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UNIVERSIDAD DE ANTIOQUIA

FACULTAD DE INGENIERIA
DEPARTAMENTO ING. DE MATERIALES

SURFACE
THERMODYNAMIC
1
2
Martin Eduardo Hurtado . Ivn Carlos Prentt .
Thermodynamic of Materials
Period 2016-1

Abstract
The surfaces thermodynamics comprises phenomenon that we are present in everyday
life, which can process easily, but the time to give them a theoretical understanding
about the topic this we are out of hand. The surfaces thermodynamics it focuses on the
study of the thermodynamics properties presents in regions where separate two different
phases.
Solids have surface tension, but this is more difficult measure. Substances liquids is
more easy measure and see the change in the surface tension, for example the water,
when this is introduce in a capillary or glass, form an angle tangent with the surface,
this is for the internal forces of the fluid, the particles on the surface are attracted drawn
into the fluid, causing the surface contract.
A thermodynamic state is defined by two intensive and independent thermodynamic
properties, thermodynamic properties that are easier to establish by direct measurement
are the pressure, temperature and volume, these properties depend on important factors
such as Gibbs free energy and entropy. Thermodynamic surfaces are a relationship
between pressure (P), volume (v) and temperature (T), which generates a surface in
which one can distinguish the different phases of matter and processes phase change.

Keywords
Surface thermodynamic properties, surface tension, Gibbs Free energy, Entropy.

Introduction
If we consider a liquid in equilibrium with its vapor, the molecules inside of liquid
experience attractive forces that cancel on average. The forces are equal (on average) in
all directions. Conversely, the surface molecules experience a net attractive force into
the liquid, since we can disregard interactions with the molecules of steam. In energy
terms, the surface molecules have an internal energy higher than the molecules within
the liquid because these experiencing less attractive interactions. The system will tend
to minimize its surface to minimize their energy.
One of the properties of surface tension indicates that, as the liquid has greater cohesive
forces, will have a higher surface tension. However, keep in mind that the surface
tension is linked to the temperature and nature of the liquid.
We can understand the surface tension as a kind of elastic membrane difficult "enter"
into the liquid. By this phenomenon, some insects have the ability to land on water
without sinking.
Suppose an interfacial surface of area A between two phases and . The number N of
molecules in the interfacial region will be proportional to the area. If we increase this
area in an amount dA, will increase the number of superficial molecules dN. The
molecules are more stable within the phase, will be required a work dw proportional a
dN and therefore dA to carry to the surface and likewise increase the interfacial area.
Consequently, the surface will push back against any curvature in much the same way
as a ball pushed uphill will push back to minimize its gravitational potential energy.
Superficial tension

Image 1. Superficial tension in the water


For understand what is of thermodynamics of surfaces, is necessary to provide a

description of the system that concerns us. Wet systems consist of three phases and the
separation between them is called interface. The surface chosen to describe the location
of the interface is called interface or surface of Gibbs.
Therefore we refer to an interface such as the imaginary interface between two phases
and interphase as the three-dimensional region of transition between two phases.

Image 2. Separations between phases in a system.


The existence of these two phases is unfavorable from the energetic point of view
because there is excess energy stored in the interfaces and there is always a tendency to
diminish the interfacial area.
The tendency to reduce the area is the response of the system thermodynamic to reduce
the free energy because it depends on factors such as pressure, temperature and
chemical potential. This energy is known as free energy superficial or interfacial and is
measured in j/m2
When splitting a solid, the amount of energy required is 2gA, where 2A is the area
created (one A on each side). This energy is less than that needed just to break the
bonds, since there is atomic and electronic relaxation. The surface energy is always
positive because the atoms are less bound at the surface.
Since sublimation creates new surface, let us start the estimate of the work to create a
new surface with the heat of sublimation dHsubl, typically 6.8 10-19 J/atom for metals.
Removing an atom from the surface leaves a hole. Let us assume that the hole is cubic,
with a side of area a=10-15 cm2, the average area per atom at the surface. Before
removing the atom, the cube had a surface area a, the hole has a surface area 5a. The net
change is thus 4a = 410-15 cm2. Thus, g = 6.8 10-19 / 4 10-15 J/cm2 = 1.7 104 J/cm2. In practice, it is found that instead of 0.25 dHsubl, g 0.16 dHsubl.

