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Gibbsian Surface Thermodynamics

Janet A. W. Elliott*

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ABSTRACT: Gibbsian composite-system thermodynamics is the

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framework governing the equilibrium of composite systems,

including systems that at equilibrium have more than one value
of pressure because of the action of surface tension, semipermeable
membranes, or fields, and thus cannot be treated as simple systems.
J. W. Gibbs’s paper that lays out composite-system thermody-
namics, “On the Equilibrium of Heterogeneous Substances”,
communicated in two parts in 1876 and 1878, is widely regarded
as one of the most important pieces of scientific literature of its
century. Many scientists adopted and stressed the importance of
Gibbsian thermodynamics. In 1960, H. B. Callen wrote a textbook
that made Gibbsian composite-system thermodynamics more
accessible to thermodynamicists. However, Callen’s book left out
Gibbs’s work on curved fluid interfaces and did not treat the complicated nonideal systems of interest to today’s thermodynamicists.
In this Feature Article, I have attempted to convey in a comprehensive manner the framework of Gibbsian composite-system
thermodynamics including in detail the treatment of systems with interface effects and with nonideal, multicomponent phases. This
work lays out the relationships between important equilibrium equations including the following: the Gibbs−Duhem equation, the
Gibbs adsorption equation, the Young−Laplace equation, the Young equation, the Cassie−Baxter equation, the Wenzel equation,
the Kelvin equation, the Gibbs−Thompson equation, and the Ostwald−Freundlich equation, including nonideal and
multicomponent forms. Equations of state that are often useful for Gibbsian composite-system thermodynamics are reviewed
including adsorption isotherms and our own work on two semiempirical equations of state: the Elliott et al. form of the osmotic virial
equation and the Shardt−Elliott−Connors−Wright equation for the temperature and composition dependence of surface tension. I
summarize the work of our group developing Gibbisan composite-system thermodynamics including new equations for such things
as the curvature-induced depression of the eutectic temperature or the removal of azeotropes by nanoscale fluid interface curvature.
Gibbsian composite-system thermodynamics has broad applications in biotechnology, nanostructured materials, surface textures and
coatings, microfluidics, nanoscience, atmospheric and environmental physics, among others.

1. INTRODUCTION tively). Many principles and equations must be added to these

Thermodynamics is the study of mathematical relationships
arising from physical laws governing energy and entropy.1 In
different disciplines, the word thermodynamics brings different
subsets of the topic to mind. A mechanical engineer may think of
energy balance and entropic efficiency of devices used in a power
generating thermodynamic cycle. A chemical engineer may
think of multicomponent phase equilibrium or chemical
reaction equilibrium in liquids and vapors. A materials engineer
may think of thermodynamic phase diagrams of solids. A
physicist may think of using thermodynamics to unite the
fundamental theories of general relativity and quantum
mechanics or to understand the thermodynamic properties of
a cosmological object. A physical chemist may think of quantum
statistical calculations of molecular energy levels. In the
historical approach to thermodynamics, the subject is under-
stood in terms of the first and second laws of thermodynamics
(energy balance and the entropy increase principle, respec-
laws: principles and equations that at first glance appear to be
unrelated, owing to the haphazard way in which they were
discovered by a myriad of esteemed scientists starting in the
1600s up until 1876. Then, in one of the most important pieces
of scientific literature of the 19th century, J. Willard Gibbs
published in two parts his famous paper, “On the Equilibrium of
Heterogeneous Substances”, that recast thermodynamics as a
mathematical study, showing that, from a small number of
postulates, the previous thermodynamic results could be
obtained by mathematical derivations of multivariable calculus.2
Received: June 29, 2020
Revised: September 6, 2020
Published: October 22, 2020

