Escolar Documentos
Profissional Documentos
Cultura Documentos
Definiciones Generales
Mineral = especie mineral
Variedad mineral
Cristal
Sustancia amorfa
% en peso en la Corteza
Oxigeno
30.0
46.60
Hierro
35.0
5.00
Silicio
15.0
27.70
Magnesio
13.0
2.09
Nquel
2.4
<1
Calcio
1.1
3.63
Aluminio
1.1
8.13
Sodio + Potasio
<1
5.40
El resto
<1
1.41
Se observa que casi la mitad de la corteza esta formada por oxigeno (% en peso), y
adems ocupa casi el 94% de su volumen. Esto se refleja directamente en los minerales
existentes en la corteza. El oxigeno es el anin mas predominante en la corteza, por ello
se comprende el porque los silicatos son los ms abundantes en la corteza. Entonces, se
puede decir, a escala atmica, que la corteza terrestre consiste esencialmente de un
empaquetamiento de aniones oxgenos con cationes metlicos intersticiales,
principalmente silicio. Adicionalmente, la corteza contiene cantidades significantes de
otros compuestos oxigenados tales como los xidos y carbonatos.
Aunque la corteza esta compuesta bsicamente de minerales hechos con solo ocho
elementos, los otros 90 elementos que naturalmente ocurren estn presentes. Es
importante mencionar que muchos elementos que son necesarios en nuestra sociedad
tienen una abundancia muy baja. Por ejemplo, el cobre que se presenta como un metal
nativo y en una variedad de minerales de la clase sulfuros, esta solamente presente en
una concentracin de 55 ppm aproximadamente. Algunos elementos estn acumulados
en minerales particulares; el Pb, por ejemplo se le encuentra mayormente en el mineral
galena (PbS). Por otra parte, algunos elementos como por ejemplo el Rb estn
dispersados en bajas concentraciones en minerales formadores de roca y nunca en un
mineral de Rb.
La existencia del gran nmero de minerales hasta ahora reconocidos, puede ser
explicada por dos variables principales:
1. Qumica del cristal
2. Estructura del cristal
Por ejemplo, una composicin qumica dada puede resultar en un nmero de minerales
distintos que difieren en la estructura cristalina (polimorfismo). Similarmente, la misma
estructura cristalina puede dar lugar a un nmero diferente de minerales dependiendo de
la composicin qumica. As, la estructura de la halita (NaCl), es comn a un gran
nmero de muy diferentes minerales con diferentes cationes y aniones (minerales
isoestructurales).
La formula de la esfalerita es: ZnS, pero la esfalerita CASI SIEMPRE tiene cantidades
importantes de hierro (adems de otros elementos tales como Cd, Tl, Mn, etc). El hierro
esta ocupando posiciones que debieron ser ocupadas por el Zn.
Hay tres factores que determinan si una solucin slida puede ocurrir, y determina la
cantidad de solucin slida que puede ocurrir.
1. El tamao del in, tomo o molculas que estn siendo sustituido por otros (no mayor
a 15%, si difiere entre 15 y 30% la sustitucin es rara o limitada, si el radio difiere en
ms del 30% la sustitucin es improbable).
2. La carga o estado de la valencia de los iones envueltos en la sustitucin. El
requerimiento fundamental para la estabilidad del mineral es que la neutralidad
elctrica del mineral debe existir.
3. La temperatura a la cual la sustitucin tiene lugar. La extensin de la sustitucin esta
determinada por la naturaleza de la estructura y la temperatura de formacin de la
sustancia (T altas de sustitucin, debido al incremento de la vibracin de los iones)
Termometra geolgica: Una vez que el grado de sustitucin atmica ha sido
determinado para una sustancia dada para diferentes temperaturas y presiones, la
composicin de sus ocurrencias naturales anlogas puede ser considerada para
indicar la temperatura y presin de formacin de dicha sustancia.
Tipos de sustitucin
Catinico o Aninico Simple, es el tipo ms simple, en el que la carga y el tamao del
in sustituto es el mismo que el in remplazado. En la siguiente tabla la sustitucin est
indicada por el signo"=".