Material
Tungsten
(solid)
Iron (solid)
Iron (liquid)

( gJ/m2)
2.9

Mercury(liquid)
Wter

0.5
0.07

2.2
1.9

0.03
0.01

MgO

1.2

Acetic acid
Nitrogen
(liquid)
Helium (liquid)

0.0003

Dependent Superficial Tension by Temperature


Superficial tension dependent of the temperature, decreasing when it increases. If we
have the liquid in equilibrium with its vapor, the differences between the phases
decrease, as we approach the critical temperature, Tc, time disappears interphase and
there is a single phase (supercritical fluid). Thus for a temperature or above Tc = 0. As
expected decreases as T increases to Tc.
From a point of view molecular, the increases of the temperature, is traduced in a
higher kinetic energy of molecules, this allow overcome more easily the attractions
existent between them and pass more easily to the interface.
The next figure shows the anisotropy of the surface tension relative to <111> for lead as
a function of temperature.

1. Variation superficial tensin by temperatura.

1. Table tension superficial of someone substances to different temperatures.


Capillary rise
A liquid contained in a tube with a small radius develops a large pressure difference
between internal and external pressures. For example, if a capillary tube is placed inside
a liquid, it is observed that the liquid rises in the tube. The liquid level rises up the tube
until the hydrostatic pressure of the rising liquid column balances the internal pressure.

Between point A and point B, both are in the liquid and at the same level P=0

Between point B and point C interface flat (zero curvature or infinite radius of
curvature R), P=0

Entre el punto C y el punto E, ambos dentro de un gas de densidad despreciable,


P = g h = 0 (because = 0)

Between point D and point E located a curved interface, the Laplace equation
indicates

P =

gh

2
r

= Density difference between liquid and gas phases


g = Gravitational constant
h = Heigth of the capillary column

Thermodynamic Tensin
Spontaneity from the thermodynamic is determined by the free energy Gibbs, G, in this
determination is incorporated the work dA, for the closed system in there are not
variation in the number of molecules dNi= 0, it is obtained from the first law of
thermodynamics, variation internal energy in terms of heat Q, Work W, like dU= dQ +
dW. Now the variations of heat in a reversible process in function of entropy: dQ= TdS,
if the work is only volume and pressure due the surface area, as a result dW= -PdV +
dA, then replacing obtaining the internal variation energy.
dU = dQ + dW

dQ= TdS

dW= -PdV + dA

dU = TdS - PdV + dA
The same way for obtained the free energy Gibb.
G = H-TS = (U+PV) -TS
dG =dU+PdV+VdP-TdS-SdT.
Substituting in the last equation the expression dU:
dG = VdP - SdT + dA
Now when P and T are constant, dP = 0 and dT=0.
dG= dA = (dG/dA)p,t > 0
As >0, if dA <0 then dG <0, this means the surface interfacial present a tendency to
contract spontaneously. So, Gibb energy increases the surface and equilibrium
condition, to T and P constant, the system reduce the area to minimal, so that energy
Gibb is minimal.
The tendency to minimize surface energy is a defining factor in the morphology and
composition of surfaces and interfaces. Minimization of energy leads to a spherical
equilibrium shape in an isotropic liquid (in the absence of gravity). In crystalline solids,
the surface tension depends on the crystal plane and direction. Thus, the equilibrium

shape of a crystal is not obtained by minimizing the surface area but the integral
g(n)dA, where n is an orientation vector. Because g is low for some crystal planes,
faceting is energetically favored, even if it implies a larger surface area. It is important
to note that the formation of the equilibrium shape requires sufficient mobility (or fast
kinetics), not just thermodynamics. Equilibrium shapes can be calculated but it is easier
to use a graphics method, the Wulff construction. The surface tension is plotted in polar
coordinates vs. the angle with respect to a particular direction. The minimization
mentioned above implies constructing the surface from the inner envelope of planes
perpendicular to the radius vector
Temperature Dependence of Specific Surface Free Energy
For the temperature range that are typically used in the studies of surface tension, G s =
. Temperature dependence can be determined by differentiating with respect to
temperature.

