microstructures; it is legitimate to talk about the
chemical potential of the water at the scale of the soil sample. There is a
relationship between the chemical potential at equilibrium and the average
water content of the medium. To overcome hysteresis phenomena,
isotherms will be established in either desorption or sorption, e.g.,
desorption isotherms for three media, wood, agar gel and coffee albumen,
are given in Figure 7.
The activity of a relatively incompressible liquid are little influenced
by total pressure [2, p. 210]. If the reference pressure is atmospheric
pressure, the chemical specific mass potential of the water is deduced from
(44):
RT
 w (T , Patm )   w0 (T , Patm )  ln( a w ( w, T )) (48)
Me
Wood, experimental
1.2
Wood, GAB
Agar gel, experimental
Agar gel, GAB
Average water content (/)
1
Coffee, experimental
Coffee, GAB
0.8
0.6
0.4
0.2
0
0 0.2 0.4 0.6 0.8 1
Water activity (/)
Figure 7. Desorption isotherm of water in various media and GAB modeling. For agar
gel, the water content scale should be multiplied by 100.
Modeling of Adsorption-Desorption Isotherms
Desorption isotherms may be in different forms (Figure 8).
IV
Water content (/)
II
I III
0 Activity (/) 1
Figure 8. Some forms of isotherm.

When water content tends to saturation content, activity tends to 1

which corresponds to the value of the chemical reference potential,
generally taken as zero; aw = 1 is asymptotic although the maximum water
content value cannot exceed the saturation water content.
Type I is encountered for media with spread porosity. The part of the
curve, concavity turned down, corresponds to the creation of a monolayer.
Then there is progressive variation of the activity following the formation
of multilayers. The vertical part in the vicinity of aw = 1 corresponds to the
filling all the compartments of the medium. Type I is encountered in many
soils, notably for those used in this chapter.
In its middle part, type II is characterized by variable activity over a
limited range of liquid contents. This variation in activity reflects the
presence of porosity with a strong impact on water activity, e.g., fine grains
or clay slips. Since this porosity is saturated, a steep variation in water
content around aw = 0 is observed. This results in fast variation of e which
tends towards   . There is therefore an increase in water bonds which is
probably due to the formation of layers on the surface of the solid.
Type III is an extension of type I. In the neighborhood of aw = 0, there
is no downward-facing curvature. Compared with type I, at equal water
content, activity is higher and therefore chemical potential is lower. The
solid-water interaction is weaker than in case I near aw = 0. This type of
isotherm is encountered in for natural rubber.
Type IV reveals the presence of several structurally homogeneous
adsorption sites with filling proceeding site by site
Isothermal models are available in the literature. We are interested in
type I, often found in soils and complex media (Figure 7). The BET model
describes adsorption on a flat, homogeneous surface. The GAB model is an
extension of the BET model. It shows three constants: Cg associated with
the adsorption energies of the first and second layers; K g associated with
the binding energies of the following layers; and Xm , the adsorbate
content corresponding to the monolayer. The GAB model is also

applicable to types II and III; if X is the water content, it is of the form:
X mC g K g
X  aw (49)
(1  K g a w )(1  (C g  1) K g a w )
Coefficients of the model are calibrated on experimental isotherms,

e.g., Table 5 shows the coefficients for wood (amaranth), agar gel and
coffee endosperm. In the last column of this table is the slope at the origin.
Figure 7 shows a good match in GAB relationship for activities below 0.9.
As with the tensiometer curves, the chemical heterogeneity of the
surfaces and their roughness are responsible for hysteresis phenomena in
the activity-adsorbate content relationship.
Table 5. Coefficient of the GAB model for three materials
Xm Cg Kg
X / a w ( X  0 )
Wood (amaranth) 0.0626 4.71 0.851 0.251
Agar gel 12.33 17.225 0.810 1.716
Coffee Endosperm 0.0632 12.777 0.871 0.703
Figure 9. Graphical representation of the opposite of the chemical potential of water

for two soils: SLA and SM.
Figure 9 shows changes in the absolute value of the chemical potential

of water in two soils of similar composition: SLA (Table 2) and SM
(which has a slightly higher clay content). Measurements are made using a
tensiometer for SLA, desorption isotherms for both SLA and SM and filter
paper for SM. In this figure, the measurements are consistent: the
tensiometry results carry on from the isothermal measurements for the
SLA and the filter paper measurements extend the isotherm estimates.
Moreover, SM being more argillaceous than SLA, in absolute value, the
curve for the SM is located above that for the SLA. Filter paper covers a
measurement interval of between 1000 and 10000 J/kg meaning a
possibility of complete coverage of the water domain in the soil.
Desorption Isotherm for a Volatile Organic Compound (VOC)

in Soil
The saturated salt solution method is only applicable for water. For
media partially saturated with a volatile organic compound (VOC) a
mechanical method has been developed. The measuring device is called an
activimeter [6].
Gas pressure
Piston
Sample
Time
Pressure transducer
(a) (b)
Figure 10. Apparatus for measuring the activity of a pure liquid in a soil - activimeter.
When a mixture of air and VOC gas is compressed in the presence of a

medium containing liquid VOC, the partial pressure of the air obeys the
ideal gas law while the partial pressure of the VOC in the gaseous state
remains equal at equilibrium vapor pressure. The medium containing the
liquid VOC is placed in a closed, isothermal chamber, the volume of which
can be modified by a piston (Figure 10a). The semi-permeable VOC vapor
membrane is the upper surface of the sample. A sequence of volume
increments is performed and a total equilibrium pressure p *gi is
established for each increment (Figure 10b). Applying the law of perfect
gases in air, the total pressure of the gaseous phase, at each equilibrium i,
is:
RT
p *gi  pvi*  na i
(50)
vo   v j
j 1
In this relationship, pvi* is the equilibrium partial pressure of the

liquid. Since the volume variations v j are small, the liquid content varies
little during the experiment and the pressure p*vi can be equated with the
equilibrium partial pressure pveq for the liquid content w . vo is the volume
initially occupied by the gaseous phase and na is the number of moles of air
in the chamber. Three increments v j are in principle necessary and
sufficient to determine the three unknowns, pveq , vo and na .. To increase
the accuracy of the method, 6 to 8 volume increments are included. The
solution of the system (50) is obtained by a least-squares method.
Knowledge of p veq gives the chemical potential at the temperature and
pressure of the experiment.
(%)
6
en eau(%)
5 Lozano Présente étude
Water content
teneur 4
3 SLA, Salt solutions

2
1 SLA, Activimeter
0
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1
activité de(/)l'eau a w
Activity
Figure 11. Comparison of the desorption isotherm of water in SLA determined by the
saturated solution method and the activimete
Figure 12. Desorption isotherm for water, heptan and trichlorethylen in SLA.
Figure 11 shows the isotherms of water in SLA as determined by the

saturated salt solution method and activimeter. Concordance is good which
validates the mechanical method, the saline solution method having been
well characterized.
Figure 12 shows the isotherms at 30°C, obtained by the activimeter for
water, heptan, trichlorethylene (TCE) in clay loam sand (SLA). It is this
ability to deal with different liquids that constitutes the advantage of
activimeter.
EXPERIMENTAL RESULTS ON THE VARIATION OF