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In that paper, Gibbs invented many of the cornerstones of
physical chemistry such as chemical potential. The 299 page,
700 equation tome by Gibbs is fairly inaccessible to all but the
most diligent of well-trained thermodynamicists. Many
scientists, including Ostwald3 and Guggenheim,4 adopted and
stressed the importance of Gibbsian thermodynamics. In 1960,
Herbert B. Callen wrote a textbook presenting the Gibbsian
postulatory approach in a clear and pleasing manner, and his
textbook is used in many thermodynamics graduate courses to
this day.5 Although an excellent treatise on thermodynamics in
its own right, Callen’s book does not cover one important part of
Gibbs’s famous paper: the treatment of systems with curved fluid
interfaces.
Many of the thermodynamic principles with which people are
most familiar are only valid for simple systems. A simple system is
one that at equilibrium has constant values of intensive properties
throughout. Systems that cannot be treated as simple systems
include systems that have multiple pressures at equilibrium due
to the action of surface tension of a curved fluid interface, due to
the presence of a semipermeable membrane, or due to the action
of fields. The important contribution of Gibbs’s famous paper
was to develop the thermodynamics of composite systems. A
composite system is a system composed of a number of constituent
subsystems, each of which may be treated as a simple system. A
composite system may or may not itself be a simple system. This
allows the application of rigorous thermodynamics to many
nonsimple systems including biological systems with semi-
permeable membranes, systems with field-induced pressure
gradients, and systems with highly curved fluid interfaces (drops,
bubbles, emulsions, foams, aerosols, and multiphase fluids in
solid porous media) that occur in almost every manufacturing
and resource industry; are the basis for novel surface, colloidal,
microfluidic, and nanofluidic technologies; are central to
environmental processes; and are the focus of much of modern
science.
The objectives of this article are to outline briefly the methods
of Gibbsian composite-system thermodynamics, with specific
attention to its application to systems with curved fluid
interfaces, and to review several recent applications.
2. GIBBSIAN COMPOSITE-SYSTEM
THERMODYNAMICS METHOD
“The single, all-encompassing problem of thermodynamics is
the determination of the equilibrium state that eventually
results after the removal of internal constraints in a closed,
composite system.”5
The steps of Gibbsian composite-system thermodynamics are
i. Define the system so that the mathematical constraints are
clear and the problem is posed to answer the question you
want.
ii. Perform a unified derivation of the complete set of
equations that must be satisfied for equilibrium by setting
the differential of the composite-system entropy to zero
subject to the mathematical constraints. This can be done
algebraically for some problems and with the calculus of
variations and the method of Lagrange multipliers for
others.
iii. Analytically or numerically solve the coupled conditions
for equilibrium from step ii using specific equations of
state, yielding particular equilibrium states that satisfy the
conditions for equilibrium. The equations of state do not
come from within the postulatory equilibrium composite-
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system thermodynamics of Gibbs but must be found
separately. Equations of state may be found by making
empirical measurements of some variables and then using
Gibbsian thermodynamic relationships involving partial
derivatives to get the equations in the desired forms.
Alternatively, equations of state may be derived from
statistical thermodynamics.
iv. Formally identify which function acts as the thermody-
namic potential (equivalently free energy). Plot this
potential versus the variable or variables of interest and
examine the number and nature of extrema to provide
relative stability of different equilibrium states that satisfy
the conditions for equilibrium, thus determining the
behavior of the system. Maxima and inflection points in
the free energy correspond to unstable equilibria and
minima correspond to stable equilibria.
Following each and every one of steps i−iv above prevents the
pitfalls of much surface thermodynamics research that uses
equations from different steps derived with inconsistent
assumptions, or uses a rigorous approach in one step but not
in another. For different geometries, there are specific parts of
the steps above that provide challenge and opportunity for
innovation and fundamental contribution. In specifying the
system (step i), it is important to use insight to define the system
to ask the right question. The derivations in step ii may also be
challenging; new mathematics may be required. In finding
solutions to the conditions for equilibrium (iii) and performing
the stability analysis (iv), new equations of state may be needed.
Even with the equations of state, performing the stability analysis
is not trivial; new analytical and computational techniques are
often required.
2.1. Finding the Conditions for Equilibrium. The
procedure to derive the conditions for equilibrium begins with
the statement that at equilibrium the entropy of an isolated
composite system is an extremum subject to the constraints on
the system, including importantly conservation of energy. Thus,
we begin by setting
dS C = ∑ dS j = 0
j (1)
where SC is the entropy of the composite system, Sj is the
entropy of simple subsystem j, and the summation is over all
subsystems that make up the composite system which may
include as one of the subsystems a surrounding reservoir that
interacts with the system. An alternative approach, that was the
original approach of Gibbs,2 is to extremize the energy of an
isolated system subject to entropy being held constant. These
two approaches are formally equivalent due to the requirement
that entropy be a monotonically increasing, first-order,
homogeneous, differentiable function of the internal energy
that is invertible (see pages 56 and 57 of the Ox Bow Press
version of Gibbs’s paper2 and page 28 of Callen’s book5). The
approach of beginning with eq 1 is more intuitive and
convenient for many problems, and so, it is the approach
adopted here.
Next, the entropy of each subsystem in eq 15 is replaced with
the appropriate differential form of an Euler relation. For bulk
subsystems, the differential Euler relations take the form (eq 12
of Gibbs’s paper,2 eq 2.6 of ref 5):
1 Pj j μi j
dS j = j
j dU + dV − ∑ dNij
T Tj i
Tj (2)
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where Uj, Vj, and Nji are the internal energy, the volume, and the
number of moles of component (molecular species) i,
respectively, in the subsystem j; along with Sj these are the
extensive variables of the bulk subsystem. Tj, Pj, and μji are the
temperature, the pressure, and the chemical potential of
component i, respectively, in the subsystem j; these are the
intensive variables of the bulk subsystem. The summation is over
all molecular species present in the bulk subsystem.
Interfaces between two bulk subsystems are treated as
additional subsystems (i.e., separate interface phases). In
Gibbs’s approach, interface phases are modeled by the
combination of a phase having area but no volume (a dividing
surface) with surface excess properties accounting for all effects
of the interface. By mathematically uniquely placing the dividing
surface, all thermodynamic variables of the surface are
accounted for in a way that captures all effects of the interface.
This is an important concept to understand because it is not to
say that the approach of Gibbs can only be applied to interfaces
that have no reach into the adjoining bulk phases, but rather that
the excess molecules and energy of that reach must be added to
the presence of a uniquely defined infinitely thin surface to
completely describe the system. For each interface, the
differential Euler relations take the form (eq 501 of Gibbs’s
paper2)
1 σj j μi j
dS j = d U j
− dA − ∑ dNij
Tj Tj i
Tj (3)
where, Aj is the area of the dividing surface, and Sj, Uj, and Nji are
the surface excess entropy, the surface excess internal energy,
and the surface excess number of moles of component i,
respectively, of interfacial phase j; these are the extensive
variables of the interface subsystem. Tj, σj, and μji are the
temperature, the interfacial tension, and the chemical potential
of component i, respectively, of the interface j; these are the
intensive variables of the interface subsystem. The summation in
eq 3 is over all components (molecular species) present in the
interface subsystem. Which components are present in the
interface subsystem depends on the choice of how to uniquely
place the dividing surface. The Gibbs Dividing Surface approach
is to place the dividing surface such that one of the components
in the bulk phases is not in excess at the interface; this is the usual
choice for flat surfaces. The Gibbs Surface of Tension approach,
typically used for curved interfaces, is to place the dividing
surface such that the property of interfacial tension is
independent of curvature; in this case, all components will be
in excess at the interface. Note that interfacial tension of
interfacial phase j is defined
i ∂U j y
σ j = jjjj j zzzz
k ∂A {S j , Nij (4)
where the subscripts indicate that the derivative is taken with
surface excess entropy and surface excess numbers of moles of all
components of the interfacial phase held constant.
Once the differential Euler equations are substituted into eq 1,
the equation is in terms of differentials of the extensive variables,
but not all of these differentials are independent. Next, the
constraints that describe the relationships between changes in
the extensive variables are enumerated.
Conservation of energy is required. In the absence of fields,
this means that
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∑ dU j = 0
j (5)
where the summation is over all subsystems (bulk phases or
interface phases) that can exchange energy with one another. A
conservation of energy constraint is required for each set of such
connected subsystems.
Continuity requires
∑ dV j = 0
j (6)
where the summation is over all bulk phases that have a freely
moving boundary between them. A continuity constraint is
required for each set of such connected bulk phases.
Conservation of mass requires
∑ dNij = 0
j (7)
where the summation is over all subsystems that can exchange
molecules of component i. Conservation of mass constraints is
needed for each set of such connected phases. Separate
conservation of mass constraints are needed for each
component.
There are further geometrical constraints that are imposed by
the particular system under consideration. Typically, changes in
areas of interfaces are related by geometry to changes in bulk
phase volumes and areas of other interfaces. For example, for a
spherical drop of liquid of radius r surrounded by vapor, a
change in the area of the liquid−vapor interface ALV is related to
a change in the volume of the drop VL by
2 L
dALV = dV
r (8)
Finally, there may be other types of constraints imposed, for
example, by complex mechanical connections or stoichiometry
of chemical reactions. See example 1 on page 51 of ref 5 for a
worked problem with an interesting constraint imposed by the
mechanical connections of different parts of a composite system
by pistons connected by rods, and homework problem 2.9-1 on
page 58 of the same reference for a formally equivalent chemical
reaction equilibrium with the constraint imposed by stoichiom-
etry.
Once the differential Euler equations of the form of eqs 2 and
3 are substituted into eq 1, along with constraints of the form of
eqs 5−7, along with further geometrical or other constraints of
the defined composite system, and the like terms collected, the
extremization of entropy will now be written as an equation of
the form below
∑ (expression that depends d(extensive variable) = 0
on intensive variables )
(9)
where the differentials of independent variables that remain in
eq 9 are all independent because all relationships between
extensive variables have been applied. Because we are interested
in finding the conditions that make entropy an extremum for all
virtual displacements about equilibrium, eq 9 must be true for all
possible differentials of the extensive variables; therefore, the
coefficients in front of each independent variation must each be
set equal to zero. The equations that result from setting the
coefficients to zero form the complete set of conditions for
equilibrium that the system must satisfy.
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Fully described worked out examples of applying this
procedure to find the conditions for equilibrium for a wide
range of particular systems may be found in refs 5−15.
This procedure yields all the conditions for all three of
thermal, chemical, and mechanical equilibrium for a given
system. Some of the conditions for equilibrium that might be
found from this procedure follow:
thermal equilibrium:
Tj = Tk
for all subsystems j and k that can exchange energy,
chemical equilibrium:
μi j = μik
for all components i that can exchange between subsystems j and
k, and
∑ νμ
i i = 0
i (12)
for each independent reaction with stoichiometric coefficients
νi, and a wide variety of mechanical equilibrium conditions as
described below.
For two phases j and k separated by a freely moving uncurved
boundary, the mechanical equilibrium condition is
P j = Pk
For two phases A and B separated by a fixed, rigid,
semipermeable membrane through which can pass the solvent,
but not the solute on side A (Figure 1 a), the chemical−
mechanical equilibrium condition is
P A − PB = Π
Figure 1. Definition of variables for some of the systems of interest.
(a) Osmotic pressure difference across a semipermeable membrane.
(b) Sessile drop. (c) Fluid lens. (d) Cassie−Baxter wetting state.
(e) Wenzel wetting state. (f) Phase in a gravitational field.
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where Π is the osmotic pressure which depends on the
concentration on side A. (See eq 77 of Gibbs’s paper,2 eq 13.38
of ref 5, and pages 97−98 of ref 16.)
For a curved fluid interface, the mechanical equilibrium
condition is the Young−Laplace equation (eq 500 of Gibbs’s
paper2):
ij 1 1 yzz
P j − P k = σ jk jjj z
jR
k 1 R 2 zz{
+
(15)
(10)
where P is the pressure of the bulk phase inside the curvature, Pk
j
is the pressure of the bulk phase outside the curvature, σjk is the
interfacial tension of the interface between bulk phases j and k,
and (1/R1 + 1/R2) is twice the mean curvature of the interface.
(11) For a sessile drop of liquid, L, on a solid, S, surrounded by a
vapor, V (Figure 1 b), an additional mechanical equilibrium
condition to the Young−Laplace equation is the Young equation
(eq 672 of Gibbs’s paper2):
σ LV cos θ = σ SV − σ SL (16)
where, θ is the contact angle that the liquid−vapor interface
makes with the solid as measured through the liquid. The
contact angle that results from eq 16, or the equilibrium contact
angle on a smooth surface, is often called the Young contact
angle.
For a fluid lens of one liquid, L, on another liquid, L′,
surrounded by a vapor, V (Figure 1 c), there are two Young
(13) equations:9
σ LV cos β + σ LL′cos α = σ L′V (17)
σ LV sin β = γ LL′sin α (18)
where the angles α and β are as defined in Figure 1 c. Only eq 17
(14)
appears in Gibbs’s paper (as eq 561).2 As the number of curved
fluid interfaces intersecting one another in the system increases,
the number of Young equations that are in the set of equilibrium
conditions increases. One independent angle is required to
specify the intersection of one curved interface with a flat
interface; two independent angles are required to specify the
intersection of two curved fluid interfaces with a flat interface,
etc. Also, a Young−Laplace equation (eq 15) applies for each
curved fluid interface.
For a sessile drop sitting on a smooth but chemically
heterogeneous surface, or equivalently for a drop sitting on a
rough surface, where the drop does not penetrate the surface
roughness (the Cassie−Baxter wetting state, Figure 1 d), the
mechanical equilibrium condition (in addition to the Young−
Laplace equation for the liquid−vapor interface) that results
from the Gibbsian composite-system entropy extremization is a
line-fraction form of the Cassie−Baxter equation.14 In the case
of a smooth heterogeneous solid made up of different materials i,
the line-fraction Cassie−Baxter equation is14
cos(θCB) = ∑ λicos(θi)
i (19)
where θCB is the Cassie−Baxter contact angle shown on Figure 1
d, and the line fraction λi is the fraction of the three-phase
contact line that contacts material i with the Young contact angle
of θi. Equation 19 can be adapted to give the contact angle of a
drop sitting on a flat rough surface, where the drop does not
penetrate the surface roughness:
cos(θCB) = λ cos(θY ) − (1 − λ) (20)
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where line fraction λ is the fraction of the circumference of the
spherical cap in Figure 1 d that rests on the flat, but intermittent,
solid surface, and θY is the Young contact angle of the solid
surface.
For a sessile drop sitting on a rough surface, where the drop
penetrates into the surface roughness (the Wenzel wetting state,
Figure 1 e), the mechanical equilibrium condition (in addition
to the Young−Laplace equation for the liquid−vapor interface)
that results from the Gibbsian composite-system entropy
extremization is a new line-roughness form of the Wenzel
equation:15
cos(θ W ) = ρ cos(θY ) (21)
where θW is the Wenzel contact angle shown in Figure 1 e, and ρ
is the three-phase line roughness with a specific definition that
both accounts for the increased length of the three-phase contact
line over the length of the spherical cap circumference and takes
into account the orientation that the liquid−vapor interface
intersects the vertical portions of the solid (see ref 15 for more
description of the definition of ρ). Note that eq 21 is a simplified
form of the new Wenzel equation that is valid when the
contribution of the liquid in between the surface features is
negligible.15
For a fluid phase in a gravitational field (Figure 1 f), the
condition for chemical−mechanical equilibrium is (eq 234 of
Gibbs’s paper2)
μi j + Migz = const i (22)
for each component i and each phase j, where Mi is the molar
mass of component i, g is the magnitude of acceleration due to
gravity, z is the elevation above a reference, and consti is a
constant.
For a curved fluid interface in a gravitational field, the
mechanical equilibrium condition is2,8
ij 1 1 yzz dσ
PIj − PIk = σ jk jjj
z+
jR R 2 zz{
jk
k 1
+ cos ϕ
dz (23)
where PjI is the pressure of the bulk phase j inside the curvature at
a point on the interface, PkI is the pressure of the bulk phase k
outside the curvature at that point on the interface, σjk is the
interfacial tension of the j−k interface at that point on the
interface, R1 and R2 are the principal radii of curvature at that
point on the interface (defined as positive if phase j is inside the
curvature), z is the elevation of the point on the interface above a
reference, and ϕ is the angle that the normal to the interface at
that point on the interface makes with the vertical direction.
Unlike eqs 13−22, the mechanical equilibrium condition in eq
23 is not well-known. Equation 23 appears as eq 613 of Gibbs’s
paper,2 but it seems to have gone unnoticed by all but a few
researchers17 for 130 years. Gibbs had performed the derivation
of the conditions for equilibrium of a sessile drop in a
gravitational field in two unconnected parts, one for the curved
interface in a gravitational field and one for contact with the
solid.2 In 2008, Voitcu and Elliott provided a unified derivation
of all conditions for equilibrium of a sessile drop in a
gravitational field, arriving simultaneously at eqs 10, 11, 16,
22, and 23.8 Although the last term in eq 23 may be negligible in
many practical circumstances, it may become important at larger
field magnitudes.
2.2. Equations of State. In order to make a calculation of an
equilibrium state of the system in terms of measurable and/or
controllable variables, the conditions for chemical, thermal, and
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mechanical equilibrium must be combined with equations of
state that relate the variables of the system. Equations of state are
not found from within Gibbsian composite-system thermody-
namics and must be added separately, typically found from
measurements of the relationships between system variables or
from statistical mechanics based on assumptions or calculations
of molecular energies. The equations of state may be in a form
relating the intensive properties, i.e., μ−P−T equations for bulk
phases or μ−σ−T equations for interface phases, or the
equations of state may be in other forms depending on the
variables naturally appearing in measurements or statistical
ensembles from which the equations of state are found, e.g., P−
V−T equations, μ−N−T equations, or σ−N−T equations.
2.2.1. Gibbs−Duhem and Gibbs Adsorption Equations.
Two important relations of thermodynamics need to be
mentioned: the Gibbs−Duhem relation and the Gibbs
adsorption equation.
From the postulates of thermodynamics about the mathe-
matical properties of thermodynamic variables, the Euler
relations of thermodynamics may be written for each bulk
phase j (eq 55 of Gibbs’s paper,2 eq 3.6 of ref 5)
U j = T jS j − P jV j + ∑ μi j Nij
i (24)
and for each interfacial phase j (eq 502 of Gibbs’s paper2)
U j = T jS j + σ jAj + ∑ μi j Nij
(25)
i
Taking the derivative of eq 24 and subtracting eq 2 (rearranged
for dUj) reveals the Gibbs−Duhem relation (eq 97 of Gibbs’s
paper, eq 3.14 of ref 5):
S j dT j − V j dP j + ∑ Nij dμi j = 0
(26)
i
Taking the derivative of eq 25 and subtracting eq 3 (rearranged
for dUj) reveals the Gibbs adsorption equation (eq 508 of
Gibbs’s paper2):
S j dT j + A j dσ j + ∑ Nij dμi j = 0
i (27)
Equations 26 and 27 serve to illustrate that changes in the
intensive properties are not independent and must be related by
equations of state. Equations 26 and 27 are also useful equations
in converting equations of state from one set of variables to
another.
2.2.2. Some Bulk-Phase Equations of State for Use in
Gibbsian Composite-System Thermodynamics. There are
more thermodynamic equations of state than there are
thermodynamicists. Below are listed only a sample of equations
of state that have been useful in applications of Gibbsian
composite-system thermodynamics.
The ideal gas law is
PV = NRT (28)
where R is the universal gas constant. Substituting the ideal gas
law (eq 28) in the Gibbs−Duhem relation (eq 26) for a single
component and integrating at constant temperature yields the
dependence of ideal gas chemical potential on pressure:
i P y
μ(T , P) = μref (T , P ref ) + RT lnjjj ref zzz
kP {
(29)
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where Pref is a reference pressure and μref is the chemical
potential at that reference pressure.
For an incompressible substance, molar volume v does not
depend on pressure. Substituting this into the Gibbs−Duhem
relation (eq 26) for a single component and integrating at
constant temperature yields the dependence of chemical
potential on pressure for an incompressible substance:
ref ref ref
μ(T , P) = μ (T , P ) + v(P − P ) (30)
ÄÅ ÉÑ
A useful chemical potential equation for a slightly
Å Ñ
isothermal compressibility ÅÅÅÅκT = − v ∂P ÑÑÑÑ into the Gibbs−
compressible substance can be obtained by substituting constant
ÅÇ TÑ Ö
1 ∂v
( )
Duhem relation (eq 26) for a single component and integrating
at constant temperature to get18
1 developing such activity coefficient models is thermodynamic
μ(T , P) = μref (T , P ref ) − (v|P − v|P ref )
κT (31)
For a temperature range over which a substance can be
assumed to have a constant molar entropy s, the Gibbs−Duhem
relation (eq 26) for a single component can be integrated at
constant pressure to find the chemical potential dependence on
temperature:19
μ(T , P) = μref (T ref , P) − s(T − T ref ) (32)
For substances at a temperature far enough from the reference
temperature that entropy cannot be assumed to be constant, the
chemical potential dependence on temperature can be obtained
by substituting the identity (∂s/∂T)P = CP/T, where CP is the
constant-pressure molar heat capacity, into the Gibbs−Duhem
relation (eq 26) for a single component and integrating at
constant pressure to get
μ(T , P) = μref (T ref , P) − s ref (T − T ref )
T T C
∫ ∫
− ref ref P dT dT
T T T (33)
For an ideal dilute solution with solvent 1 and solute 2,
considering the entropy of mixing and assuming N2 ≪ N1 yields
(eqs 13.33 and 13.34 of ref 5)
μ1(T , P , x 2) = μ10 (T , P) − RTx 2 (34)
where x2 = N2/(N1 + N2) is the mole fraction of solute and
μ01(T, P) is the chemical potential of pure solvent at the given
temperature and pressure, and
μ2 (T , P , x 2) = ψ (T , P) + RT ln(x 2) (35)
where ψ(T, P) is a concentration-independent function. For a
solute with a solubility limit, eq 35 can be rewritten in terms of
ji x zy
the saturation mole fraction x2∞ as
μ2 (T , P , x 2) = μ20 (T , P) + RT lnjjj 2 zzz
jx z
k 2∞ {
(36)
where μ02(T,P) is the chemical potential of pure solute at the
given temperature and pressure.
There are many equations of state for nonideal multi-
component solutions of which excellent collections and
explanations can be found in refs 16 and 20. Herein, I mention
only two empirical approaches that are convenient to use with
Gibbsian composite-system thermodynamics: activity ap-
proaches and the osmotic virial equation. The idea of the
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empirical approaches is to add corrections into the ideal dilute
solution approaches and then fit to actual data to get a
parametrization of the corrections that is valid for a specific
solution.
In the activity approach,16,20,21 the chemical potentials of
solvent 1 and solute 2 are written as
μ1(T , P , x1) = μ10 (T , P) + RT ln(γ1x1) (37)
and
μ2 (T , P , x 2) = ψ (T , P) + RT ln(γ2x 2) (38)
where γi is the activity coefficient of species i, and ai = γixi is called
the activity. A variety of models have been developed to capture
the dependence of activity coefficients on various variables and
to facilitate fitting to data.16,20 An important concept in
consistency; that is, once the functional form of the activity
coefficient of one species is determined, the functional form of
the second species is not allowed to be arbitrarily assigned, but
rather eqs 37 and 38 along with their activity coefficient models
must satisfy the constant-temperature, constant-pressure form
of the Gibbs−Duhem equation (eq 26), i.e.
∑ Nij dμi j = 0
i (39)
2.2.2.1. Osmotic Virial Equation. In the osmotic virial
equation approach,21−29 the correction to the ideal, dilute
solution model is in the form of a polynomial expansion of the
concentration dependence of the solvent chemical potential.
This polynomial expansion can be done in different concen-
tration units, with each different polynomial expansion giving
rise to a different solution theory consistent with different
underlying assumptions. In terms of molality, m2 (moles of
solute 2 per kg of solvent 1), the chemical potential of the solvent
is given by
μ1(T , P , m2) = μ10 (T , P) − RTM1π (40)
where M1 is the molar mass of solvent and the osmolality π is
written as a polynomial expansion of molality
π = m2 + B2 m22 + C2m23 + ... (41)
where B2 and C2 are, respectively, the second and third osmotic
virial coefficients for use with molality. While there are
thermodynamic approaches for computing values of the osmotic
virial coefficients (see page 132 of ref 16), this is more
complicated than for the gaseous virial coefficients, and the
much more practical use of eq 41 is to treat the osmotic virial
coefficients as empirical constants obtained by fitting to
experimental measurements of osmolality. The osmotic virial
equation was originally developed in terms of molarity by
MacMillan and Mayer22 and later in terms of molality and mole
fraction by Hill.23,24 It is a widely used equation of state for
aqueous solutions in biology, such that osmometers that
measure freezing-point depression, osmotic pressure, or vapor
pressure (phenomena resulting from phase equilibrium equality
of chemical potentials) give readouts in osmolality.
Our group has made several contributions to the osmotic
virial equation. First, we proposed a simple extension for
electrolytes25
π = k 2m2 + B2 (k 2m2)2 + C2(k 2m2)3 + ... (42)
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where k2 could be referred to as a dissociation constant of