K = Na
Mg = Fe = Mn
Cl = Br
(KCl - KBr)
Fe = Zn
(Zn,Fe)S (esfalerita)
Na+Si4+ = Ca2+Al3+
Mg2+Al3+ = Fe2+Ti4+
Polimorfismo
Ideomorfismo
Hipogeno = Endogeno : energa interna de la tierra
Exgeno = Supergeno: energa del sol
epigentico singentico
Inversin reversible = Inversin enatiotropica
Inversin irrevesible = Inversin monotropica
Exsolucion o desmezcla
Seudomorfismo
Mineral metamictico
Esontaneo
reversible
como la energa de nucleacin. Esto es reconocido cuando se observan que los lquidos
pueden ser superenfriados (enfriados varios grados por debajo de la temperatura de
cristalizacion), o ser supersaturado cuando los cristales debera estar estables. En
esencia, los cristales deben estar hechos para formar o por addicin de nucleos o
impartiendo suficiente energa para sobrepasar la energa de nucleacin.
Transporte
El crecimiento de cristales requiere que tanto el transporte de "nutrientes" al lugar del
crecimiento y el transporte del calor lejos del lugar. Para entender lo ltimo, se debe
recordar que la primera ley de la termodinmica dice que la energa debe ser
conservada. La cristalizacin en equilibrio requiere que la fase cristalina tenga una
energa ms baja que la fase reactante, la energa en la forma de calor debe ser liberada
durante la cristalizacin. Esto es conocido como el calor latente de la cristalizacin. A
menos que este calor sea removido o transferido al cuerpo mayor de la solucin, la
cristalizacin es debilitada, debido al incremento en temperatura resulta en tomos con
energa tan alta para pegarse al cristal en crecimiento. La velocidad de cristalizacin,
por lo tanto depende de cuan rpidamente el calor latente de cristalizacin puede ser
removido de las superficies del cristal en crecimiento.
El calor latente removido no es el mismo en todas las partes de la superficie del cristal.
Por ejemplo calor latente es disipado mas rpidamente del vrtice de un cristal cbico
que de sus lados o caras, debido a que el volumen de la solucin que es capaz de
absorber calor por unidad de volumen es mayor para un vrtice que para un lado. Una
cara del cubo disipa calor menos efectivamente, y por lo tanto deber crecer ms
lentamente que los lados o los vrtice. El acumulamiento local de calor latente no
disipado en las caras y un excepcionalmente rpido crecimiento de los lados y los
vrtices puede producir crecimientos dendrticos. Dendritas son comunes en cristales
naturales y sintticos (hechos por el hombre) y son reconocidos por sus finas,
protuberancias como rboles y formas como ramas. Estas formas requieren una
cristalizacin extremadamente rpida y/o sper enfriamiento importante.
Otro factor relacionado que puede tambin producir cristales dendrticos o esquelticos
es la formacin de gradientes de concentracin en la interfase del crecimiento del cristal
y soluciones circundantes. Un cristal en crecimiento debe tener continuamente una
fuente fresca de reabastecimiento (i.e., saturada) de la solucin si el crecimiento es
proceed a una velocidad constante. Por que si no, la solucin se volver no saturada con
respecto a los componentes del cristal. Otra vez, este fenmeno favorece el crecimiento
en las esquinas, seguido de los lados y finalmente las caras.
Bajo condiciones de crecimiento lento,
ni el calor de disipacin ni la difusin
jugaran un rol importante. Sin embargo,
bajo condiciones de enfriamiento rpido
y/o alto grado de sper saturacin, este
fenmeno puede dominar el proceso de
crecimiento y resultar en cristales que
tienen poco parecido a sus formas
euhedrales. Esto se muestra en la figura
a la derecha growth rates at corners and
edges, produced strange forms. If caried
to extreme these processes can lead to
crystals that are hollow (hopper crystals)
o dendritas.