CHEMICAL POTENTIAL VESUS WATER CONTENT
Variations in chemical potential in a complex medium are established

for the media and liquids in Table 6. Column 1 lists the media studied
which range from soils to products of biological origin through gels. The
test temperature is given in column 2. Measurement method(s) are given in
column 3. For soils, measurements were made by tensiometry and the
saturated saline solution (SSS) method. For food industry media and gels,
the SSS method was used. For coffee, the mechanical method was used for
heavy activities. For tests on soils and liquids other than water, only the
mechanical method can be used. Information on the structure of the
medium is specified in column 4; there are media whose solid phase is
granular and media whose solid phase is continuous. The media of
biological origin have a cellular structure. The media may be two-phase
(solid-liquid) or contain a gas phase as well. The liquid phase is usually
water except for tests on heptane and trichlorethylene (column 5).
Maximum water content wsat is specified in column 6 when known. For
media such as latex, pasta, cocoa and coffee, the value given in column 6
corresponds to the maximum value found in the literature. Highly
deformable gels, such as agar gel and alumina gel can adsorb a large
amount of water which can lead to disintegration of the medium in which
case it is impossible to define a saturation water content.
Chemical potentials are calculated using Equation (46) for a capillary
medium and Equation (48) for a hygroscopic medium. The reference state
corresponds to the pure liquid with a flat free surface at the temperature T
and atmospheric pressure; the activity is then taken equal to 1.
Figure 13a shows the variation of the chemical potential of supposedly
pure water in three soils as a function of water content. Figure 13b
concerns certain materials. Figure 13c relates to food industry products.
Figure 13d compares water, heptane and TCE in SLA.
Although the media have very different modes of water binding, the
general shape of the curves is preserved. The chemical potential as a
function of water content is obviously increasing. With the chosen

reference, chemical potential tends towards the potential of the capillary
medium when water content tends towards saturation.
Table 6. Media and liquids used
Material Tempera- Method Structure Liquid Wsat

ture
SLA (France) 30°C tensiometry, Granular, triphasic Water 0.29
SSS
SLA (France) 30°C Mechanical Granular, triphasic heptan 0.18
method
SLA (France) 30°C Mechanical Granular, triphasic Trichloro- 0.42
method ethylen
Fine sand 30°C tensiometry, Granular, triphasic Water 0.26
(Burkina- SSS
Faso)
Clay (France) 30°C tensiometry, Granular, triphasic Water 0.34
SSS
Latex 60°C SSS Continuous solid Water ?
Ivory Coast phase, biphasic
Wood – 60°C SSS Continuous solid Water 0.4
Amarante phase triphasic
(Guyana)
Alumina gel 30° SSS Granular. Triphasic Water >2.6
for w>1 biphasic for
w<1
Agar gel 30°C SSS Continuous solid Water >10
phase, biphasic
Pasta 20°C,80°C SSS Continuous solid Water >1
phase biphasic
Cacao bean 40°C SSS Cellular, biphasic Water 0.95
(Mexico)
Coffee bean 35°C SSS, Cellular, biphasic Water 1.5
(Mexico) Mechanical
method
Isotherms are sensitive to temperature. There is an increase in chemical

potential with temperature, e.g., for the SLA-water system, with a water
content of 2%, the chemical potential of the water goes from -250 000 to -
100 000 J/kg when the temperature rises from 20°C to 60°C. The effect of
the total pressure of the gas phase is low.
(J/kg)
potential(J/kg)
0 0
0 0 0.1 0.1 0.2 0.2 0.3 0.3 0.4 0.4 0.5 0.5 0.6 0.6 0.7 0.7
(J/kg)
(J/kg)
-50000
-50000
11 -100000
33 22
chimique (J/kg)
Chemicalpotential
-100000
11
Potentiel chimique (J/kg)
Chemical potential
33
potential
-150000
-150000
22 11 Sand
Sand
-200000
2 Clay
2 Clay
-200000
1 Alumina gelgel
ChemicalPotentiel
3 SLA -250000 1 Alumina
Gel d'alumine
3 SLA -250000
2Gel d'alumine
Agar
Caoutchouc gelnaturel
Chemical
-300000 2 Agar
Caoutchouc gel
naturel
Gel d'agar
-300000 3GelNatural
d'agar rubber
-350000
3 Natural rubber
-350000
Water content (/)
Water content (/) (a) -400000
(a) -400000
Teneur en eau (/) (b)
Water
Teneurcontent
en eau (/) (/) (b)
Water content (/)
0
Potentiel chimique (J/kg) (J/kg)
0 0,01 0,02 0,03 0,04 0,05 0,06

00 3 0.1 0.2 0.3 0.4 0.5 0.6 0.7
(J/kg)
(J/kg)
00 0,01 0,02 0,03 0,04 0,05 0,06

-50000 0
3 0.1 0.2 0.3 0.4 0.5 0.6 0.7
3
(J/kg)
0
-50000
-50000
-100000
2 Café -50000
3 2
12 1 coffee
potential
Pates alimentaires (80°C) -100000 2
chimique (J/kg)
-100000
1 Water
potential
Café Eau
12 coffee
potential
-150000
1 PastaPates(80°C)
cacao
alimentaires (80°C) -100000
1
1 Eau
Water
Chemical potential
-150000
-150000
-200000 23 Pasta
Cacao(80°C)
cacao
albumen -150000
1 2 TCE TCE
-200000
3 Cacao albumen ChemicalPotentiel
-200000
2 TCE3TCEHeptan
Heptane
-250000 -200000
-250000
3 Heptane
Heptan
Chemical
-250000
-300000 -250000
-300000
Chemical
-300000 -300000
-350000 -350000
Teneur en eau (/)
-350000 Water content (/) (c) -350000
-400000
Teneur en eau (/)
Water content (/) (c) -400000 LIquidTeneurcontent
en liquide (/) (/) (d)
LIquid content
Teneur en liquide (/) (/) (d)
Figure 13. Chemical potential of water in various media. (a): soils and water. (b): gels
and water. (c): agri-food products and water. (d): SLA and water, heptan, TCE. For
agar gel, the water content scale should be multiplied by 100.
Field of Validity of the Different Methods
Figure 14 represents absolute chemical potential (logarithmic scale) for

some media of Table 5. It highlights three different intervals:
 Between 0 and about -500 J/kg, the tensiometric method is

applicable and gives the chemical potential of water in the
capillary state. For food media and gels, it is impossible with the
porous stones that are currently available to create a connection
between the middle water and the reservoir of a tensiometre.
 Between -500 and about -5000 J/kg, conventional methods do not
work. The calibration curve of the filter paper suggests that
measurement may be feasible in this interval.
 Below -5000 J/kg, the method based on isotherms gives excellent

results. The activity meter is to be classified in this category.
1000000
Wsat, Wood=0,34
Wsat , Coffee=1.5
Wsat, Coffee=1,5
100000
10000 Clay Coffee

Chemical potential (J/kg)
albumen
1000
Wood
100
SLA
linear approximation
10
Sand
1
0 0,2 0,4 0,6 0,8 1 1,2 1,4
0,1
Water content (/)
Figure 14. Logarithmic scale representation of the absolute value of the chemical
potential of water for various media.
In this figure are represented linear approximations in the vicinity of

the saturation. The vertical lines obtained are asymptotes when the medium
tends towards saturation. For soils, note the continuity of the curves during
the transition from the capillary state to the hygroscopic state resulting
from the generality of definition (4). It will be noted that the measurement
techniques used—apart from the last—are the same as those used to define
and measure a quantity called “suction” in soil science. The quantities used
to define and measure it, namely pressure in the tensiometer, relative
humidity of the gas phase and weight of the paper, are empirical quantities.
Suction does not have a single definition or properties that link it to
thermodynamics, physical chemistry or mechanics. On the other hand, the
chemical potential defined by (4) inherits the whole corpus of these basic
disciplines and it is, therefore, particularly suitable for addressing new
scientific fields, particularly thermo-chemi-mechanical couplings, as will

be shown in the following section.
STUDY OF CHEMICAL POTENTIAL

UNDER VARIOUS CONDITIONS
Subsequently, we propose to present developments in various cases

that illustrate coupling in a complex medium:
 Effect of a solute on the chemical potential of water and the

species in solution in the case of a capillary soil.
 Osmotic dehydration.
 Application of gas phase pressure in a soil.
 Effect of a stress tensor on the chemical potential of water in an
elastic gel.
For the last two cases, a formulation of free energy, entropy, internal
energy will be given.
Sol Partially Saturated with Water or Pure Liquid in the

Capillary Field
Two liquids in the same complex medium are considered separately.