electrolyte solute 2, but it is important to note that k empirically
accounts for more electrolyte effects that just dissociation; so,
the value obtained from fitting to data might not indicate an
actual degree of electrolyte dissociation. Equation 42, truncated
to second order with only two empirical parameters (k2 and B2),
fits sodium chloride solution data as accurately as the Pitzer−
Debye−Huckel equation, a more sophisticated electrolyte
theory requiring 6 empirical parameters.25
Second, we fit experimental data to provide parameters
(dissociation constants and osmotic virial coefficients) for
aqueous solutes of interest for applications in cryobiology
(sodium chloride, potassium chloride, dimethyl sulfoxide,
glycerol, propylene glycol, ethylene glycol, ethanol, methanol,
mannitol, sucrose, dextrose, trehalose, hemoglobin, bovine
serum albumin, ovalbumine,26 and hydroxyethyl starch27).
Third, we contributed combining rules for the osmotic virial
coefficients that when combined with the osmotic virial Figure 2. Predictions (not fits) by the Elliott et al. form of the
equation mixing rule yield the following equations (to third multisolute osmotic virial equation compared with experimental
measurements. The triangles, circles, and squares represent exper-
order) for chemical potential of the solvent in a multisolute imental measurements for each of the multisolute solutions, while the
solution with r − 1 solutes:25,28 colored solid lines represent predictions (not fits) of eq 44 for each
corresponding solution. The triangles (purple) represent data from
μ1(T , P , m2 , m3 , ..., mr ) = μ10 (T , P) − RTM1π
r ÄÅÅ (B + B ) ÉÑ
(43) Hildebrandt’s thesis33 for an aqueous solution of dimethyl sulfoxide

ÅÅ i ÑÑ
π = ∑ kimi + ∑ ∑ ÅÅÅ kimikjmj ÑÑÑÑ
(DMSO) and NaCl, at a solute mass ratio of DMSO:NaCl = 2:1. The

Å ÑÑ
r r

i=2 j=2 Å
circles (blue) represent data from Elliott et al.28 for an aqueous solution

ÅÇ ÑÖ
j
2
i=2
r r r solution of bovine serum albumin (BSA) and ovalbumin, at a solute
+ ∑ ∑ ∑ [(CiCjCk)1/3 kimikjmjkkmk ]
i=2 j=2 k=2 (44)
Importantly, eq 44 can be used to make predictions of osmolality
(and therefore freezing-point depression, osmotic pressure,
vapor pressure, etc.) for solutions with one solvent and many
solutes (r components in total) using only tabulated dissociation
constants and osmotic virial coefficients from single-solute
solutions and not requiring fitting to any multisolute solution
data. The combining rules in eq 42, namely
Bi + Bj
Bij =
2 (45)
and
Cijk = (CiCjCk)1/3 (46)
are referred to for the gaseous virial equation as “Guggenheim’s
̈ approximation”. However, we point out in Zielinski et al.29
naive
that because the osmotic virial equation mass balance has one
more degree of freedom than the gaseous virial equation (due to
the presence of a solvent), the reasons that make these
combining rules inappropriate for the gaseous virial equation
do not apply to the osmotic virial equation. The multisolute
osmotic virial equation, eq 44, is extremely useful because this
single equation can make accurate predictions for combinations
of many types of solutes such as organic solvents,25,26,28,30
alcohols,25,26,28,30 sugars,26,30 starches,27 proteins,26,28 electro-
lytes,25,26,30 and ionic31 and nonionic32 micelle-forming
surfactants, whereas most thermodynamic solution theories
are only applicable to a small class of molecules and cannot be
used for mixtures of molecules from different classes. Three
examples are shown in Figure 2.
Fourth, we point out an important feature of the multisolute
osmotic virial equation. Because the contribution of each solute
species is represented by a polynomial, and adding polynomials
10865
of DMSO and glycerol, at a solute mass ratio of DMSO:glycerol = 2:1.
The squares (green) represent data from Yousef et al.34 for an aqueous
mass ratio of BSA:ovalbumin = 3:2. The inset at top left provides a
closer look at the lower end of both the molality and osmolality axes.
Reproduced with permission from ref 29. Copyright 2017 American
Chemical Society.
yields polynomials, multiple molecular species may be
represented by a single “grouped solute”, and we show that
using such a grouped-solute approach is mathematically
equivalent to having treated each species individually in the
multisolute osmotic virial equation.29 This means that the
multisolute osmotic virial equation can be applied to circum-
stances where the individual molecular solute species cannot be
enumerated, such as the cytoplasmic solution inside a living
cell.29,35−37
Fifth, we derived a solute chemical potential equation29,38 that
is thermodynamically consistent with the solvent chemical
potential of the multisolute osmotic virial equation, presented
here in molality units:29
μs (T , P , m2 , m3 , ..., ms , ..., mr )
r
= ksψs + RTks[ln(M1ms) + ∑ [(Bii + Bss )kimi]
i=2
r r
3
+ ∑ ∑ [(CiiiCjjjCsss)1/3 kimikjmj]]
2 i=2 j=2 (47)
where, ψs is a constant that depends only on temperature and
pressure and is specific to solute s, and M1 is the molar mass of
the solvent.
2.2.2.2. Chemical Potential Equations with Multiple
Dependencies. Finally, note that, through combinations of eq
34−38, 40, 43, or 47 for chemical potential dependence on
composition with equations for chemical potential dependence
on pressure (eq 29, 30, or 31) or temperature (eq 32 or 33),
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chemical potential equations with multiple dependencies can be
found.
For example, consider the need to compute the colligative
freezing-point depression caused by the presence of a solute in
the absence of any curvature effects of the ice−solution interface
(see Figure 3).
Figure 3. Composite system to consider for freezing-point depression.
For clarity, I will assume an aqueous solution, but all that
follows can be generalized by replacing the word water with the
word solvent. Assuming that a solid composed of pure water is in
equilibrium with an aqueous solution with one solute, the
thermal and mechanical conditions for equilibrium in eqs 10 and
13 indicate that the solid and liquid are at the same temperature
and pressure. The chemical potential equilibrium condition for
the pure water solid and the water in the liquid solution can thus
be written from eq 11 as
μ1S (Tfp , P) = μ1L (Tfp , P , m2)
(48)
where Tfp is the freezing point of the solution. Setting the
freezing point of pure water, T0fp, as the reference temperature,
the chemical potential of the solid pure water ice can be written
from eq 32 as
μ1S (Tfp , P) = μ10 (Tfp0 , P) − s10S(Tfp − Tfp0)
(49)
s0S
where is the molar entropy of pure water solid ice, assumed
1 thermostatistical model used to describe a gas-phase molecule),
for this example to be a constant that is independent of
temperature. Combining eqs 32 and 40 yields the chemical
potential of the water in the liquid solution:
μ1L (Tfp , P , π ) = μ10 (Tfp0 , P) − s10L(Tfp − Tfp0) − RTfpM1π
(50)
where s0L
1 is the molar entropy of pure water in liquid form,
assumed to be constant. Substituting eqs 49 and 50 into 48 and
rearranging yields the freezing-point depression for an aqueous
solution with osmolality π:19,26,28,39
RTfp0M1π
(s10L − s10S)
Tfp0 − Tfp = RM1π
1+
(s10L − s10S) (51)
where the judicious choice of reference temperature as the
freezing point of pure water enabled the reference chemical
potentials to cancel out.
2.2.3. Some Surface Phase Equations of State for Use in
Gibbsian Composite-System Thermodynamics. As with the
bulk-phase equations of state, I list herein only a few of the
surface-phase equations of state that have found use in Gibbsian
composite-system thermodynamics, namely, several adsorption
isotherms and one empirical equation for the dependence of
surface tension on temperature and composition.
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2.2.3.1. Adsorption Isotherms. Adsorption isotherms are
equations that describe the relationship between the number of
adsorbed molecules on a surface (surface excess moles of the
component of interest), Nσ, and the controllable variables of
temperature, T, and additional independent variables of the
adjoining bulk fluid phase such as pressure in an adjoining
single-component gas phase, PG, or composition in the case of an
adjoining multicomponent fluid phase. Because the equilibrium
of a composite system consisting of a surface phase and
adjoining bulk fluid phase requires equality of chemical
potentials for the component adsorbed on the surface and in
the adjoining fluid phase, adsorption isotherms can also be
expressed by the adsorbed component chemical potential
equation with which they are consistent, which is written in
terms of the variables of the adsorbed phase. Adsorption
isotherm equations can have their foundation in empirical
measurements of adsorption or statistical mechanical deriva-
tions starting with assumptions about properties of the molecule
of interest in the adsorbed and adjoining bulk phases.
A well-known adsorption isotherm is the Langmuir
adsorption isotherm, which is the isotherm for noninteracting
adsorbed molecules that adsorb from a gas phase onto fixed
adsorption sites on a solid that can hold at most one molecule on
a site. The Langmuir adsorption isotherm40 (eq 7-10 of ref 41)
and the corresponding chemical potential for the adsorbed
molecules (eq 7-8 of ref 41) are given by
MPG
N σ (T , A , PG) =
P + 1/(φGq σ )
G
(52)
ÄÅ ÉÑ
ÅÅ ÑÑ
and
μ (T , A , N ) = RT lnÅÅÅ Å ÑÑ
σ σÑ
ÅÅÇ (M − N )q ÑÑÑÖ
Nσ
σ σ
(53)
respectively, where M is the number of adsorption sites which is
proportional to surface area A, φG is a function of temperature
(the temperature dependence of which depends on the
and qσ is the statistical mechanical partition function of a single
adsorbed molecule. For the Langmuir adsorption isotherm, qσ is
a function of temperature. Ward and Elmoselhi42 and Elliott and
Ward43 developed an extension to the Langmuir adsorption
isotherm that allowed for interaction between adsorbed
molecules making qσ a function of both temperature and the
surface density of adsorbed molecules.
The Brunauer−Emmett−Teller (BET) isotherm describes
adsorption from a gas onto a solid with fixed adsorption sites
where, rather than being limited to one molecule per adsorption
site, any number of molecules can adsorb on a given adsorption
site leading to the amount adsorbed becoming infinite as the gas-
phase saturation pressure is approached and a liquid condenses
on the surface. The BET adsorption isotherm is given by44 (see
also eqs 7-36 to 7-38 of ref 41)
PG
MC P
N σ (T , A , PG) = ∞
PG PG PG
(1 − )(1 −
P∞ P∞
+ CP
∞
) (54)
where M is the number of adsorption sites which is proportional
to surface area A, and P∞ is the saturation pressure (pressure at
which the gas condenses) which is a function of temperature.
While the temperature-dependent constant C can be found from
a rather simplified statistical thermodynamics derivation to be
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the ratio of the single-molecule partition function of molecules N σ (T , x 2L) Kx 2L

in the first layer of adsorbed molecules to the single-molecule
partition function of molecules in the second and later layers (eq
7-37 of ref 41), in practice C is used as an empirical fitting
parameter, and the most common usage of the BET isotherm is
as a fit to nitrogen adsorption data to measure surface area of
porous materials (the BET surface area).
Ward and Wu proposed the ζ-isotherm for adsorption from a
gas onto a solid with fixed adsorption sites where a cluster of
molecules can adsorb at a given adsorption site and there is a
finite maximum number of molecules per cluster:45
≡ Γ = Γ∞
A 1 + Kx 2L (58)
where Γ is the surface coverage of adsorbed surfactant molecules
per unit surface area, Γ∞ = M/A is the maximum possible surface
coverage of adsorbed surfactant molecules, xL2 is the mole
fraction of surfactant in the liquid phase, and K is a temperature-
dependent parameter. Recognizing that changing the units of
the solute concentration from mole fraction simply changes the
value and units of K, it is common to see eq 58 written in
solution concentration units other than mole fraction.
Zhu and Gu48 proposed a general isotherm as an extension of

ÅÄÅ (1 + ζ ) Ñ
ÑÑ
É
N σ (T , A , PG)
PG Å
Mcα P ÅÅÅÅ1 − (1 + ζ ) α P ÑÑ
eq 58

∞Å
ÑÑ
ÑÑÖ
ζ

ÅÇ
PG PG K (c 2L)n
( ) ( )
ÄÅ É
+ ζ αP

Å Ñ
(1 + ζ ) Ñ
Γ = Γ∞

PG Å ÑÑ
∞ ∞

1 − α P ÅÅÅÅ1 + (c − 1)α P − c α P
1 + K (c 2L)n
ÑÑ
= (59)

∞ Å
ÅÇ
PG PG
( ) ∞ ∞
( )
where α and c are temperature-dependent parameters and ζ is
the maximum number of molecules that can adsorb in one
cluster. The ζ-isotherm has been found to provide a good
representation of experimental data for adsorption from a gas or
vapor onto a wide variety of solids for which the data is not well-
represented by the BET adsorption isotherm, and to provide a
means to obtain values of important material properties from
adsorption measurements.46,47
For adsorption at a fluid interface with no fixed adsorption
sites, we take advantage of the chemical potential equilibrium
between the adsorbed molecules and the solute molecules in the
adjoining bulk fluid phase. For example, if there is an ideal, dilute
solution of surfactant (surfactant solute 2 in solvent 1) in
equilibrium with surfactant adsorbed at a fluid interface,
equating the chemical potential of surfactant in solution (from
a combination of eqs 30 and 36) to the chemical potential of the
surfactant adsorbed at the fluid interface that can contain at most
M adsorbed molecules (using the chemical potential corre-
sponding to Langmuir adsorption eq 53) yields
ij yz
μ20,ref (T , P ref ) + v20(P − P ref ) + RT lnjjj L 2 zz
j x (T , P) zz
xL
k 2∞ {
ÑÑ
ÑÖ
(55)
cL2
where is the concentration of surfactant in the liquid phase.
Originally, n was understood to be the number of surfactant
molecules in a hemimicelle adsorbed on a solid from a liquid
(loosely analogous to ζ in the ζ-isotherm) but practically can be
left as an empirical fitting parameter to describe a wide variety of
fluid−solid adsorption isotherms. Equation 59 (sometimes
referred to as the Langmuir−Freundlich isotherm) is able to
reproduce experimental features such as “S-shaped” adsorption
isotherms. Wang, Xu, and Acosta used this isotherm for each
layer of a bilayer to successfully describe adsorption of
surfactants on iron oxide nanoparticles.49
Finally, note that, by substituting any particular adsorption
isotherm chemical potential equations into the Gibbs adsorption
equation, eq 27, noting that isotherms are at constant
temperature, and integrating, important relationships may be
found between surface tension and adsorption isotherm
parameters and controllable variables of the adjoining bulk
phase, such as gas-phase pressure or liquid-phase solute
concentration. These relationships are commonly exploited to
obtain adsorption isotherm parameters from surface tension
measurements or to obtain inaccessible surface tension values
from knowledge of adsorption isotherm parameters.46,50−52
2.2.3.2. Shardt−Elliott−Connors−Wright Equation for
Surface Tension. The liquid−vapor surface tension depends

ÅÄÅ ÑÉÑ
on temperature and liquid-phase composition. Inserting
Å ÑÑÑ
= RT lnÅÅÅÅ Ñ
temperature-dependent pure species surface tensions into the

ÅÅÇ (M − N σ )q σ ÑÑÑÖ
σ
N Connors−Wright model for the composition dependence of
(56) surface tension at a single temperature gives a useful empirical
equation describing the surface tension dependence on
where qσ is the single-particle partition function for surfactant temperature and composition:53
molecules adsorbed at the fluid interface, assumed to be a
ÄÅ ÉÑ
ÅÅ b(1 − x1) ÑÑÑ
function of temperature. Rearranging eq 56 yields σmix(T , x1) = σ2(T )
Å
− ÅÅÅ1 + ÑÑx1[σ2(T ) − σ1(T )]
Ä ÅÅÇ 1 − a(1 − x1) ÑÑÑÖ
l
o σ ij μ20,ref yz ÅÅÅ v20 ÑÉÑ |
N σ (T , x 2L) =
o L
mq expjj RT zzexpÅÅÅ RT (P − P ref )ÑÑÑÑ/x 2L∞o
o }x 2
k { Å
Ç Ñ
Ö
M n ~
(60)

l Ä ÑÉ L |
o σ ij μ20,ref yz ÅÅÅ v20 ref Ñ Ñ o L
1+m oq expjj RT zzexpÅÅÅÅÇ RT (P − P )ÑÑÑÑÖ/x 2∞}
where a and b are constants that are independent of temperature
ox 2
n k { ~
and composition. The benefit of eq 60 is that, compared with
(57) other approaches, a minimum amount of data is required to
obtain the parameters to make predictions for any temperature
and composition. The temperature-dependent functions σ1(T)
ÅÄÅ v 0 ÑÉÑ
Assuming the pressure effect on chemical potential of the

expÅÅÅ RT2 (P − P ref )ÑÑÑ ≈ 1 (i.e., neglecting the Poynting correc-

surfactant in a liquid solution is negligible, and σ2(T) can be found by fitting data for the temperature

ÅÅÇ ÑÑÖ
dependence of pure component 1 and pure component 2, and
the constants a and b can be found by fitting data for
tion), xL2∞ can be considered to be a function of temperature composition dependence at a single temperature (for example,
only, and eq 57 yields a Langmuir-like adsorption isotherm: room temperature). Equation 60 (and extensions for
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components above their pure species critical points and for
mixtures of more than two components54) showed excellent
accuracy across a wide variety of mixtures, including 15 different
aqueous mixtures,53 15 different hydrocarbon and organic
mixtures,54 and a ternary mixture of methanol/ethanol/water.54
2.3. Combined Conditions for Equilibrium That Reveal
the Effects of Curved Interfaces. For a state to be a
and treating the liquid as compressible.58 Also, for a single-
component fluid, Wang et al. compared eq 64 to treating both
the liquid and vapor phases with a cubic equation of state and
reviewed other works.59
Ward and Levart presented a form of the Kelvin equation for
the equilibrium radius of a bubble (critical radius for nucleation)
in a liquid with a dilute amount of dissolved gas:60

ÅÄÅ v10L L É
thermodynamic equilibrium state, it must satisfy all three of

nLÑ Ñ
2σ LV
P1∞ÅÅÅ RT (P − P1∞) − 2L ÑÑÑ + P L
thermal, chemical, and mechanical equilibrium. A particular set

of combined conditions for equilibrium are of interest: those
describing phase equilibrium across a curved interface. The
combination of eq 10 for thermal equilibrium, eq 11 for chemical
equilibrium, and eq 15 for mechanical equilibrium across a
curved interface, along with chosen equations of state for the
bulk phases, yields a single equation quantifying how interfacial
curvature and interfacial tension shift thermal or chemical
equilibrium.
2.3.1. Kelvin Equation. The Kelvin equation describes the
change in equilibrium vapor pressure above a curved liquid
interface from that above a flat interface. Consider a single-
component liquid droplet surrounded by its vapor. Noting from
eq 10 that the temperatures of the liquid and vapor phases are
equal, eq 11 for chemical equilibrium requires
μ V (T , P V ) = μ L (T , P L ) (61)
Assuming that the vapor is an ideal gas (eq 29) and assuming
ÅÇÅ n1 Ñ
RC =
ÑÖ
n2L
( )−P
n2L∞
L
(65)
where P1∞ is the flat-interface saturation pressure of the pure
liquid, v0L L L
1 is the molar volume of the pure liquid at P and T, n2 is
the molar concentration of gas dissolved in the liquid phase, and
nL2∞ is the saturation molar concentration of dissolved gas (i.e.,
the amount that would be dissolved in the liquid phase were the
liquid to be in equilibrium with a gas phase across a flat interface,
described for example by Henry’s law). Note that eq 65 has been
written with a positive interface curvature defined as curved
toward the vapor (i.e., a vapor bubble) in contrast with eq 64
that was written with a positive interface curvature defined as
curved toward the liquid. Ward’s and Levart’s treatment of
curved interface phase equilibrium in a dilute liquid−gas
solution was used by Zargarzadeh and Elliott for nucleation of
drops and bubbles at solid interfaces with a variety of
geometries.61,62

ij PV yz
that the liquid is incompressible (eq 30), eq 61 may be written With the goal of elucidating the effect of interface curvature on

μref (T , P∞) + RT lnjjj zzz = μref (T , P∞) + v L(P L − P∞)

jP z
multicomponent vapor−liquid equilibrium phase diagrams

k ∞{
across the complete composition range of the liquid and the
vapor, Shardt and Elliott incorporated activity coefficients to
(62) capture the thermodynamic nonideality of the liquid phase
Due to the careful choice of the reference pressure as the (while still treating the vapor phase as an ideal gas) and derived
saturation vapor pressure at a flat interface, P∞, the reference forms of the Kelvin equation describing the vapor-phase

Ä ÉÑ|
pressure at the bubble point13,63
l 0L Å
ji P zy
chemical potentials cancel, yielding
o vi ÅÅÅÅ V
o i1
LV j 1 zyz ÑÑo
Ño
RT lnjjj zzz = v L(P L − P∞) m
γi LxiLPi∞expo ÅÅPbubble + σ jj j zz − Pi∞ÑÑÑo }
jP z o Å j R1 z ÑÑÑÖo
V

o RT ÅÅÇ o
k ∞{ n k 2{ ~
V
Pbubble = ∑ +
(63) i
R
(66)
Substituting the mechanical equilibrium condition at a curved
interface, eq 15 into eq 63, yields the complete Kelvin equation and at the dew point13,63
for the difference in the vapor-phase pressure PV above a curved V

ij yz
liquid interface from the saturation pressure of a flat interface Pdew =

jj zz
jj zz
P∞:7,11,55,56

ji P zy ji 1 1 zyz
−1

jj zz
RT lnjjj zzz = v Lσ LV jjj zzz + v L(PV − P∞) jj∑ Ä
Å V ÉÑ zz
jP z jR
V

jj vi0L Å Ñ zz
V yi

k { k { jj i γ LPi∞exp ÅÅP + σ LV − Pi∞ÑÑÑÑ zz

j RT Å ÅÅÇ dew z
+

k
{ ÑÖ
} {
R
∞ 1 2 (64)
i ( 1
R1
+
1
R2 )
where the equation has been written with a positive interface
(67)
curvature defined as curved toward the liquid (i.e., a liquid
droplet). W. Thomson (Baron Kelvin) was the first to note that a where the sums are over all components i, is the activity γLi
curved liquid−vapor interface would alter the vapor-phase coefficient of component i in the liquid phase, xLi is the mole
pressure,57 but the equation he proposed was missing the last fraction of component i in the liquid phase, Pi∞ is the flat-
term, which could not be understood until Gibbs’s later paper.2 interface saturation pressure of pure component i, v0L i is the
For that reason, eq 64 is called the complete Kelvin equation, but molar volume of pure liquid component i, and yVi is the mole
a more apt name might be the Gibbs−Kelvin equation fraction of component i in the vapor phase. Shardt and Elliott
recognizing Gibbs’s insight underpinning the derivation of eq presented numerical methods for solving eqs 66 and 67 along
64. with requisite balance equations to draw isothermal composi-
Equation 64 applies for a single-component liquid−vapor tion phase diagrams63 and isobaric composition phase
system where the liquid is treated as an incompressible diagrams.13 The isobaric phase diagrams are more challenging
substance and the vapor is treated as an ideal gas. Several to draw because of the strong temperature dependence of the
authors have made extensions to eq 64 for nonideal or parameters γLi , Pi∞, v0L
i , and σ which are almost independent of
LV

multicomponent phases.13,18,58−63 For a single-component 13

pressure. The success of eq 67 combined with the Shardt−
fluid, Melrose introduced treating the vapor as a nonideal gas Elliott−Connors−Wright equation for surface tension, eq 60,
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for predicting dew temperatures of nitrogen/argon mixtures in 2 where the reference state for the chemical potentials has been
nm capillary pores is shown in Figure 4. chosen as the liquid-phase pressure and the corresponding
freezing point at a flat interface, T0fp, so that the reference
chemical potentials cancel out of the equation. Substituting the
mechanical equilibrium condition (eq 15) for the solid−liquid
pressure difference into eq 71 yields the Gibbs−Thomson
equation for interface curvature-induced freezing-point depres-
sion:19,66−69

v Sσ SL ijj 1 1 yzz
S j
jj z
(s − s ) k R1 R 2 zz{
Tfp0 − Tfp = L
+
(72)

where for eq 72 as written, (1/R1 + 1/R2), which is twice the

mean curvature, is defined as positive when the solid is inside the
curvature.
The Gibbs−Thomson effect of curvature-induced freezing-
point depression means that ice can be prevented from growing
into small spaces at temperatures below the normal freezing
Figure 4. Predictions (not fits) by eq 67 of adsorption and desorption point, a phenomenon that is responsible for the action of
dew temperatures as functions of nitrogen mole fraction for antifreeze proteins70,71 and can cause ice-lensing in soils leading
nitrogen(1)/argon(2) mixtures in a capillary with a radius of 2 nm to frost heave.72,73 Karlsson et al. demonstrated that the Gibbs−
compared with experimental measurements of adsorption and Thomson equation was consistent with experimental measure-
desorption at a vapor-phase pressure of 300 kPa from Alam et al.64 ments of the inhibition of ice growth through biological pores
The surface tension of the nitrogen/argon mixtures as a function of and gaps with diameters or gap dimensions ranging from 0.7 to
temperature and pressure was predicted by eq 60. The schematic of the 35 nm.69 The Gibbs−Thomson effect was exploited to build
classical model of adsorption and desorption is adapted from Donohue supercapacitors with aqueous electrolytes that remained func-
and Aranovich.65 Reproduced from with permission from ref 13.
Copyright 2018 American Chemical Society.
tional to −30 °C because a nanostructured polyampholyte
electrolyte could maintain liquid water for ion transport within
its nanopores at low temperatures.74,75
Liu et al. derived a Gibbs−Thomson equation for the
Here, I note that eqs 66 and 67 can be extended for a nonideal curvature-induced freezing-point depression in a nonideal
vapor phase by incorporating fugacity coefficients solution:12

0L Å
Ä ÉÑ|
γi LxiLϕi∞Pi∞ l
V

o vi ÅÅÅÅ V
o i1 1 zyz ÑÑo
Pbubble =

LV j Ño
RTfp0M1π

j
(Ä ) ÉÑ +
zz − Pi∞ÑÑÑ}
1 1
v1Sσ SL
expm ÅPbubble + σ jj ÅÅ
+
o RT ÅÅÅÅÇ ÑÑo ÑÑ
o j R1 z
ÑÖo (s10L − s10S)ÅÅÅÅ1 +
(s10L − s10S)