Crecimiento del cristal
A distinctive feature of many crystals is their ability to grow to predictable shapes that
are bounded by flat planes (faces). As we have seen the external morphoogy is directly
related to the internal structure and symmetry. One of the earliest systematic work on
this relationship was that of Bravais, who in 1860 stated that the most prominent faces
of a crystal are those that are parallel to internal planes having the greatest density of
lattice points. This statement became known as the "law of Bravais". Bravais also
noted that a high density of lattice points is always associated with a large interplanar
spacing (d) perpendicular to the plane. Conversely, planes with small interplanar
spacing are associated with low density of lattice points.
The figure to the left illustrates this
concept using a 2-dimensional lattice.
Notice that the simpler the Miller
indices, the higher the density of lattice
points, and the larger the d-spacing
between the planes. It is a general
observation that the dominant faces in a
crystal tend to have simple Miller
indices. Therefore, (001) faces will tend
to be more prominent than (103) faces.
Although exceptions do exist, this is a
useful rule to follow in indexing
observed faces on a crystal.
Twinning in Crystals
Crystals commonly occur in groups, either with other crystals of the same kind, or with other minerals.
This individual crystals composing any group may have various relationships to each other. In the
majority of cases these relations are irregular and result from accidental conditions of growth. All of the
crystals of one mineral in a group may grow with crystallographic axes in completely random directions,
or they may occur in a parallel (oriented) fashion (common in metamorphic rocks).
Twins often appear to consist of two or more individual crystals symmetrically united.
A twin can be described as a rational, symmetrical intergrowth of two or more
individuals of the same mineral. Twins are distinctly different from the random
mechanical intergrowths that are symmetrically unrelated. In the context of twinning,
rational means that the two portions of the twin have a point, a line or a plane in
common, and symmetrical means that the parts of the twin are related by some
crystallographic symmetry operation, such as reflection, rotation or translation. The
plane on which the twinned crystals are joined is called the composition plane. Twinned
crystals can be described as:
Simple Twins: if composed of only two parts.
Multiple Twins: if more than two orientations are present.
Contact Twins: if the two parts are joined along a uniform plane.
Penetration Twins: if two or more parts of a crystal appear to penetrate each other, the
surface between the parts being irregular. (e.g., staurolite).
There are basically two kinds of
such symmetrical arrangements
which we can observe in crystals. In
the first case, the individual parts of
the twin lie as if reflected across a
mirror plane. This plane is known
as the twin plane. Generally, but not
always, the twin plane is the same
as the growth or composition plane.
In the second case, the individual
parts of the twin are rotated 180O
with respect to each other, around a
rotation axis known as the twin
axis. If you consider the constraints
imposed by translational symmetry,
it should be apparent that a regular
plane of mirror symmetry in a
crystal cannot also serve as a twin
plane for a twinned crystal. No
operation of symmetry elements
present in the normal crystal can
produce
a
new
geometric
arrangement of the parts.
Figure 6-8 is a simplified attempt to
illustrate how a twin might form during the growth of a crystal. If we start with a layer
of atoms, (shown as the solid circles), and imagine adding another layer on top of A,
there are two choices for the placement of the next layer. Spheres comprising the next
layer may be placed above the void labeled C, or alternatively above the void labeled B
(dashed circles). Which position is actually filled is normally determined by the
equilibrium energy of the crystal in the two possible states. Schematically, the energy is
shown in the figure with energy minima corresponding to the B and C "sites". The
energy minimum associated with site B is lower, and hence the normal equilibrium
distribution would be to place the next layer in the B position. Energetically, site B is
the most stable position for growth. However, if the energy difference between C and B
is small, it is possible that an atom or ion may arrive at C rather than at B and the
thermal agitation is not large enough to move the new atom or ion to the B position. If
this happens, the position/direction of all future growth will be altered from the normal
orientation. With this perspective, growth twins can be viewed as "accidents" during the
growth process.
Twins can also form after a crystal has
grown. Such twins are known as
transformation twins, and may develop
during polymorphic transformation (e.g., bquartz transforming to a-quartz) or during
deformation. Figure 6-9 illustrates the
possible formation of a transformation twin
developing as a result of shearing of the
crystal lattice. In this case shear in a N-S
direction distorts the lattice and eventually
results in glide. Note that in this case the
twin plane is a glide plane.