1
Thus, temperature dependence of surface tension leads to the specific surface entropy.
Temperature dependence of g predicting by a semi-empirical equation (van der Waals
and Guggenheim:
2
Where 0= at T = 0 K, Tc = critical temperature (temperature at which condensed
phase no longer can exist) and n is a constant that varies from 11/9 for organic
substances to 1 for metals. Notice = 0 when T Tc.
Another empirical relationship for metals:

Where m = melting point of the metal; is in dynes per centimeter.


Specific surface enthalpy can be determined from the specific free energy and entropy
(eq. 1):

Specific Surface Energy and Heat Capacity


At constant pressure the heat absorbed upon creation of unit surface area is given by Eq.
4. If volume is constant, then we can immediately see that the specific surface energy
and specific surface enthalpy are equal to each other:

Specific Heat Capacity


Remember the heat capacity, C, is defined as C = dq/dt. This leads to:

Take derivative with respect to temperature of equation 4 to find the heat capacity at
constant pressure.

Also, using H = G + TS and taking the derivative of both sides with respect to T leads to

Surface heat capacity is equal to T times temperature derivative of entropy at constant


pressure. On metal surfaces Cv and CP are usually consider approximately equal to each
other. Accurate surface tension measurements should lead to accurate estimates of
surface heat capacity.
Multicomponent Systems
A fundamental aspect from the chemical point of view, is the modification of the
properties of interphases with the composition. In the thermodynamic treatment of the
surface of multicomponent system, we
Exist two approximations:
In 1940 Guggenheim develop a model which considers the interfacial layer as a phase
three-dimensional.
Above, in 1878, Gibbs developed model in which the interface is a surface with zero
volume. This model is the one that will work.
In the Gibbs model, the phases are separated by an area of zero thickness, the surface
Gibbs divide. The location of the surface is in principle arbitrary, but it is logical placing
it within the interfacial region.
The model system chosen such that their extensive properties (total volume V, energy
internal U, entropy S, number of moles of each component or) are equal to the system
real. Moreover the and phases model is defined to have the same intensive
properties in the real system. Logically the extensive properties of each one of the
phases of the model can not be the same as in the real system, as we have 'Deleted' part
of the system (the interfacial region). Thus, the volume of the phases V and V
Surface Energy and Surface Composition of Two Component Systems
A metal B dissolved in low concentrations in metal A will have a tendency to segregate
to the surface of A, if it forms a strong surface bond.

At all bulk concentrations of B, some of the B atoms will be at the surface of A as a


result of the surface bulk equilibrium. Formation of a strong surface chemical bond
between A and B, greatly enhances concentration of Enhancement in concentration of B

occurs when heat of desorption of B from the surface of A > heat of vaporization of pure
B If B atoms form weaker chemical bonds with A surface atoms compared to the bulk,
B atoms will be repelled from the surface and the surface concentration; surface
concentration will be less than predicted by bulk
Concentrations. Strength of A B bond strongly depends upon the reactivity of the
surface, which strongly depends upon the crystal orientation. Concentration of B in the
surface region is compared to its concentration in the bulk. The surface excess is where
nB = number of moles of B in the surface above the number of moles in the bulk region
what would contain the same number of moles of atoms as that part of the surface.

Glossary
Interphase: Intervalo entre dos fases sucesivas
Uphill: Empujar hacia arriba
Sinking: Hundimiento
Measured: Medida
Bond: Enlace
Average: Promedio
Treatment: Tratamiento

Bibliographic
Oscar A. Jaramillo Salgado- UNAM- Thermodynamic para ingeniera mayo 8 del
2013
Surface Energy University of Virginia
(http://www.virginia.edu/ep/SurfaceScience/Thermodynamics.html)
Neumann, A. Wilhelm - Applied surface thermodynamics
Maxwells Thermodynamic Surface. 1

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