We denote by ne and ni the numbers of moles of water e and liquid i, S
the entropy, T the temperature, we and wi the water content and the
content of i. The volume of the voids ( Vvoid ), can be determined for the soil
saturated by water or i:
we  s wi  s
Vvoid  
 e*  i* (51)
With the molar chemical potentials, for a pure water, Pe being the
pressure of water, the Gibbs-Duhem relation is written:
Se dT  V dPe ( we )  ne dem ( we )  0 (52)
For the pure liquid i, occupying the same volume V:
S i dT  V dPi (wi )  ni dim (wi )  0 (53)
In an isothermal evolution, subtracting (53) and (52):
 V (dPe ( we )  dPi ( wi ))  ne dem ( we )  ni dim ( wi )  0 (54)
It is admitted that for volume V, the geometries of the poral space

portions occupied by the solution and the pure water are identical.
According to Laplace’s law (27),  e ( we ) and  i ( wi ) being the surface
tension of the two liquids:
Pi ( wi )  i ( wi )
 (55)
Pe ( we )  e ( we )
Using the mass chemical potential:
em
e  (56)
Me
im
i  (57)
Mi
Reporting in (54):
 i ( wi )
 V dPe ( we )(1  )  ne M e de ( we )  ni M i di ( wi )  0
 e ( we ) (58)
The volume, V is written:
ne M e
V 
e* (59)
Or:
ni M i
V 
i* (60)
(58) becomes:
dPe ( we )  i ( wi ) nM
(  1)  de ( we )  i i di ( wi )  0
e *
 e ( we ) ne M e (61)
dPe ( we )
The quantity
 e* is the differential of the chemical potential of
the water, with (59) and.(60), (61) becomes:
 e* i ( wi )
de ( we )  di ( wi )  0 (62)
i* e ( we )
By integrating from the reference state:
 e* i ( wi )
i ( wi )  e ( we ) (63)
i* e ( we )
This relationship makes it possible to calculate i ( wi ) if  e ( we ) is

known and vice versa.
Chemical potential of water or ethanol
0
0 0,2 0,4 0,6 0,8 1 1,2
-100 Experimental
tensiometre ETHANOL
-200 Deduced
from (63)
(J/kg)
-300
-400 Deduced
from (63)
WATER
-500
-600
Experimental,
filter paper
-700
Saturation degre of water or ethanol (/)
Figure 15. Comparison of the chemical potential of ethanol measured at the chemical
potential calculated by (63) and vice versa.
Figure 15 compares the chemical potential of the water obtained with

the filter paper technique to values obtained for ethanol by tensiometry.
The values obtained by (63) are represented. In order to respect the
condition vis-a-vis equal volumes, the degree of saturation (SR) is used as
the abscissa. The numerical values adopted are the following:
 e*  1000kg / m3 ,  i*  789kg / m3 ,  e ( xi  0)  0,071N / m

 i ( xi  1)  0,022 N / m .
The error of the order of 10%, is certainly attributable to the difference

in experimental technique; this figure validates the proposed approach and
in particular the assumption of identical geometry of the two phases in the
soil.
Figure 15 shows that the chemical potential values of water and
ethanol vary little and remain close to the saturation value. If the solution is
diluted, Raoult’s law can be used, with Raoult coefficient: KR = 3200 for
water at 25°C:
pveq ( SR, xi )  K R (1  xi ) (64)
Across its domain of validity, this relationship gives the equilibrium

pressure of the water vapor and allows deduction of the chemical potential
of the water in the presence of ethanol in a capillary domain:
RT
 e (SR, xi )   e (SR, xi  0)  ln( K R (1  xi )) (65)
Me
For a given value of xi , the last term of (65) is constant. Curves

describing variation of the chemical potential of water in a soil solution can
be deduced from the curves relating to pure water by translation.
Osmotic Effect, Osmotic Dehydration
Figure 16 illustrates the phenomenon of osmotic dehydration. An agar

gel ball initially containing water is placed in polyethylene glycol (PEG)
solutions of various densities. There is a significant decrease in the
diameter of the ball over time; this decay can only be due to the loss of
water from the ball. This effect is all the more marked when the molar
mass of PEG is large. The phenomenon is more important as the molar
fraction or mass concentration is large.
When the solute molecules are not impeded by the solid phase,
transport of a solute is a combination of movement by filtration of the
phase and solute diffusion transport. These mechanisms do not make it
possible to explain the change in the ball’s diameter observed in Figure 16.
For a molar mass of 6000 g/mole, the volume of the sphere is divided by
2.5 which suppose strong fluxes of the liquid phase. Figure (17) shows the
internal structure of the agar gel at 830% water content; the solid phase, in
white, has pores of about 0.1 microns and the liquid phase, in gray,
occupies all of the pore space.
40
Diameter of the ball (mm)
38
30%, M= 4000 g/mol
36
34
40%, M= 1500 g/mol
32
40%, M= 4000g/mol
30
28 40%, M=6000g/mol
26
0 5 10 15 20 25
Time (h)
Figure 16. Kinetics of the diameter of an agar gel bead immersed in Poly-Ethylene-
Glycol (PEGC) solutions, for various molar masses and various concentrations.
The size of the solute molecules is not negligible compared to that of

the pores so diffusion is hindered by interactions between the solute and
the solid phase. These interactions can have two sources:
 Mechanical: the solid phase exerts efforts of attraction or friction

on the solute molecules; the molecules are partly trapped.
 Electrical: the charged solutes are subject to attractive forces on
the part of the electric double layers on the surface of the solid.
Figure 17. View of the internal structure of the agar gel for a water content of 830%.
Solid phase in white, liquid phase in grey.
The concentration of solute is maximum at the surface of the sphere

and decreases towards the center because of the phenomenon of retention.
According to the Gibbs-Duhem relationship (7), at uniform temperature
and total pressure:
ni  i , k  n e  e , k  0 (66)
The chemical potential gradient of the water is opposite to that of the

solute chemical potential so the flow of water is directed towards the
outside of the sphere.
To analyze the osmotic dehydration experiments, consider a medium
composed of an isotropic porous skeleton with its voids entirely occupied
by a solution. The following assumptions are made:
 A continuous liquid phase can be established through a porous

stone so that the experiment shown in Figure 18 can be carried out.
 The temperature of the system is uniform and constant,
 The solution at the pore scale is incompressible and ideal.
 A solute gradient is established.
It is necessary to distinguish transport of the whole solution (index l),

transport of the solvent, i.e., water in this case (index e) and transport of
solutes (indices i). For apparent densities, the notations l ,  e , i are
preserved. l* , e* , i* , are the real densities at the pore scale.
notations l ,  e , i are preserved. l* , e* , i* are the real densities at the pore scale .
,
Semi permeable
membrane for water
Porous stone
Complex medium Solution Pure Water

(A) (B) (C)
Figure 18. Device for evaluating the chemical potential of water in a mixture contained
in capillary porous medium.
The porous medium containing the binary mixture in (A) is in

communication through a porous stone with the compartment (B)
B
containing the liquid phase alone. It ensures the same pressure in B p l as
*
the pressure of the liquid phase in the pores of A pl with:
plB  pl* (67)
An ideal semi-permeable membrane to water separates compartments

