Beruflich Dokumente
Kultur Dokumente
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
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.
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
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
Between point D and point E located a curved interface, the Laplace equation
indicates
P =
gh
2
r
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:
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
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