Twinning in Plagioclase Feldspar
One of the most spectacular and yet common
examples of twinning occurs in plagioclase.
Plagioclase is triclinic and hence there are no
planes or axes of symmetry to place restraints on
the possible planes or axes of twinning. The
twinning observed in plagioclase is not of the
simple type, but consists of many repeated twins.
The actual twin units are typically too small to be
seen with the naked eye. They are termed
polysynthetic twins, consisting of successive
layers arranged in an alternating fashion.
The easiest way to understand these principles is to consider mineral polymorphs -- two
or more minerals with the same chemical composition, but with different crystal
structures (e.g., graphite and diamond). Enthalpy is ultimately controlled by bond
strengths, and entropy (or degree of randomness) is directly related to the ways in which
individual atoms are arranged in a crystal's structure. Hence, different polymorphs
musts have different enthalpies and entropies, and we should also predict that both H
and S will vary with temperature and pressure differently between polymorphs. The
end result is that a given pressure and temperature, one polymorph will have the lowest
Gibbs Free Energy, and will be stable under those conditions. At some other
combination of T and P, however, another polymorph will have the lowest Gibbs Free
Energy, and will thus be stable under those conditions. A familiar example of this
control on mineral stability is graphite and diamond. We know that diamond is only
stable relative to graphite at very high pressures. This stability relationship is shown in
the Figure 10-7 and 10-8.
Given the stability relationships between graphite and diamond, we might ask why we
ever see diamond at the surface of the Earth. It is clearly unstable, relative to graphite.
The reason why diamond persists is that the conversion to graphite is largely controlled
by kinetic factors. If you recall the structure of diamond, it consists of a uniform 3dimensional array of covalent-bonded carbon atoms. In order to convert this structure
to that of graphite, those bonds must first be broken. As shown schematically in Figure
10-8 the energy barrier (called G of activation) separating graphite and diamond is very
high. Consequently, at the low temperatures of the Earth's surface, diamond is
kinetically stable, and does not invert to the graphite structure.
The figure below shows the stability relations for the various polymorphs of SiO2. Note
how the presence of a particular polymorph may be used to estimate the P-T conditions
at which the mineral formed.
These examples demonstrate that pressure (P) and temperature (T) play the most
fundamental roles in determining the stability of individual minerals. This is most
clearly seen if the mineral has polymorphs, as shown in the diagrams above. T and P
are the most important parameters in controlling all chemical reactions -- not just
polymorphic reactions. Indeed, all reactions identified on composition-space
(chemographic) diagrams are primarily functions of temperature and pressure. For
example, we saw in the last lecture that when considering the chemographic relations
between olivine, pyroxene and quartz, we can deduce the balanced chemical reaction
among these minerals to be:
Fe2SiO4 + SiO2 <==> 2FeSiO3
Thermodynamics require that each state of the system (Fe2SiO4 + SiO2 or alternatively
2FeSiO3 ) be stable only in a defined region of P-T space.
In ternary systems, chemographic diagrams identify chemical reactions by either direct
combination (a phase surrounded by three other phases (A+B+C = D) or by the crossing
of tie lines on a triangular composition diagram. The figure to the right shows the
ternary system CaO - SiO2 - Al2O3 described in the last lecture. Note that the tie line
(simply lines connecting two minerals) between grossular and quartz crosses that
connecting anorthite and wollastonite. The tie lines that cross represent the products and
reactants in a balanced chemical reaction. In this case, the reaction is as follows:
grossular + quartz + anorthite + 2wollastonite
Ca3 Al2Si3O12 + SiO2 <==> CaAl2Si2O8 + 2CaSiO3
This reaction is said to be discontinuous because
it introduces a new phase or phase assemblage.
Mineral reactions may also be continuous
when they do not introduce new minerals, but
instead govern the composition of solid solution
minerals. To illustrate this concept, consider the
solid solution minerals, olivine (Mg, Fe)2SiO4
and pyroxene (Mg, Fe)SiO3. The composition
space (chemographic) relations of these minerals
is shown in the figure to the left. Note that if
you apply the concept of crossing of tie lines, a
reaction exists as follows: