GibbsThomson equation

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1. The GibbsThomson Effect, in common physics usage, refers to variations in vapor pressure
or chemical potential across a curved surface or interface. The existence of a positive
interfacial energy will increase the energy required to form small particles with high
curvature, and these particles will exhibit an increased vapor pressure. SeeOstwald
Freundlich equation.
2. More specifically, the GibbsThomson effect refers to the observation that small crystals are
in equilibrium with their liquid melt at a lower temperature than large crystals. In cases of
confined geometry, such as liquids contained within porous media, this leads to a
depression in the freezing point / melting point that is inversely proportional to the pore size,
as given by the GibbsThomson equation.
Contents
[hide]
1 Introduction
2 GibbsThomson equation for particles
3 GibbsThomson equation for liquids in pores
4 Simplified Gibbs-Thomson equation
5 History
6 References
Introduction[edit]
1. The technique is closely related to using gas adsorption to measure pore sizes, but uses the
GibbsThomson equation rather than the Kelvin equation. They are both particular cases of
the Gibbs Equations of Josiah Willard Gibbs: the Kelvin equation is the constant
temperature case, and the GibbsThomson equation is the constant pressure case.
[1]

2. This behaviour is closely related to the capillary effect and both are due to the change in bulk
free energy caused by the curvature of an interfacial surface under tension.
[2][3]

3. The original equation only applies to isolated particles, but with the addition of surface
interaction terms (usually expressed in terms of the contact wetting angle) can be modified
to apply to liquids and their crystals in porous media. As such it has given rise to various
related techniques for measuring pore size distributions, seeThemoporometry and
Cryoporometry.
4. The GibbsThomson effect lowers both melting and freezing point, and also raises boiling
point. However, simple cooling of an all-liquid sample usually leads to a state of non-
equilibrium super cooling and only eventual non-equilibrium freezing. To obtain a
measurement of the equilibrium freezing event, it is necessary to first cool enough to freeze
a sample with excess liquid outside the pores, then warm the sample until the liquid in the
pores is all melted, but the bulk material is still frozen. Then, on re-cooling the equilibrium
freezing event can be measured, as the external ice will then grow into the pores.
[4][5]

This is in effect an "ice intrusion" measurement (cf. Mercury Intrusion), and as such in part may
provide information on pore throat properties. The melting event can be expected to provide more
accurate information on the pore body.
GibbsThomson equation for particles[edit]
1. For an isolated spherical solid particle of diameter in its own liquid, the Gibbs-Thomson
Equation for the structural melting point depression can be written:
[6]

2.
3. Where:
T
mB
=Bulk Melting temperature

sl
= solidliquid interface energy (per unit area)
H
f
= bulk enthalpy of fusion (per gram of material)

s
= density of solid
The "4" in the above equation comes from the spherical geometry of the solid-liquid interface.
Note: is used for the pore size rather than for a number of reasons :
It is consistent with the original published notation.
The equation can be used with planar geometry (with a change of constant).
For consistency with the related StrangeRahmanSmith equation where the symbol is
used for the differential operator.
GibbsThomson equation for liquids in pores[edit]
Very similar equations may be applied to the growth and melting of crystals in the confined
geometry of porous systems. However the geometry term for the crystal-liquid interface may
be different, and there may be additional surface energy terms to consider, which can be
written as a wetting angle term . The angle is usually considered to be near 180. In
cylindrical pores there is some evidence that the freezing interface may be spherical, while
the melting interface may be cylindrical, based on preliminary measurements for the
measured ratio for in cylindrical pores.
[7]

Thus for a spherical interface between a non-wetting crystal and its own liquid, in an infinite
cylindrical pore of diameter , the structural melting point depression is given by:
[8]


Simplified Gibbs-Thomson equation[edit]
The GibbsThomson equation may be written in a compact form:
[9]


where the Gibbs-Thomson Coefficient assumes different values for different
liquids
[6][7]
and different interfacial geometries (spherical/cylindrical/planar).
[7]

In more detail:,
[1][10]


Where : is a geometric constant dependent on the interfacial shape,
is a constant involving parameters specific to the crystalline solid of solidliquid system,
and
is an interfacial energy term.
History[edit]
By 1906, the German physical chemist Friedrich Wilhelm Kster (1861-1917) had
predicted that since the vapor pressure of a finely pulverized volatile solid is greater than
the vapor pressure of the bulk solid, then the melting point of the fine powder should be
lower than that of the bulk solid.
[11][12]
Investigators such as the Russian physical
chemists Pavel Nikolaevich Pavlov (1872-1953) and Peter Petrovich von Weymarn
(1879-1935), among others, searched for and eventually observed such melting point
depression.
[13]
They recognized that the depression occurred when the change in
surface energy was significant compared to the latent heat of the phase transition, which
condition obtained in the case of very small particles.
[14]

Neither Josiah Willard Gibbs nor William Thomson (Lord Kelvin) derived the Gibbs
Thomson equation.
[15]
Also, although many sources claim that British physicist J. J.
Thomsonderived the GibbsThomson equation in 1888, he did not.
[16]
Early in the 20th
century, investigators derived precursors of the GibbsThomson equation.
[17]
However,
in 1920, the GibbsThomson equation was first derived in its modern form by two
researchers working independently: Friedrich Meissner, a student of the Estonian-
German physical chemist Gustav Tammann, and Ernst Rie (1896-1921), an Austrian
physicist at the University of Vienna.
[18][19]
These early investigators did not call the
relation the "Gibbs-Thomson" equation. That name was in use by 1910 or earlier;
[20]
it
originally referred to equations concerning the adsorption of solutes by interfaces
between two phases equations that Gibbs and then J. J. Thomson derived.
[21]
Hence,
in the name "Gibbs-Thomson" equation, "Thomson" refers to J. J. Thomson, not William
Thomson (Lord Kelvin).
In 1871, William Thomson published an equation describing capillary action and relating
the curvature of a liquid-vapor interface to the vapor pressure:
[22]


where
= vapor pressure at a curved interface of radius
= vapor pressure at a flat interface ( ) =
= surface tension
= density of vapor
= density of liquid
, = radii of curvature along the principal sections of the curved interface.
In his dissertation of 1885, Robert von Helmholtz (son of
German physicist Hermann von Helmholtz) showed how
the Ostwald-Freundlich equation

could be derived from Kelvin's equation.
[23][24]
The Gibbs
Thomson equation can then be derived from the Ostwald-
Freundlich equation via a simple substitution using the
integrated form of the ClausiusClapeyron relation:
[25]


The GibbsThomson equation can also be derived directly
from Gibbs' equation for the energy of an interface between
phases.
[26][27]

It should be mentioned that in the literature, there is still not
agreement about the specific equation to which the name
"Gibbs-Thomson equation" refers. For example, in the case of
some authors, it's another name for the "Ostwald-Freundlich
equation"
[28]
which, in turn, is often called the "Kelvin
equation" whereas in the case of other authors, the "Gibbs-
Thomson relation" is the Gibbs free energy that's required to
expand the interface,
[29]
and so forth.