B and C; C contains pure water. The pressure difference between these
compartments is equal to the osmotic pressure. Noting pe the pressure in
C:
  plB  p e (68)
Since the gas phase is assumed to be at atmospheric pressure, the

pressures used in (68) are the effective pressures. The mass chemical
potential reference is zero at atmospheric pressure. At equilibrium, the
mass chemical potential of the water component is the same in B and C. It
is evaluated in C:
pe plB  
e   (69)
 e*  e*
This relationship relates the chemical potential of the water component

to osmotic pressure.  being difficult to measure, equilibrium partial
pressures are used. The partial pressures of vapor in equilibrium with water
B 0
in compartment B: p ve ( xi ) and compartment C: pve , are assumed to be
known. Ignoring the compressibility of the fluids, the osmotic pressure is
given by [2, p.216]:
RT p ve0 RT e* pve0

 ln = ln (70)
Ve* p veB ( xi ) M e pveB ( xi )
Where Ve* is molar volume of water. The chemical potential of water

can also be in the form of:
plB ( we , xi ) RT pveB ( xi )
 e ( we , xi )   ln (71)
 e* Me pve0
The effect of the interfaces (first right-hand side of (71)) is

superimposed on the effect of the solute (2nd term on the right of (71)).
The first term of (71) can be measured with a tensiometer limited to
compartment B. The second is given by the partial pressure of water above
a free solution of the same composition as the liquid phase of the medium
In a non-equilibrium thermodynamics framework, the law of water

transport using (71) reveals the osmotic pressure weighted by a coefficient
between 0 and 1, [7]. When the solute accumulation zone is limited to the
surface of the ball, it behaves like a perfect membrane permeable to water
only. This analysis is in line with Staverman’s approach to biological
membranes.
Chemical Potential, Free Energy and Entropy

in a Non-Deformable Soil, Partially Saturated with Pure Water
In the two cases presented below, the method used comprises the
following steps:
 System definition and choice of state variables.