ÑÑ
R1 R2

o k 2{ o
Tfp0 − Tfp =
n ~ ÑÑÖ
∑
ÅÇ
V
+ RM1π RM1π
ϕi ̂ R 1+
i
(s10L − s10S) (s10L − s10S)
(68) (73)
V

jij zyz
Pdew = The first term on the right-hand side of eq 73 is the capillary
jj zz
jj zz
−1
freezing-point depression (which depends on solution concen-
jj∑ ÄÅ ÉÑ zz
jj zz
tration through osmolality π), and the second term on the right-
V
ϕî yiV
jj i vi0L Å
ÅÅPV ÑÑ zz
jj Ñ zz
RT Å ÅÅ dew i∞Ñ
Ñ
hand side of eq 73 is the solution freezing-point depression. In
k
{ Ç
( )−P ÑÖ
} {
1 1
γi Lϕi∞Pi∞exp + σ LV R1
+ R2
cases where RM1π/(s0L 1 − s1 ) ≪ 1, eq 73 can be linearized with
0S

respect to osmolality to give an equation where the capillary

(69) freezing-point depression does not depend on solution
where ϕi∞ is the fugacity coefficient of pure vapor component i concentration, and the solution freezing-point depression is
and ϕ̂ Vi is the fugacity coefficient of component i in the vapor- proportional to osmolality.19 However, care should be taken
phase mixture. because for concentrated solutions such a linearization may be
2.3.2. Gibbs−Thomson Equation. The Gibbs−Thomson significantly in error.39 Equation 73 reduces to eq 51 in the case
equation describes curvature-induced freezing-point depression. of a flat solid−liquid interface (infinite principal radii of
Thermal and chemical equilibrium (eqs 10 and 11) at a solid− curvature R1 and R2) and reduces to eq 72 in the case of a
liquid interface of a single-component system requires that at the pure liquid (π = 0).
freezing point Tfp Equation 73 can alternatively be written in terms of the
activity coefficient of the solvent (the component that freezes) in
μS (Tfp , P S) = μL (Tfp , P L) (70) the liquid-phase mixture, γL1 , and liquid-phase mole fraction of
Assuming that the liquid and solid are incompressible (eq 30), solvent, xL1 , rather than osmolality12
and that eq 32 applies for the temperature dependence of both RTfp0 ln(γ1Lx1L)
(Ä
v1Sσ SL
1 1
) ÉÑ −
ÅÅ
solid and liquid phases, eq 70 may be written +
ÑÑ
− s10S)ÅÅÅÅ1 −
(s 0L − s 0S)

ÑÑ
R1 R2
Tfp0 − Tfp = 1 1

ÅÇ ÑÑÖ
ref
μ (Tfp0 , L
P ) − s (Tfp − S
Tfp0) S
+ v (P − P ) L S
R ln(γ1Lx1L) R ln(γ1Lx1L)
(s10L 1 − 0L 0S
(s10L − s10S) (s1 − s1 )
ref
=μ (Tfp0 , L L
P ) − s (Tfp − Tfp0) (71) (74)

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Figure 5. (a) Fit of the two-parameter Margules activity coefficient equation to the flat-interface experimental solid−liquid equilibrium data80 for the
water/glycerol system at a pressure of 1 atm. (b) Using the activity coefficients obtained from the flat-interface solid−liquid phase diagram, eq 76 was
used to predict the depression of the freezing liquidus and eq 80 was used to predict the depression of the precipitating liquidus for mean curvature
(1/R1 + 1/R2)/2 of 1/(10 nm) curved toward the solid. Predictions are done over a range of possible glycerol solid−liquid interfacial tension values
because of a lack of data for a precise calculation. Adapted (with additional annotations here in panel a) with permission from ref 12. Copyright 2017
American Chemical Society.

and either of eqs 73 or 74 can be rearranged as a single fraction if The Ostwald−Freundlich equation can explain the desirable
desired: increase in solubility of pharmaceutical formulations with
smaller particle sizes.78 Pouralhosseini et al. used the

Tfp0 − Tfp =
(
v1Sσ SL
1
R1
+
1
R2 ) + RT M π
0
fp 1 Ostwald−Freundlich equation to explain the asphaltene solid
size dependence of the phase behavior of asphaltene/toluene/
(s10L − s10S) + RM1π (75) polysterene mixtures.79
Eslami and Elliott77 and Liu et al.12 derived versions of the

Tfp0 − Tfp =
v1Sσ SL ( 1
R1
+
1
R2 ) − RT ln(γ x )
0
fp
L L
1 1
Ostwald−Freundlich equation for nondilute solutions. For
example, Liu et al.’s equation is12
(s10L − s10S) − R ln(γ1Lx1L) (76)
0
Tfp,2 − Tprecipitation
2.3.3. Ostwald−Freundlich Equation. The Ostwald−
Freundlich equation describes the increased solubility that a
highly curved solid precipitate has in a solution. Assuming that a =
(
v2Sσprecipitate
SL 1
R1
+
1
R2 ) − RT 0 L L
fp,2 ln(γ2 x 2 )

pure solid precipitate is in equilibrium with a solution of that (s20L − s20S) − R ln(γ2Lx 2L) (80)
solute requires (eqs 10 and 11)
where xL2 is the osmole fraction of solute in the liquid phase in
μ2S (T , P S) = μ2L (T , P L , x 2L) (77) equilibrium with solid precipitate 2 at the precipitation
0
where xL2 is the mole faction of the solute in the liquid solution. temperature Tprecipitation. Tfp,2 is the equilibrium freezing
Substituting eqs 30 and 36 into eq 77 yields temperature of pure solute.

ij x L yz
μ2S (T , P S) = μ20 (T , P S) − v20L(P S − P L) + RT lnjjj L2 zzz
The equivalence of the nonideal Ostwald−Freundlich

jx z
equation, eq 80, with the nonideal Gibbs−Thomson equation,
k 2∞ {
eq 76, was noted by Liu et al.12 Equations 76 and 80 are the
equilibrium equations for a pure solid with a curved interface in
(78) equilibrium with a solution, the only difference being whether
Substituting eq 15 into eq 78, canceling the reference chemical the solid is made up of frozen solvent (component 1, eq 76) or
potential, and rearranging yields the Ostwald−Freundlich precipitated solute (component 2, eq 80). Equations 76 and 80

ÄÅ 0L SL É
yzÑÑÑÑ
equation:3,12,76,77
ÅÅ v σ i 1
can be used together to describe the effect of solid−liquid

Å j
jj zzÑÑ
x 2 = x 2∞expÅÅÅ
interface curvature (or equivalently solution confinement which

ÅÅ RT jj R1 R 2 zz{ÑÑÑÑÖ
k
1
ÅÇ
L L 2 enforces a solid−liquid interface curvature for solid nucleation)
+
(79)
on a binary solid−liquid phase equilibrium diagram across the
entire composition range.
where xL2∞ is the saturation mole fraction of solute in a liquid in Note that, without deriving actual forms of the Gibbs−
equilibrium with a flat solid−liquid interface, and xL2 is the Thomson or Ostwald−Freundlich equations, with eq 661 of his
enhanced saturation mole fraction in the liquid in equilibrium paper and the discussion that follows, Gibbs provided the setup
with a solid−liquid interface that is curved toward the solid. for solid−fluid equilibrium (in the case of no solid stresses other
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The Journal of Physical Chemistry B
than isotropic pressure) as the combination of the equality of
chemical potentials with the Young−Laplace equation.2
Figure 5a shows the flat-interface solid−liquid phase diagram
for water(1)/glycerol(2). The freezing liquidus is on the left-
hand side of the diagram, and the precipitating liquidus is on the
right-hand side of the diagram. If a liquid water/glycerol solution
with low solute concentration is cooled, the freezing liquidus is
reached and pure water ice freezes out of solution. If a liquid
water/glycerol solution with high solute concentration is cooled,
the precipitating liquidus is reached and pure solute glycerol
precipitates out of solution. Figure 5b shows how eqs 76 and 80
predict that solid−liquid interface curvature will depress both
the freezing liquidus and the precipitating liquidus.
2.3.4. Curvature-Induced Shift of Eutectic Temperature.
The freezing liquidus and precipitating liquidus meet at the
eutectic point. The eutectic point is important because the
eutectic concentration defines what solid will first come out of
solution as a liquid solution is cooled and also because no liquid
can exist below the eutectic temperature. Figure 5b shows that
the Gibbs−Thomson and Ostwald−Freundlich effects will also
depress the eutectic temperature and shift the eutectic
concentration. The eutectic concentration may be shifted up
or down from the flat-interface eutectic composition depending
on the relative magnitudes of solid−liquid interfacial tensions of
the frozen ice and precipitated solute. Noting that, at the eutectic
mole fraction of solute in the liquid, xE, the freezing temperature
and precipitating temperature are equal, eqs 76 and 80 can be
rearranged for Tfp and Tprecipitation, respectively, and equated to
yield an equation for the curvature-affected eutectic composi-
tion in a binary system:12
v1Sσice
SL
( 1
R1
+
1
R2 )−T 0 0L
fp,1(s1 − s10S)
R ln[γ1L(1 − x E)] − (s10L − s10S)
=
v2Sσprecipitate
SL 1
R1( +
1
R2 ) − 0
Tfp,2(s20L − s20S)
R ln(γ2Lx E) − (s20L − s20S)
(81)
The eutectic composition found from eq 81 can be substituted
into either eq 76 or eq 80 to obtain the curvature-depressed
eutectic temperature. Depression of the eutectic temperature by
curvature of the solid−liquid interface (or equivalently solution
confinement which enforces a solid−liquid interface curvature
for solid nucleation) is the reason that liquid water (amorphous,
mobile water molecules) can exist in a water/sodium chloride
solution confined in nanochannels in a nanostructured
polyampholyte hydrogel at temperatures as low as −49 °C
which is far below the water/sodium chloride normal eutectic
temperature of −21 °C.75
2.4. Procedure for Finding and Examining the System
Free Energy. Sections 2.1−2.3 have described the first three
steps of Gibbsian composite-system thermodynamics: (i)
describe the system so that the mathematical constraints
corresponding to the system description are clear; (ii) derive
the conditions for thermal, chemical, and mechanical equili-
brium by extremizing entropy subject to the constraints; and
(iii) combine the conditions for equilibrium with equations of
state for each phase to arrive at equations that can be solved to
find the properties of interest when the system is in a particular
equilibrium state. The first three steps are very useful in that one
can use the resulting equations to compute many things of
interest. However, they do not indicate the number of individual
states that satisfy the equilibrium conditions for a given system,
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and they do not indicate the nature of those equilibrium states
(stable, metastable, or unstable). For these things, we must find
which free energy acts as the thermodynamic potential for a
given system and examine the extrema of this function.
The free energy of the system is the energy of the system that
is available to be changed on a path toward equilibrium once
thermodynamic and physical requirements for a given system
have been imposed. The free energy will be a global minimum at
stable equilibrium, a local minimum at metastable equilibrium,
and a maximum or inflection (or saddle in multidimensions) at
unstable equilibrium. When a system that is not in equilibrium
evolves toward equilibrium, the entropy of the system plus the
surrounding reservoir tends to increase, subject to conservation
of energy, conservation of mass, continuity of volume, and any
other system-specific constraints. This evolution will occur until
it is no longer favored, i.e., entropy becomes a maximum, at
which point the system will be in a stable equilibrium state and
will not change further. Thus, another way of defining free
energy is the energy that when minimized corresponds to
entropy being maximized subject to constraints. The method of
finding what function acts as the free energy of a given system
follows that described for a single bulk phase on pages 87−91 of
the Ox Bow Press version of Gibbs’s paper2 and pages 153−159
of Callen’s book.5 Detailed descriptions of how to find what
function acts as the thermodynamic potential or free energy of a
composite system that is not a simple system (e.g., a multiphase
system with a curved fluid interface with interfacial tension
effects) in a way that is consistent with Gibbsian composite-
system thermodynamics have been given by Ward and Levart,60
Elliott,7 Elliott and Voitcu,81 and Zargarzadeh and Elliott.11
Briefly, as a system evolves toward equilibrium, Planck’s
statement82,83 of the second law of thermodynamics states that
for macroscopic spontaneous changes
ΔS reservoir + ΔS system ≥ 0 (82)
when the system plus surrounding reservoir form an isolated
system. This is subject to conservation of energy,
ΔU reservoir + ΔU system = 0 (83)
Combining eqs 82 and 83 with any applicable conservation of
mass equations of the form of eq 7, any applicable continuity of
volume equations of the form of eq 6, and any conditions for
equilibrium that explicitly describe the interaction of the system
with the reservoir, one arrives at an equation of the form
Δ(free energy) ≤ 0 (84)
wherein the relevant free energy is identified. Additional
conditions for equilibrium (i.e., those equilibrium conditions
that describe relationships among constituent subsystems of the
system, rather than relationships with the reservoir) can be
substituted in the free energy to write the free energy in other
convenient forms. Finally, to make use of the free energy, it is
evaluated with respect to a reference state and then plotted with
respect to a system variable, or variables, of interest to identify at
which values the free energy is an extremum (global minimum,
local minimum, inflection point (saddle), or maximum).
Extrema occur at places where the first derivative of the free
energy vanishes. The number of different extrema identifies the
number of different states that satisfy the conditions for
equilibrium. The second derivative of the free energy identifies
the nature of each of those equilibrium states: global minima
correspond to stable equilibrium states, local minima corre-
spond to metastable equilibrium states, and maxima correspond
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to unstable equilibrium states. Inflection points with respect to
one variable of interest, or saddle points with respect to multiple
variables of interest, also correspond to unstable equilibrium
states, albeit where the system is stable with regard to some
changes and unstable with respect to other changes.
As an example, consider the system shown in Figure 6a. A
single-phase liquid system is contained in a piston−cylinder
Figure 6. (a) Schematic diagram of a single-phase liquid system
contained in a piston−cylinder device which imposes the temperature
and pressure of the surrounding reservoir on the system. (b) Schematic
diagram of a multiphase fluid system with a vapor bubble surrounded by
liquid contained in a piston−cylinder device which imposes the
temperature of the surrounding reservoir on the system, and the
pressure of the surrounding reservoir on the liquid phase.
R
device which imposes the reservoir temperature, T , and the
reservoir pressure, PR, on the system. The piston−cylinder
device and its interface with the liquid is considered to form part
of the reservoir, and the system is only the liquid. The difference
form of the fundamental relation for the reservoir can be written
ΔU R = T R ΔS R − P R ΔV R + ∑ μiR ΔNiR
(85)
i
because they are imposed by the reservoir and can therefore be
brought inside the Δ), yields
Δ(U L − T LS L + P LV L) ≤ 0 (93)
identifying the free energy (the expression inside the brackets in
eq 93) as the Gibbs free energy of the liquid. Gibbs free energy is
defined as G = U − TS + PV. So, we see that for a single-phase
liquid system with its temperature and pressure fixed by an
external reservoir, maximizing entropy of the system plus the
reservoir subject to constraints is the same as minimizing the
Gibbs free energy of the liquid.
As another example, consider the system shown in Figure 6b.
A liquid−vapor system is contained in a piston−cylinder device
which imposes the reservoir temperature on the system and the
reservoir pressure on the liquid phase. The piston−cylinder
device and its interface with the liquid are assumed to belong to
the reservoir. Conservation of energy, eq 83, implies
ΔU R = −ΔU L − ΔUV − ΔU LV (94)
Continuity of volume implies
ΔV R = −ΔV L − ΔV V (95)
The conditions for equilibrium that explicitly describe the
interaction of the system with the reservoir are
T R = T L = T V = T LV (96)
and
PR = PL (97)
Equation 82 implies that for any macroscopic spontaneous
changes as the system evolves toward equilibrium
ΔS R ≥ −ΔS L − ΔS V − ΔS LV (98)
Substituting eqs 87 and 94−98 in eq 85 yields
Δ[(U L − T LS L + P LV L) + (UV − T VS V )

Conservation of energy, eq 83, implies + (U LV − T LVS LV ) + P LV V ] ≤ 0 (99)

ΔU R = −ΔU L (86) or
The system does not exchange mass with the reservoir, so for Δ(GL + F V + F LV + P LV V ) ≤ 0 (100)
every species in the reservoir
where F is the Helmholtz free energy, defined as F = U − TS. The
ΔNiR = 0 (87) free energy in the brackets in eq 100, or similar ones, has been
given the symbol B since it corresponds to none of the well-
Continuity of volume implies known free energies.7,11,56,60,81
ΔV R = −ΔV L (88) Equation 99 can be written in another form. Substituting
Euler relations eqs 24 and 25 into the free energies inside the
The conditions for equilibrium that explicitly describe the brackets of eq 99 yields
interaction of the system with the reservoir are
TR = TL (89) B = (P L − PV )V V + σ LVALV + ∑ μiL NiL + ∑ μi V NiV
i i
and
+ ∑ μi LV
NiLV
PR = PL (90) i (101)
Substituting eqs 86−90 in eq 85 yields The Laplace equation, eq 15, is a condition for equilibrium that
L L
0 = ΔU + T ΔS + P ΔV R L L (91) is internal to the system. When eq 15 is substituted into eq 101,
the free energy may be written
Equation 82 implies that for any macroscopic spontaneous
changes as the system evolves toward equilibrium 2σ LV V
B=− V + σ LVALV + ∑ μiL NiL + ∑ μi V NiV
R L R eq
ΔS ≥ −ΔS (92) i i

Substituting eq 92 in eq 91, and rearranging (noting that T and L + ∑ μi LV

NiLV
PL are constant with respect to the evolution toward equilibrium i (102)

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The Journal of Physical Chemistry B
Figure 7. (a) Nucleation of a liquid drop on a rigid surface. (b) Nucleation of a liquid drop on a fluid surface. (c) Free energy versus water drop volume
for drop nucleation on a fluid (dodecane) substrate or rigid substrate with the same interfacial tensions where T = 22 °C, PV = 2700 Pa, σLV = σwater =
72.43 mN/m, σSV = σ L′V = σdodecae = 25.3 mN/m, and σSL = σ L′L = σwater−dodecae = 53.7 mN/m. Adapted (with additional annotations here) with
permission from ref 9. Copyright 2011 American Chemical Society.
where Req is the radius of the vapor bubble at equilibrium.
So, we see that, for a liquid system with its temperature and
pressure fixed by an external reservoir, maximizing entropy
subject to constraints is the same as minimizing the Gibbs free
energy of the liquid. However, for a system that consists of liquid
with an internal vapor bubble with the system temperature and
liquid pressure fixed by an external reservoir, maximizing
entropy of the system plus reservoir subject to constraints is the
same as minimizing the system free energy B.
Examples of evaluating the free energy with respect to a
reference state and plotting versus a variable of interest to
understand the system behavior are shown in Figures 7 and 8. In
Figure 7, the free energy is examined for a water drop nucleating
from water vapor on either a rigid or fluid surface in a system
surrounded by a reservoir that imposes the reservoir temper-
ature on the system and the reservoir pressure on the vapor
phase.9 In either case, there is one unstable equilibrium state
(place where the free energy is a maximum). The value of the
free energy at the unstable equilibrium quantifies the energy
barrier that must be overcome in order for a nucleation event to
take place. The difference in energy barriers indicates that
nucleation occurs more readily on a fluid surface than on a rigid
surface with the same interfacial tension values.9
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In Figure 8, the free energy is examined for a bubble growing
out of a water−nitrogen solution where the nucleation happens
inside a finite conical pit in a solid.62 In the case examined, there
are two equilibrium states. There is an unstable equilibrium at a
small bubble size indicating the energy barrier that must be
overcome for the bubble to nucleate inside the cone, and there is
a stable equilibrium at a larger bubble size that occurs when the
bubble is pinned at the cone mouth.62 Depending on the values
of system parameters, the final stable equilibrium state may
occur inside the cone, pinned to the corner of the cone, or
outside the cone.62
3. APPLICATIONS OF GIBBSIAN COMPOSITE-SYSTEM
THERMODYNAMICS
While Gibbs created the underlying fabric for composite-system
thermodynamics,2 it was not until various equations of state
could be used to solve the conditions for equilibrium and
compute the free energy for a particular circumstance that the
true power of the framework could be wielded. Gibbsian
composite-system thermodynamics governs the behavior of any
system with two or more fluid systems in equilibrium and as new
experimental techniques, technologies, and scientific questions
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Figure 8. Equilibrium states of a bubble starting with a convex meniscus in a finite cone submerged in a liquid−gas solution. (a) Free energy versus
height of the center of the liquid−vapor interface. (b) Magnification of the energy axis for free energy versus height of the center of the liquid−vapor
interface, to show the maximum and minimum points. The system is set to be at 25 °C and a liquid pressure of 1 atm, with the liquid initially containing
2.5 × 1019 molecules (4.15 × 10−5 moles) of water and 3 × 1014 molecules (4.98 × 10−10 moles) of nitrogen (initial degree of saturation of 1.089). The
cone mouth radius, w, is 50 μm, and the half cone apex angle, β, is 45°. The contact angle, θ, is considered to be 10°. The status of the bubble (inside, or
pinned to the corner, or outside the cone) is shown with different line types. Reproduced with permission from ref 62. Copyright 2019 American
Chemical Society.