 A limited second-order development of free energy.
 Introduction of calorimetric and thermomechanical coefficients
into the limited development.
 State equations, especially chemical potential and entropy.
We will note f , u, s : the free energy, the internal energy, the entropy
per unit mass of medium, fˆ , uˆ, sˆ the same functions per unit of volume of a
~~~
phase; the functions f , u , s relating to the solid phase mass unit.
System Definition
The system consists of a solid non-deformable skeleton with its pores
occupied by pure water in the capillary state and a gas, considered as a
single chemical species of molar mass M g ; this gas can be under pressure.
The thermodynamic system considered is constituted by the material
contained in the solid phase volume unit. Apparent densities  g and  e
represent the masses of the gaseous and liquid phases in the system. The
liquid phase is supposed to be incompressible at the pore scale. The real

density of the solid phase is also uniform and constant. The volume
fractions of the solid, liquid and gaseous phases are defined by:
vs  s
ns   (72)
v  *s
ve  e w s
ne    * (73)
v  e* e
vg g  w
ng    1  ns  ne  1  s*  *s (74)
v g
*
s e
With the ideal gas law, the real density of the gas phase is connected to
the pressure of the phase by:
Mg *
 *g  pg
RT (75)
And the apparent density by:
Mg
 g  ng p*g (76)
RT
Calculation of the Chemical Potential

To characterize the medium, the temperature T, the mass of water and
the mass of gas are adopted as state variables. The analysis is limited to an
infinitesimal transformation in the vicinity of a reference state (noted 0)
during which the thermodynamic and mechanical coefficients can be
considered constant. For this transformation, the increments of state
variables are:
T  ( T  T0 ) , e  ( e  e0 ) ,  g  (  g   g 0 ) (77)
The free energy per unit volume of solid phase is defined by:
f̂  û  Tŝ (78)
it is approximated by its limited second-order development:
ˆ ˆ ˆ 2 ˆ
ˆf  fˆ  ( f ) T  ( f )   ( f )   1  f T 2
T  e  g 2 T 2
0 0 0 e 0 g
1  2 fˆ 2 1  2 fˆ 2  2 fˆ  2 fˆ  2 fˆ
     T   T   e g
2  e 2 2  g 2 T e T g  g  e
e g e g
(79)
With relationships (2) and (4):
fˆ
sˆ  ( )  , (80)
T e g
f̂
e  ( )T , g (81)
 e
f̂
g  ( )T , (82)
 g e
Relationship (79) is written:

c
fˆ (T ,  e ,  g )  fˆ (T0 ,  e 0 ,  g 0 )  sˆo T   e 0 e   g 0  g  m T 2 
2T0
1  e 1  g   g  g
e 2   g2  e Te  T g  e  g
2  e 2  g T T  e
(83)
The mass heat per unit volume of solid phase is defined by:
𝜕𝑠̂
𝑐𝑚 = 𝑇0 (𝜕𝑇)𝜌𝑒, ,𝜌𝑔 (84)
We notice:
e
de  ( )T , (85)
e g
 g
dg  ( )T , e (86)
 g
e
d eT  ( ) ,
T e g (87)
 g
d gT  ( ) , (88)
T e g
 g
d ge  ( )T , g (89)
e
With these definitions, free energy is of the form:

c
fˆ (T ,  e ,  g )  fˆ (T0 ,  e 0 ,  g 0 )  s 0T   e 0 e   g 0 g  m T 2
2T0
de dg
  e 2   g2  d eT T e  d gT T g
2 2
(90)
It is admitted that the superficial layers do not affect the behavior of

the gas phase, it behaves like a perfect gas of pressure:
RT p*g
g ( T , p )   ( T ) 
*
g

g ln( *  ) (91)
Mg pg
Where  g ( T ) is the reference chemical potential at reference


* *0
temperature T and pressure p g . For the local reference state p g :
RT p*0
 g0 ( T , p*g0 )   g ( T )  ln( *g ) (92)
Mg pg
The variation of chemical potential with respect to the local reference

state:
RT p*g
g ( T , p )   ( T , p ) 
*
g
0
g
*0
ln( *0 )
g (93)
Mg pg
We deduce from this relationship:
 g  g p*g RT 2 1
dg  ( )T , e  ( ) (94)
 g p  g
*
g M g ng p*g
 g
d ge  ( )T , g  0 (95)
 e
Relationships (82), (90) and (92) give:
p*
d gT T  R ln( *g0 )  d g g (96)
Mg pg
With (94) and (76):
p* p*
d gT T  R (ln( 1  *g0 )  *g ) (97)
Mg pg pg
With pg  pg the logarithm being approximated by the first term of

*0 *
its limited development:
d gT  0 (98)
With (80), (81) and (82), the state equations are given by:
f̂ c
ŝ  ŝ0  ( )e , g  m T  d eT e (99)
T T0
f̂
e  e 0  ( )T ,m g  d eT T  d ee
e (100)
f̂
g  g 0  ( )T , e  d g g (101)
 g
In order to reduce to variables that are more easily accessible to the

measurement, the change of variable, ( T , e ,  g )  ( T , w, p g ) is carried out,
*
with:
e  w s (102)
d w   s de (103)
dT   s d eT (104)
The state equations become:
cm
ŝ  ŝ0  T  dT w (105)
T0
dT
e  e 0  T  d ww
s (106)
RT p*g
g  g 0  ln( * 0 ) (107)
Mg pg
Let the expression of the free energy in the neighborhood of a state

( T0 , w0 , p*g0 ) :
Mg c
fˆ (T , w, p *g )  fˆ (T0 , w0 , p *g0 )   s 0T   s  e 0w  n g  g 0p *g  m T 2
RT 2T0
dw 2 ng
 s w  * p *g2  d T Tw
2 2 pg
(108)
Coefficient cm can be approximated by a barycentric relation. The mass

heat of the medium as a whole is equal to the sum of the mass heats of the
various constituents before mixing weighted by the apparent densities of
the constituents. In more complex cases, the coefficient cm can be
determined by calorimetry on the medium as a whole.
The experimental techniques described in the previous section make it

possible to establish the surfaces e ( T , w ) , p g to be fixed. These surfaces
*
(Figure 19) illustrate the significance of the coefficients d w ( T , w ) and

dT (T , w) .
Saturated media
e T
medium

w d ( ) *
p * w w T , pg
g
 T+dT
d ( )
T T w , p*g
T
T-dT
Figure 19. Graphical illustration of coefficients dT and d w .

In the context of the hypotheses that lead to the relation (108), the
knowledge of, cm ( T , w ) , d w ( T , w ) , dT ( T , w ) , allows formulation of the
functions f̂ ( T , w ) and ŝ( T , w ) ; û( T , w ) is deduced from (78).
Elastic Gel, Saturated, Subject to Constraints
System Definition
We examine the case of a deformable medium consisting of a
continuous solid skeleton with its pores entirely occupied by pure water
[8,9]. It is assumed that the porous skeleton is macroscopically
homogeneous and that the medium as a whole (skeleton + water) in the

undrained state is elastic. The medium is subjected to a total stress  ij which
is distributed between the liquid and solid phase. The hypothesis of small
transformations is adopted. The deformations relate to two material points
of the solid phase.
We consider the thermodynamic system consisting of the material
contained in the solid phase mass unit with a volume v  1 / s . This
system is closed for the solid phase and open for the liquid phase. To
characterize the medium, the water content w, the deformation of the solid
skeleton  ij and the temperature T are adopted as state variables. During
transformation, the behavior of the medium is linearized around a
reference state defined by ( T0 , w0 , ij ) .
0
~
The free energy ( f ) of the system per unit mass of skeleton is defined
by:
~ ~ ~
f  u  Ts (109)
Where u ~ and ~s are the internal energy and entropy per unit mass of
skeleton. The mass water is:
w s
me  w (110)
s
Influence of Constraints on the Chemical Potential

For small variations of state variables around the reference state:
T  ( T  T0 ) , w  ( w  w0 ) , ij  (  ij   ij0 ) , (111)

the free energy potential is approximated by its second order limited

development:
~ ~ ~ ~ ~
~ ~0 f f f 1 2 f 1 2 f
f  f  ( ) 0 T  ( ) 0  kl  ( ) 0 w  T 
2
 kl2
T  kl w 2 T 2
2  klj
2
~ ~ ~ ~
1 2 f 2 f 2 f 2 f
 w 2
 T    T w   kl w
2 w 2 T kl Tw  kl w
kl
(112)
For this system, the relationship of Gibbs (1) is written:
~ 1
df  ~s dT   kl d kl  e dw (113)
s
With:
~
~s  ( f ) (114)
 ,w
T kl
~
f
 kl   s ( )T ,w,  pq ,pk et ql (115)
 kl
~
f
e  ( )T , pq (116)
w
Reporting in (112):
~ ~ ~  s ~s 2
 s f (T , w,  kl )   s f (T0 , w0 ,  kl   s s0 T   kl  jl   s  e w 
0) 0 0
T
2 T
1  kl 2  s  e 2  kl  
  kl  w  T ki   s e Tw  kl  kl w
2  kl 2 w T T w
(117)
An increment of water content results in a complementary term in the

thermoelasticity relationship, namely I kl the Kroneker tensor:
1   
 kl   kl  (tr ) I kl   T TI kl  ( kl ) ,T w (118)
E E w
Assuming that the deformation resulting from the water content

increment is isotropic, the water expansion coefficient is defined by:
I kl  (𝜕𝜀𝑘𝑙) (119)
𝜕𝑤 𝜎,𝑇
The deformation and constraint increments are expressed by:
1  
 kl   kl  ( tr )I kl  T TI kl   wI kl (120)
E E
 kl   (tr kl ) I kl  2  kl  3K T TI kl   *wI kl (121)
With the relation of elasticity:
1 2
tr kl  tr kl (122)
E
Where E is the modulus of elasticity and  the Poisson’s ratio. The

compressibility module being defined by:
E
K (123)
3(1  2 )
* translates the stress increase under an increment of water content at

constant temperature and deformation. By multiplying (110) and (121) by
I kl :
 *  3K (124)
The heat of the constant strain system is defined by:
𝜕𝑠̃
𝑐𝜀= 𝑇𝜌𝑠 ( )𝜀,𝑤 (125)
𝜕𝑇
We notice:
e
dT   s ( ) ,w
T (126)
e
dw   s ( )T ,
w
(127)
The development of free energy becomes:
~ ~ c
 s f ( T , w, kl )   s f ( T0 , w0 , kl0 )   s ~s0T   kj0  Kj   s e0w  T 2
2T0
 1
 tr 2    kl2  d ww2  dT Tw  3K ( T T   w )tr
2 2
(128)
The state equations are given by:
c
 s ( ~s  ~s0 )   T  dT w  3KT tr (129)
T0
s ( e  0 )  dT T  dww  3Ktr (130)
 kl   kl0  trI kl  2 kl  3K ( T T   w) I kl (131)
 and  are the Lamé coefficients. The last relationship can be

written:
1  3K
 kl   kl0   kl  trI kl  ( T T  w )I kl (132)
2 2 2
Multiplying this relationship by Kroneker’s tensor:
1
tr  tr kl  3( T T   w ) (133)
3K
The state functions can be inverted to perform the change of variable

( T , w, kl )  ( T , w, kl ). By substituting the trace of the deformation in
(132), it comes:
1 
 kl   kl0   kl  trI kl  ( T T   w )I kl (134)
2 6 K
By reporting (133) in (129) and (130), we obtain:

*
c
 s ( ~s  ~so )    T  dT* w  T tr (135)
T0
 s ( e  0 )  dT*T  d w*w   tr (136)
With:
~
s
c*  T s ( ) ,  c  9 KT2T (137)
T

dT*  ( )T ,  dT  9K T (138)

e
d w*   s ( )T ,  d w  9 K 2 (139)
w
The coefficients dT (126) and (127) d w being defined at constant

deformation, their experimental determination requires blocking of the
deformations while leaving the system open. When operating at
* *
atmospheric pressure, it is easier to determine dT and d w to deduce dT and
dw from it.
Determination of the isotherms in variables T, w,  kl establishes the
surfaces e ( w,T ) ,  to be fixed (Figure 19). These surfaces make it
possible to determine the coefficients d w* and dT . The coefficients c* and  *

can be studied experimentally. The elastic coefficients E and  of the
whole medium in the undrained state can be subjected to mechanical tests.
~
These coefficients being known, f is deduced from (128), ~
s from (135)
and u~ from these two potentials. The effect of stresses on chemical

potential is deduced from (136).
CONCLUSION
The concept of chemical potential provides a theoretical basis for the

different quantities used to determine the binding of water or any other
chemical species in a complex medium, particularly soil. Given its
fundamental nature—at equilibrium and in the absence of active
transport—the potential of a chemical species has the same value in all
subsystems that can exchange this species. Chemical potential is the same
in any micro structure as in the complex system as a whole; it is legitimate
to speak of the chemical potential of a species in a complex equilibrium
system.
With respect to temperature, pressure or stress, measurement of
chemical potential presents particular difficulties. In terms of heat, the
surface of the thermometer or thermocouple is the semi-permeable
membrane. An elastic device is used to communicate the force of this or
measure its deformation. In the case of chemical potential, there is no
universal membrane; the membrane must be matched to the species and the
structure of the medium. It seems, however, that current measurement
modalities make it possible to measure the chemical potential across a
wide range, from a value close to zero.
The chemical potential concept links the physics of complex media to
the basic disciplines of thermodynamics, chemistry and mechanics. It
makes it possible to take into account couplings between phenomena
treated by these different disciplines with the introduction of superficial
phase effects absolutely essential. This may involve the introduction of a
stress tensor, an electric field, one or more solutes and, in the case of soil
chemistry, the superficial phase effect.
This document concerns thermodynamic equilibrium. In the field of
non-equilibrium [10], i.e., when the macroscopic state of the medium
varies from one point to another, temperature, pressure or stress and
chemical potential make it possible to formulate dissipation. The chemical

potential gradient is involved in the expression of material transfer
dissipations: phase filtration [11], species diffusion, chemical reactions and
phase changes [12, 13]. The exploitation of dissipation yields laws based
on known relations in the classical cases. Dissipation and chemical
potential pave the way to addressing new conditions in complex media
when superficial layers play a major role.
REFERENCES
[1] Job, G., Hermann F. 2006. “Chemical potential-a quantity in search

of recognition.” European Journal of Physics 27:353-371.
[2] Guggenhein. E.A. 1965, Thermodynamique. Translated by Doukhan
J.C. Paris: Dunod. [Guggenhein. E.A., Thermodynamics.
Amsterdam: North-Holland Publishing Company]
[3] Callen. Herbert B. 1985. Thermodnamics and an introduction to
thermostatistics. New York: John Wiley & Sons.
[4] Hulin, M., Hulin, N., and Veyssié. M. 1994. Thermodynamique.
Paris: Dunod.
[5] Sibley, J.W., Smyth, G.K., Williams, D.J. 1990. “A new filter
material for measuring soil suction.” Geotechnical Testing Journal
13: 381-384.
[6] Ouoba, S., Cherblanc, F., Cousin, B., Bénet, J-C. 2010. “A new
experimental method to determine the sorption isotherm of a liquid
in porous medium.” Envron. Sci. Technology 44:5914-5919.
[7] Ruiz, Thierry., Bénet, Jean-C. 1998. “Potentiels de transport d’une
solution diluée en milieu poreux.” C.R. Acad. Sci. Paris 326:415-
421. [Transport Potential of dilute solution in a porous medium.]
[8] Biot, M.A. 1962. “Mechanics of deformation and acoustic
propagation in porous media.” J. Appl. Phys 1482-1498.
[9] Mrani, Ibrahim., Bénet, J-C., Fras. G., 1995. “Transport of water in a
bi-constituent elastic medium.” Appl. Mech. Rev, ASME 48 (10) 717-
721.
[10] Kuiken. Gerard., D., G. 1994. Thermodynamics of irreversible

processes. Chichester: John Wiley & Sons.
[11] Cherblanc, Fabien., Boscus, J., Bénet, J-C. 2008. “Electro-osmosis in
gel: application to Agar-Agar.” C.R. Acad. Sci. Paris 336:782-787.
[12] Bénet, Jean-C., Lozano, A.-L., Cherblanc, F., Cousin. B. 2009.
“Phase Change of Water in a Hygroscopic Porous Medium
Phenomenological Relation and Experimental Analysis for Soil
Water.” J. Non-Equilib. Thermodyn 34:133-153.
[13] Ouedraogo, François., Cherblanc, F., Naon, B., Bénet J.-C. 2013.
“Water transfer in soil at low water content. Is the local equilibrium
assumption still appropriate?” Journal of hydrology 492:117-127.
BIOGRAPHICAL SKETCH
Jean-Claude Bénet
Affiliation: University Montpellier (France)
Education: Civil Engineer, Physics PhD and Mathematics PhD
Research and Professional Experience: Researcher at the Laboratory

of Civil Engineering. Leader of the team: “Heterogeneous media”. 35
supervised theses. 30 industrial contracts, 90 publications in journals
Honors: Officier des palmes academiques
Bénet, .J-C., Jamin, F., and El Youssouffi.M.S., 2017 “Chemical potential

of a two component liquid in porous media: The case of unsaturated