continue to be created, the number of applications is ever-
increasing.
Ward and co-workers described the nucleation and stability of
bubbles from liquid−gas solutions emerging either homoge-
neously from a liquid84 or heterogeneously from a conical solid
pit,18,60 either at constant liquid-phase pressure60 or at constant
system volume,18,84 with one motivation being the role of bubble
nucleation in decompression-sickness-caused bone death in
humans.18 McGaughey and Ward investigated the stability of
one or more single-component sessile drops in a closed volume
taking into account the wettability of the volume walls away
from the sessile drop.85 Zargarzadeh and Elliott investigated the
role of conical pit geometry and wettability of the pit walls in the
heterogeneous nucleation of bubbles and drops from either a
pure phase56 or a liquid−gas solution.62 Elliott and Voitcu81 and
Zargarzadeh and Elliott11 investigated the formation and
stability of liquid capillary bridges between a sphere and a flat
plate11,56,81 and between two flat plates.56 Zargarzadeh and
Elliott included the role of solid wettability and considered both
liquid capillary bridges and bridging bubbles.11,56 Liquid
capillary bridges pull solids together bringing paintbrushes to a
tip, pulling surface force microscope tips toward surfaces,
collapsing fine surface texture features, and causing either
desired or undesired particle agglomeration in many industrial
settings. Two important results of these thermodynamic studies
were that nanoscale confinement between two solid surfaces can
enhance or suppress phase transitions,11,81 and that nanoscale
confinement can lead to disappearance/appearance fluctuations
of the new phase far from the bulk phase critical point of the
fluid.11,62,81 Zargarzadeh and Elliott provided a thermodynamic
framework for surface nanobubbles,61 microscopic bubbles with
nanometer height (nanopancakes) that can form at hydrophobic
10874
surfaces and play a role in interactions between hydrophobic
solid surfaces in liquids.86 Eslami and Elliott used Gibbsian
composite-system thermodynamics to explain why, under
conditions where nucleation at surfaces is possible, nucleation
occurs more readily at a fluid surface (a nucleated lens-shaped
drop) than at a solid surface (a nucleated sessile drop) with the
same values of interfacial tension.9 Eslami and Elliott described
the thermodynamics of microfluidic process in which the
concentrating of a solute in an aqueous drop is controlled by the
dissolution of water into a surrounding oil phase.10,77,87 They
considered both precipitating and nonprecipitating solutes and
included the roles of both droplet curvature and precipitate
curvature. The complexity of this system can lead to multiple
equilibrium states including equilibrium states in which all water
is removed from the drops.
Ward and Sasges and co-workers used the Gibbsian
composite-system thermodynamics framework to describe the
impact of a gravitational field on the curvature and contact
angles of two fluid interfaces located at different heights while in
equilibrium with each other6,88−90 and explained several
thought-provoking experiments at normal gravitational intensity
in a university laboratory88 and at various gravitational
intensities provided by experiments in a drop shaft89 and on
board the space shuttle.90 Asekomhe and Elliott showed that
accounting for gravity-induced deformation of the fluid interface
changed the line tension inferred from capillary rise in a conical
tube by 50%.91 Eslami and Elliott described the thermodynamics
of capillary menisci acted on by a perpendicular gravitational
field across the full range of Bond numbers (capillary
diameters).92 Voitcu and Elliott provided a unified derivation
of all conditions for equilibrium of sessile drop in a gravitational
field.8
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Milne et al.51 showed that, by combining Gibbs adsorption
equations for surfactant adsorption with the equilibrium of a
sessile drop on a rough surface, analytical expressions for contact
angle of surfactant-laden sessile drops wetting rough surfaces
could be found in terms of surfactant concentration and surface
roughness parameters.50−52 Shardt et al. expanded the approach
to explain transitions between Cassie−Baxter (drop atop the
roughness trapping air) and Wenzel (drop permeating the
roughness) wetting states.52 Shardt and Elliott provided
Gibbsian composite-system derivations of new forms of the
Cassie−Baxter and Wenzel equations that emphasized that it is
roughness at the three-phase line that controls the contact angle
of sessile drops on rough surfaces14,15 and showed under what
conditions the volume of liquid penetrating the roughness can
be neglected in Wenzel wetting.15
Several of the thermodynamic models developed by our group
(including equations of state, Gibbsian thermodynamics, and
nonequilibrium thermodynamics) have been motivated by
cryobiology, the study of the response of living cells and tissues
to extremely low temperature such as the temperature of liquid
nitrogen (−196 °C) used for long-term storage ubiquitously in
cell and tissue banking for transplant medicine, in the
commercial supply of cells for research, and in managing the
supply of cells within research laboratories.19,25−30,35−39,69,93−96
In cryobiology applications, the two fluid phases in equilibrium
might be the inside and outside of a cell separated by the plasma
membrane, or pure water ice and the unfrozen fraction more
concentrated in solutes than before freezing.
In 2019 alone, there were 2719 documents published with
“nanofluidics” in the document title, abstract, or keywords
(Scopus, June 7, 2020). The equilibrium of two fluid phases
inside a solid micro- or nanopore that causes curvature of the
fluid interface is of intense interest, both because of many
practical applications (such as recovery of crude oil from shale)
and because of the interest in emerging nanoscience. Zandavi
and Ward47 measured the adsorptive uptake (capillary
condensation) of three hydrocarbon vapors in nanoporous
silica and showed that pore diameter predicted from the Kelvin
equation was consistent with an independently measured (with
transmission electron microscopy) pore diameter of 2.6 nm.
They also showed that a more sophisticated analysis where the
pressure effects on the adsorption at the solid−liquid interface
were described with the zeta isotherm gave the same pore
diameter in agreement with the measurements. Karlsson et al.69
showed that the Gibbs−Thomson equation for the growth of ice
through biological protein pores led to a single value of the
protein−water−ice contact angle for three different experi-
ments, at three different length scales, with three different
proteins, in three different laboratories, indicating experimental
agreement with the Gibbs−Thomson equation for pore
diameters from 0.7 to 35 nm. Shardt and Elliott described the
role of fluid interface curvature on isothermal63 or isobaric13
phase diagrams of multicomponent liquid−vapor phase
equilibrium. They showed excellent agreement with independ-
ent experiments for the isobaric dew temperatures of nitrogen/
argon mixtures condensing in 4 nm diameter pores in Vycor
glass.13 They also showed that the effect of nanoscale fluid
interface curvature on vapor−liquid phase equilibrium in
nanopores can be profound. Nonideal mixtures of ethanol/
water that exhibit an azeotrope (equal volatility point beyond
which separation by distillation is not possible) had their
azeotrope completely removed when the radius of curvature of
the liquid−vapor interface (curved toward the liquid) was less
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pubs.acs.org/JPCB Feature Article
than 31 nm for isothermal vapor−liquid equilibrium at 298
K.13,63 For isobaric vapor−liquid equilibrium at a vapor-phase
pressure of 1 atm, the ethanol/water azeotrope was removed
when the radius of curvature of the liquid−vapor interface
(curved toward the liquid) was less than 17 nm.13 Liu et al.12
described the effect of curvature of the ice−solution and
precipitate−solution interfaces on the solid−liquid phase
diagram across the complete composition range. Interface
curvature causes depression of the freezing liquidus and
depression of the precipitating liquidus. Importantly, interface
curvature depresses the eutectic point (the point where the
freezing liquidus and precipitating liquidus meet; below the
eutectic temperature, liquid cannot exist in the system at
equilibrium). The fact that nanoporosity can suppress freezing
and allow equilibrium liquid water to exist at low temperatures is
being exploited to design energy storage devices with aqueous
electrolytes with excellent low-temperature performance.74,75,97
Liu et al.97 explored the impact on freezing of nanoscale
confinement and concentrations of additives being used in
aqueous electrolytes for zinc−air batteries. Li et al.74 built
supercapacitors with aqueous polyampholyte hydrogel electro-
lytes with excellent performance down to −30 °C. The
nanostructured polyampholyte hydrogel maintained liquid
water in nanopores allowing ionic conductivity to continue at
low temperatures as low as −49 °C.75
4. CONCLUSIONS
Most thermodynamics textbooks cover only simple systems:
systems that at equilibrium have a single constant value of each
intensive property throughout. Systems that have multiple
pressures at equilibrium due to the action of surface tension of a
curved fluid interface, due to the presence of a semipermeable
membrane, or due to the action of fields, can be treated as
composite-systems: systems made up of multiple simple systems
in equilibrium with each other but that are not themselves
simple systems. Gibbsian composite-system thermodynamics is
a framework to treat these systems consisting of four steps: (i)
define the system and constraints, (ii) extremize entropy subject
to constraints (or equivalently extremize free energy) to derive
the complete set of conditions for equilibrium, (iii) introduce
equations of state to the conditions for equilibrium and solve for
equilibrium values of the thermodynamic variables, and (iv)
identify which function acts as the thermodynamic potential
(equivalently free energy) and examine this function to find the
number of unstable, metastable, or stable equilibrium states. In
this Feature Article, I have given an overview of Gibbsian
composite-system thermodynamics, highlighting many of the
key equations and showing how they are related to one another
in Gibbs’s comprehensive framework. Where possible, I tried to
give references to the primary literature. Ideal forms of some of
the presented equations are more than 100 years old; however,
until recently theory had been fully developed only for the least
complicated of systems (e.g., systems with only a single-
component, or only two ideal phases, or for ideal geometries).
Here I have highlighted advances made over the past 35 years to
develop Gibbsian composite-system thermodynamics for
application to systems of contemporary interest featuring the
work of my research group. As far as I know, eqs 33, 57, 68, and
69 as written are new to this work.
https://dx.doi.org/10.1021/acs.jpcb.0c05946
J. Phys. Chem. B 2020, 124, 10859−10878
The Journal of Physical Chemistry B
■
AUTHOR INFORMATION
Corresponding Author
Janet A. W. Elliott − Department of Chemical and Materials
Engineering, University of Alberta, Edmonton, Alberta T6G 1H9,
Canada; orcid.org/0000-0002-7883-3243;
Email: janet.elliott@ualberta.ca
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jpcb.0c05946
Notes
The author declares no competing financial interest.
Biography
Janet A. W. Elliott is a University of Alberta Distinguished Professor and
Canada Research Chair in Thermodynamics in the Department of
Chemical and Materials Engineering. Dr. Elliott obtained her BASc in
the Engineering Physics Option of Engineering Science, and her MASc
and PhD in Mechanical Engineering at the University of Toronto. She
has been a Visiting Professor at MIT and at the Oxford Centre for
Collaborative Applied Mathematics. Dr. Elliott’s research interests
include thermodynamics, transport, surfaces, colloids, cryobiology, and
cryopreservation. Broad thermodynamic interests include fundamental
concepts in Gibbsian thermodynamics, mathematics of functions,
combining thermodynamics with fluid mechanics, and combining
thermodynamic insight with experimental data to develop descriptions
of states and processes for a wide range of applications. Colloidal and
surface thermodynamics interests include drops, bubbles, adsorption,
solidification of colloidal suspensions, microfluidic processes, wetting,
superhydrophobic surfaces, evaporation, freezing, solidification,
nucleation, phase change in confined geometries, curved fluid
interfaces, interfacial and membrane transport, capillarity in gravita-
tional fields, thermodynamics of solutions and suspensions, and
nanoscale science. In addition, Dr. Elliott runs a collaborative,
interdisciplinary cryobiology research group with interests in
experimental and computational cryobiology and cryopreservation of
many cell and tissue types for medical and biotechnology applications.
Dr. Elliott currently serves as Associate Editor of the journal
Cryobiology, on the Editorial Advisory Boards of The Journal of Physical
Chemistry and Langmuir, and on the Editorial Board of Advances in
Colloid and Interface Science. She has previously served on the Physical
Sciences Advisory Committee of the Canadian Space Agency, the
Board of Directors of the Canadian Society for Chemical Engineering,
and the Executive Committee of the American Chemical Society
Division of Colloid and Surface Chemistry. Dr. Elliott’s research has
been recognized nationally and internationally in science and
engineering by Fellowship in the American Institute for Medical and
Biological Engineering (2019), Fellowship in the Society for Cryo-
biology (2018), Fellowship in the Chemical Institute of Canada (2015),
10876
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the Canadian Society for Chemical Engineering Syncrude Canada
Innovation Award (2008), the Natural Sciences and Engineering
Research Council of Canada Doctoral Prize (1998), the Canadian
Council of Professional Engineers Young Engineer Achievement Award
(2001), the Canadian Institute for Advanced Research Young
Explorer’s Prize (2002), and Time Magazine’s Canadians Who Define
the New Frontiers of Science (2002). Dr. Elliott has also received many
provincial and university awards including the Association of
Professional Engineers and Geoscientists of Alberta Summit Excellence
in Education Award (2017). As one student put it, “She could convince
rocks to study thermodynamics.”
■ ACKNOWLEDGMENTS
The funding agencies that supported the research in the
reviewed papers are acknowledged in the cited papers. I hold a
Canada Research Chair in Thermodynamics and acknowledge
Discovery Grant RGPIN-2016-05502 from the Natural Sciences
and Engineering Research Council (NSERC) of Canada. I am
grateful to Dr. Nadia Shardt for proofreading this article and
offering helpful suggestions.
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