soil.” Geomechanics for Energy and the Environment 9 36-45.
Kébré, M.B., Cherblanc, F., Ouedraogo, F., Jamin, F., Naon, B.,
Zougmoré, F., and Bénet, J-C., 2017 “Water in soil at small water
contents: A simple approach to estimate the relative hydraulic

conductivity in sandy soil.” European Journal of Soil Science, 68 (2).
Tiendrebeogo, E., Dissa, A,O., Cherblanc, F., Youm, I., Bénet, J-C.,
Compaore, A., and Koulidiati. J., 2015 “Characterization of Two
Different Stumps of Spirulina platensis Drying: Assessment of Water
Transport Coefficient.” Food and Nutrition Sciences, 6: 1437-1449.
INDEX
A C
activity, 5, 147, 148, 149, 150, 153, 154, calibration, 18, 20, 23, 148, 153, 163
156, 157, 158, 161, 164 capillary, x, 4, 12, 14, 86, 90, 101, 102, 134,
adhesion, 107, 115, 120, 123 150, 151, 152, 161, 162, 163, 164, 165,
adhesion force, 107, 115, 120, 123 169, 172, 174
adhesive water, 9 chemical, vii, ix, x, 5, 19, 24, 25, 42, 133,
adsorption, 14, 19, 27, 156 134, 135, 136, 138, 139, 140, 141, 142,
aeration zone, 4 143, 146, 147, 148, 149, 150, 151, 153,
agar, 154, 155, 157, 161, 163, 169, 170, 171 154, 156, 157, 158, 159, 161, 162, 163,
algorithm, 55, 57, 60, 76 164, 165, 166, 167, 168, 169, 171, 172,
aqueous solution, x, 134 173, 174, 178, 188, 189
aquifers, vii, viii, 2, 24 chemical potential, v, vii, ix, x, 133, 134,
atmospheric pressure, 102, 154, 161, 173, 135, 136, 138, 140, 141, 142, 143, 145,
187 146, 147, 148, 149, 150, 151, 153, 154,
156, 157, 158, 159, 161, 162, 163, 164,
165, 166, 167, 168, 169, 171, 172, 173,
B
174, 175, 178, 182, 188, 189, 190
chemical reactions, 5, 42, 135, 189
behaviors, 3, 93, 148
climate, 4, 24, 25, 27
binding energies, 156
climate change, 4, 25, 27
biodiversity, 23, 25
combined effect, x, 134, 136
biological activity, 5
communication, 135, 172
biological media, 135
complex medium, 135, 146, 147, 161, 165,
boundary value problem, 66
188
Brooks and Corey, 12, 13, 14, 17, 53
composition, 19, 138, 146, 158, 173
194 Index
compressibility, 45, 142, 173, 184 electrodes, 21, 23

compression, 43, 50, 67, 71, 74, 75 energy, viii, ix, x, 12, 20, 22, 133, 134, 135,
conduction, 80, 100, 101, 116, 130 136, 137, 165, 174, 182
conductivity, 12, 13, 15, 16, 17, 18, 28, 78, engineering, vii, ix, 30, 33, 34, 37, 79, 80
112, 130, 191 entropy, viii, ix, x, 133, 134, 136, 137, 140,
conservation, 25, 44, 45, 111, 112 165, 174, 182
constituents, viii, ix, x, 5, 19, 133, 134, 146, environment, vii, viii, x, 1, 2, 3, 19, 25, 45,
180 88, 133, 135
consulting, 30, 33, 34, 37 equilibrium, x, 86, 97, 100, 113, 114, 134,
correlation coefficient, 117, 124 139, 140, 141, 142, 143, 144, 145, 146,
critical state, 71, 74, 78 147, 148, 150, 152, 153, 154, 159, 169,
cycles, viii, 2, 3, 8, 18, 25, 41, 65, 66 173, 174, 188, 190
equipment, viii, 1, 19, 20, 22
ethanol, 152, 168, 169
D
evaporation, 86, 91, 128, 152
evolution, ix, 22, 42, 56, 62, 65, 74, 166
deformation, 3, 8, 9, 77, 182, 184, 185, 186,
exploitation, x, 134, 189
187, 188, 189
dehydration, x, 76, 134, 165, 169, 171
depth, viii, 1, 4, 12, 19, 26, 81, 83, 84, 87, F
88, 89, 90, 91, 105, 107, 124, 126, 128
desorption, x, 27, 134, 153, 154, 158, 160 filter paper, x, 134, 152, 153, 158, 163, 168
desorption isotherm, x, 134, 153, 154, 155, finite element, 42, 49, 70, 73, 77, 78
158, 160 finite element method, 77
diffusion, x, 19, 100, 113, 119, 131, 134, fluctuations, x, 4, 5, 92, 134
136, 170, 189 fluid, 9, 42, 45, 77, 78, 82, 93, 94, 97, 98,
diffusivity, 14, 16, 101, 116 99, 104, 109, 111, 114, 115, 120, 121,
displacement, 50, 82, 136 123, 126, 152
distribution, vii, ix, 11, 12, 13, 14, 16, 17, food, 2, 25, 26, 135, 161, 163
18, 19, 25, 79, 80, 81, 84, 86, 88, 89, 92, food industry, 161
93, 94, 97, 100, 104, 105, 106, 107, 108, food production, 25, 26
113, 114, 117, 120, 125, 126, 127, 150 food products, 135, 163
distribution function, 97, 100, 113, 114, 126 food security, 25
drainage, 18, 28, 76, 152 force, ix, 52, 80, 86, 90, 98, 99, 101, 115,
drying, viii, 8, 11, 18, 41, 43, 53, 54, 55, 56, 120, 121, 123, 126, 188
57, 58, 60, 61, 62, 65, 66, 67, 73, 78, 135 formation, 2, 119, 131, 156
free energy, 165, 174, 176, 177, 180, 182,
183, 185
E
freezing, ix, 79, 80, 81, 82, 83, 84, 85, 86,
87, 88, 90, 92, 93, 102, 103, 104, 105,
effective stresses, 7, 8
106, 107, 108, 113, 114, 117, 119, 120,
electrical conductivity, 23
electrical resistance, 21
Index 195
121, 122, 123, 124, 125, 126, 127, 128,

K
129, 130
frequency domain reflectometry, 22
kinetics, 122, 130
functions of conductivity, 12
fusion, 102, 117
L
G lattice Boltzmann model, ix, 80, 126, 129,
130, 131
GAB model, 155, 156, 157
liquid phase, 9, 14, 42, 116, 131, 143, 144,
gel, 154, 155, 157, 161, 162, 163, 165, 169,
150, 152, 161, 170, 171, 172, 173, 174,
170, 171, 190
182
geometry, 66, 70, 145, 169
liquids, 146, 152, 160, 161, 162, 165, 166
gravitational force, 98, 99, 100
low temperatures, 25
gravity, 9, 85, 91, 101, 107, 115, 116, 123
groundwater, vii, viii, 2, 3, 5, 19, 24, 81, 89
growth, 11, 23, 94, 96, 107, 118, 122, 130 M
macroscopic approach, 153

H magnitude, 24, 121, 149, 150
management, 3, 25, 35
heat transfer, 80, 93, 107, 130
mass, vii, ix, 20, 44, 45, 93, 94, 98, 99, 110,
heptan, 160, 162, 163
111, 128, 129, 133, 135, 136, 137, 139,
heterogeneity, 152, 157
140, 143, 147, 148, 151, 154, 166, 169,
humidity, 4, 5, 12, 13, 14, 18, 22, 82, 148,
170, 173, 174, 175, 177, 180, 182
164
materials, 7, 27, 77, 131, 157, 161
hydrogen, 20, 150
matrix, 8, 11, 21, 23, 47, 50, 52
hypothesis, 182
matter, 20, 25, 144
hysteresis, v, viii, 11, 18, 41, 42, 43, 53, 55,
measurement, vii, x, 4, 16, 21, 22, 23, 81,
66, 67, 78, 152, 154, 157
85, 132, 134, 135, 136, 146, 149, 150,
hysteresis loop, 67
152, 153, 158, 163, 164, 179, 188
media, x, 2, 76, 94, 129, 134, 149, 150, 154,
I 155, 156, 158, 161, 163, 164, 188, 189,
190
integration, ix, 42, 52, 55, 57, 60, 66, 69, 76, melt, 81, 91, 116, 126
77 melting, ix, 80, 88, 91, 111, 116, 117, 118,
interface, 107, 122, 123, 142, 143, 145, 151 119, 121, 126, 132
isotherms, 154, 155, 157, 158, 160, 164, melting temperature, 117, 119
187 migration, vii, ix, 79, 80, 81, 86, 93, 126,
iteration, 52, 55, 116 127
modelling, 43, 53, 69, 73, 76, 128
196 Index
models, ix, 3, 12, 13, 14, 17, 18, 28, 53, 77, porous media, 11, 13, 26, 27, 28, 42, 76, 77,
78, 80, 104, 109, 127, 129, 131, 156 78, 94, 95, 96, 107, 116, 117, 122, 126,
modulus, 45, 67, 71, 74, 184 129, 130, 131, 189, 190
moisture, viii, 2, 3, 10, 11, 12, 13, 14, 16, preservation, viii, 1, 2, 135
17, 18, 19, 20, 21, 22, 23, 41, 77, 92, 135 pressure gauge, 21
moisture content, v, 1, 2, 3, 10, 11, 12, 16, pressure gradient, 9, 123
17, 19, 20, 23, 77 pure water, 151, 161, 166, 169, 172, 174,
molar volume, 141, 144, 173 181
molecules, x, 9, 93, 134, 135, 136, 150, 170
momentum, 47, 98, 111, 114
R
mualem, 15, 16, 17
multiphase flow, ix, 42, 76, 78, 79, 96, 126
radius, 52, 117, 136, 143, 145, 149, 150
relaxation, 96, 97, 113, 114, 119
N remediation, xi, 3, 134
resistance, 21, 119, 122, 127
natural resources, viii, 1, 2, 23 response, vii, viii, 28, 41, 42, 66, 67, 69, 72,
neutron probe, 20, 23 73, 76, 77, 78, 80, 128
numerical analysis, ix, 42
S
O
saturation, viii, 4, 8, 9, 10, 11, 12, 13, 14,
organic compounds, 5 16, 18, 41, 42, 43, 44, 46, 53, 54, 55, 56,
organic matter, 5, 19, 20, 25, 94 57, 59, 60, 63, 66, 67, 68, 69, 71, 72, 75,
osmotic dehydration, x, 134, 165, 169, 171 143, 156, 161, 162, 164, 168, 169
osmotic pressure, 172, 173, 174 semi-permeable membrane, 146, 150, 152,
153, 172, 188
sensor, 21, 23, 82, 148, 150
P
shape, ix, 13, 42, 50, 62, 63, 64, 74, 135,
161
permeability, 15, 27, 47, 67, 71, 122
simulation, 62, 63, 76, 77, 104, 106, 124,
phase transformation, 93, 129
127, 130, 131
phase transitions, 130
simulations, 3, 66, 69, 80, 124
physical characteristics, 25
skeleton, 67, 71, 94, 171, 174, 181, 182
physical chemistry, 164
soil particles, 9, 86, 107, 122
physical phenomena, 150
soil pollution, 3
physical properties, 94
soil type, 6, 22
porosity, 5, 6, 7, 14, 25, 46, 53, 55, 59, 94,
soils, v, vii, viii, x, 2, 3, 4, 5, 6, 7, 8, 9, 10,
108, 109, 131, 156
12, 13, 14, 15, 16, 17, 18, 21, 23, 24, 25,
porous materials, 135
26, 27, 28, 31, 35, 38, 41, 42, 43, 44, 47,
49, 52, 69, 73, 74, 76, 77, 78, 86, 88, 90,
Index 197
91, 92, 94, 130, 131, 133, 134, 135, 153, tensiometer, 150, 151, 152, 157, 158, 164,
156, 157, 158, 161, 163, 164 173
solid phase, x, 5, 14, 45, 47, 48, 134, 135, thawing, ix, 79, 80, 81, 82, 83, 88, 89, 90,
146, 151, 161, 162, 170, 174, 176, 177, 91, 92, 93, 126, 128
182 thermal-physical properties, vii, ix, 79
solution, x, 5, 12, 18, 19, 21, 55, 128, 134, thermodynamic equilibrium, 188
136, 142, 150, 158, 159, 160, 161, 165, thermodynamics, x, 134, 137, 164, 174, 188
166, 169, 171, 172, 173, 189 three-dimensional space, 52
species, 5, 115, 135, 139, 140, 146, 165, time domain reflectometry, 22, 28
174, 188, 189 transformation, 19, 131, 139, 141, 175, 182
state, viii, ix, x, xi, 7, 12, 16, 53, 56, 57, 66, transformations, 25, 152, 182
67, 71, 88, 133, 134, 138, 139, 141, 146, transport, 2, 3, 14, 15, 31, 35, 38, 93, 94,
147, 148, 150, 159, 161, 163, 164, 168, 128, 131, 170, 172, 174, 189
174, 175, 178, 179, 180, 182, 186, 187,
188
U
stress, 7, 8, 27, 43, 74, 75, 76, 77, 78, 123,
136, 138, 165, 182, 185, 188
uniform, x, 84, 86, 87, 104, 126, 134, 136,
stress tensor, 136, 138, 165, 188
150, 171, 175
structure, vii, ix, x, 3, 9, 11, 20, 25, 79, 93,
unsaturated media, 2, 9
94, 96, 107, 122, 126, 134, 149, 161,
unsaturated soil, v, vii, viii, ix, 1, 2, 3, 4, 5,
170, 171, 188
6, 7, 8, 9, 10, 12, 17, 18, 23, 26, 27, 28,
superficial layers, vii, x, 133, 134, 178, 189
31, 35, 38, 41, 42, 43, 44, 47, 49, 55, 66,
surface area, 108, 109
69, 73, 74, 76, 77, 78, 79, 80, 81, 83, 93,
surface energy, 117
94, 96, 107, 108, 126, 127, 128, 129, 190
surface layer, x, 134, 135
surface tension, 99, 115, 122, 123, 143, 145,
166 V
vadose, vii, viii, 2, 4, 28, 128

T Van Genuchten, 12, 13, 14, 15, 16, 17, 28,
54, 66, 78
temperature, vii, ix, x, 5, 21, 24, 25, 79, 80,
vapor, 8, 99, 102, 128, 143, 145, 146, 148,
81, 82, 83, 84, 85, 88, 89, 90, 91, 92, 93,
150, 159, 173
94, 99, 101, 102, 103, 104, 105, 107,
variables, 2, 13, 15, 48, 136, 137, 138, 174,
112, 113, 116, 117, 119, 121, 126, 127,
175, 179, 182, 187
128, 133, 134, 138, 140, 141, 142, 143,
variations, x, 42, 45, 63, 67, 72, 85, 91, 127,
144, 146, 152, 153, 159, 161, 162, 165,
128, 134, 139, 159, 182
171, 175, 178, 182, 185, 188
velocity, 20, 44, 97, 98, 100, 109, 113, 114
temperature distribution, v, vii, ix, 79, 80,
viscosity, 47, 97, 114, 122
81, 83, 84, 88, 89, 93, 100, 104, 105,
Vogel and Cislerova, 14
107, 113, 126, 127
volatile organic compounds, x, 134, 135
198 Index
water evaporation, 85
W
water migration, vii, ix, 79, 80, 81, 85, 90,
93, 107, 126, 127
water, v, vii, viii, ix, x, xi, 1, 2, 3, 4, 5, 7, 8,
water resources, 4, 26, 28
9, 10, 11, 12, 13, 14, 15, 17, 18, 19, 21,
water supplies, 121
22, 23, 24, 26, 27, 28, 29, 30, 31, 32, 33,
water vapor, 148, 153, 169
34, 35, 37, 38, 41, 43, 44, 47, 49, 50, 53,
wetting, viii, 8, 11, 18, 41, 43, 53, 54, 55,
67, 71, 77, 78, 79, 80, 81, 82, 84, 85, 86,
56, 57, 58, 60, 61, 62, 63, 65, 66, 67, 73,
87, 88, 90, 91, 92, 93, 94, 96, 99, 101,
78, 99, 152
102, 103, 104, 105, 106, 107, 116, 117,
119, 120, 121, 122, 123, 124, 125, 126,
127, 128, 129, 130, 131, 133, 134, 135,
143, 148, 149, 150, 151, 152, 153, 154,
155, 156, 157, 158, 160, 161, 162, 163,
164, 165, 166, 167, 168, 169, 170, 171,
172, 173, 174, 175, 182, 184, 185, 188,
189, 190, 191

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ENVIRONMENTAL REMEDIATION TECHNOLOGIES,

REGULATIONS AND SAFETY

Additional books and e-books in this series can be found

NOTICE TO THE READER

Library of Congress Cataloging-in-Publication Data

ISBN:  HERRN

Published by Nova Science Publishers, Inc. † New York

This compilation opens with an exploration of the vadose, or

definition, the mass chemical potential of a constituent in a soil represents

remaining constant. It quantifies the action of the rest of the environment

state to that of a solution in soil opens perspectives on applications such as

UNSATURATED SOILS: ASPECTS THAT

Teresa M. Reyna*, PhD, Santiago M. Reyna, PhD

Humankind increasingly puts more pressure on natural resources.

Keywords: unsaturated soils, moisture content, unsaturated media

where the selection of representative variables and hypotheses are adjusted

interactions that can generate contamination and deterioration. Pollution

the organization of the solid components together determines the amount

soil solution. In addition, it provides the oxygen necessary for the

As it was presented in previous paragraphs, the soil is constituted by

Table 1. Porosity values for different soil types (Davis, 1969)

Material Porosity percentage

The porosity can be applied to granular material or fractured material;

Representative Elementary Volume

It should be mentioned that porosity cannot be defined as values

STATE OF TENSIONS IN UNSATURATED SOILS

Effective stresses can be defined as those functions of the total stresses

There are several expressions to determine the effective stresses for

Table 2. Expressions of effective stresses for unsaturated soils

Equation Variables Author

The deformation of partially saturated soils has been extensively

WATER IN SATURATED AND UNSATURATED MEDIA

In a saturated medium it is possible to indicate different forces in water

(1) First Absorption layer: of the order of ten molecules of thickness

probably occurs in a narrow transition zone in natural soils, over the

CURVES OF MOISTURE - SUCTION OF SOILS

In soil moisture-suction curves, it is observed that granular soils for not

HYDRAULIC FUNCTIONS OF THE SOIL

where θr and θs, residual and saturated water content, , empirical

where , n and m are empirical constants. Van Genuchten equation with

diffusivity, D = K dh/dq) that are very complicated to study the flow of

(presented by Simunek and others, 1996), modified Van Genuchten’s

Ks is the hydraulic conductivity in saturation state and l is a parameter

where hb: suction, : pore distribution index.

Table 3. Parameters for water content

Moisture models Parameters for water Parameters for models of

Brooks and Corey r, s, ,  Ks, hb, 

in infiltration studies, especially when it is desired to try to couple the

PROCESSES UNDER WHICH THE SOLUTE

The process of transporting a solute in the soil where volatilization,

MEASUREMENT OF SOIL MOISTURE CONTENT

The evaluation of soil moisture content at different suction conditions

composition of the solution phase can play a determining role in soil

A neutron probe is a sophisticated and accurate piece of equipment that

Tensiometers are widely used to measure the available water content of

Granular Matrix Sensors

pores in the gypsum blocks, allowing greater sensitivity in the range of

Time Domain Reflectometry (TDR)

The TDR system consists of an oscilloscope connected to two or three

measurements or continuous measurements by connecting the fixed

Reflectometry in the Frequency Domain (FDR)

The FDR method is also known as a capacitance probe. The electrodes

CLIMATE CHANGE EFFECTS ON SATURATED

ISBN: HERRN