Lecture 2

Today’s objectives
■ Chemical behavior of elements.
■ Crystal structure of silicates.
■ Ringwood’s rule.
■ Goldschmidit’s classification of elements.
■ Chemical reactions ( Basic thermodynamics)
■ Bowen’s reaction series.
Chemical behavior of elements
The chemical behavior of an element is governed by its electronic configuration because the
energy level of the atom is determined by the spatial distribution of its electron cloud. It is only
the most loosely bound electrons in the outermost orbitals that take part in chemical interaction
with other atoms. For example, the alkali elements (group IA of the Periodic Table), all of which
have one electron in the outermost orbital, exhibit similar chemical properties; so do the alkaline
earth metals (group IIA of the Periodic Table), all of which have two electrons in the outermost
orbital.
i. Ionization potential and electron affinity
Two concepts are useful in predicting the chemical behavior of elements: ionization potential (or
ionization energy); and electron affinity. Ions are produced by the removal of electron(s) from or
the addition of electron(s) to a neutral atom. The energy that must be supplied to a neutral atom
(M) in the gas phase to remove an electron to an infinite distance is called the ionization
potential (I).
The first ionization potential (I1) refers to the energy required to remove the first (the least tightly
bound) electron. second ionization potential (I2) to the energy corresponding to the removal of
the second electron, and so on.
Classification of elements
Electron donors (metals), such as elements of Groups 1A and IIA in the Periodic Table, which
easily lose one or more valence electrons (electrons in the outermost occupied s and p orbitals)
and become positively charged ions (cations).
Electron acceptors (nonmetals), such as elements of Groups VIA and VIIA in the Periodic Table,
which readily acquire one or more added electrons and become negatively charged ions (anions).
Noble elements (inert gases), such as the elements of Group VIIIA in the Periodic Table, which do
not easily lose or gain electrons. These elements are characterized by a complete octet of electrons
in their outermost s and p orbitals.
B, Si, Ge, As, Sb, Te, Po, and At), called metalloids (or semimetals), which
show certain properties that are characteristic of metals and other properties
that are characteristic of nonmetals. Many of the metalloids (especially Si
and Ge) are used as semiconductors in solid-state electronic circuits. Whereas
metals become less conductive with increasing temperature, semiconductors
are insulators at low temperatures, but become conductors at higher
temperatures.
Ionic substitution Ringwood’s rule
Over the years the generalizations embodied in the Goldschmidt’s rules have been found to be
fraught with many exceptions. Moreover, some ion pairs of similar size and charge, such as
Mg2+ (0.72 Å) and Ni2+ (0.69 Å), show only a moderately close association, whereas a few ion
pairs, for example Sr2+ (1.18 Å) and Hg2+ (1.02 Å), show virtually no geochemical coherence.
Obviously, there are other properties that are also important in predicting geochemical
associations.
Ringwood (1955) suggested that substitution may be limited, even when the size and charge
criteria are satisfied, if the competing ions have different electronegativities and, therefore, form
bonds of different strengths.
For example, Cu2+ (0.73 A) rarely substitutes for Mg2+ (0.72 A) because of the large difference in
electronegativity (1.90 versus 1.31), although it should from the consideration of charge and
size. Si4+ (0.26 A; electronegativity = 1.9) and Ge4+ (0.73 A; electronegativity = 2.01), on the
other hand, show strong geochemical coherence because of almost identical values of
electronegativity, despite a large difference in ionic radius.
Ringwood’s rule states that between two cations satisfying the criteria of charge and size for
diadochic substitution in a crystal structure, preference will be for the one with lower
electronegativity because it forms a moreionic, stronger bond.
In most cases, the difference in electronegativity required before elements obey this rule is
about 0.1. For example, Pb2+ (1.19 Å; electronegativity = 1.8) does not substitute easily for K+
(1.38 Å; electronegativity = 0.82) in potash–bearing minerals and hence becomes concentrated
in the residual magma.
It should be evident that the extent of ionic substitution is determined by the nature of the
crystal structure and how similar the ions are in terms of size, charge, and electronegativity.
Other factors that affect the extent of substitution are the temperature and pressure at which the
substitution takes place, elevated temperatures and lower pressures favoring increased
substitution. Higher temperatures promote greater atomic vibration and open structures, which
are easier to distort locally to accommodate cations of different sizes.
Although the rules discussed above can be applied to explain to a certain extent the
distribution of elements during many geochemical processes (especially magmatic
crystallization and metamorphic recrystallization), their application is limited because of
numerous exceptions, especially when the transition elements are involved (Burns and
Fyfe, 1967; Burns, 1973).
Goldschmidt’s classification of elements
the famous Norwegian geochemist, reached this conclusion on the basis of three kinds of
observations: (i) the composition of chondritic meteorites, which are believed to have an
average composition similar to that of the primordial Earth and to have undergone similar
differentiation; (ii) analyses of metal, slag (silicates), and matte (sulfides) produced during
smelting of sulfide ores for metal extraction; and (iii) the compositions of naturally occurring
silicate rocks, sulfide ores, and native metals.
Based on the way in which the elements distribute themselves among iron liquid, sulfide
liquid, silicate liquid, and a gas phase, Goldschmidt (1937) classified the elements into four
groups: (i) siderophile (iron-loving) elements, which prefer to form metallic alloys (e.g., Fe–
Ni alloy); (ii) chalcophile (sulfur-loving) elements, which most easily form sulfides; (iii)
lithophile (rock-loving) elements, which readily combine with oxygen to form silicate and
oxide minerals; and (iv) atmophile elements, which are commonly found in a gas phase.
It is clear from the many overlaps among the groups from the table that the classification
scheme is not perfect. Some elements show affinity for more than one group, because the
distribution of any element is dependent to some extent on temperature, pressure, and
chemical environment of the system (e.g., oxygen fugacity, competing atoms, etc.). It is,
however, a useful qualitative guide to the behavior of elements during geochemical
processes.
 Chemical Reactions
Basic Thermodynamics concepts
Thermodynamics is the science that deals with differences in and possible transfers of energy, and
in some cases of matter, among systems. It is an integral part of geochemistry because it provides a
universally applicable framework for characterizing chemical reactions that ultimately control the
distribution of elements and minerals in the Earth.
The beauty of classical thermodynamics lies in the fact that it is based on two empirical laws (and a
few consistent conventions) that are adequate to quantitatively relate a host of macroscopic
measurements such as temperature, pressure, volume, etc., without requiring knowledge of the
underlying molecular structure of the materials involved in chemical reactions. Statistical
thermodynamics (or statistical mechanics), on the other hand, is the science that relates the
properties of individual molecules and their interactions to the empirical results of classical
thermodynamics.
A limitation of thermodynamics is that it does not provide any information about the rate or
mechanism of a thermodynamically predicted chemical reaction. Some reactions, especially at low
temperatures, are so sluggish that, for all practical purposes, they do not seem to proceed at all. If
this were not the case, we would have no igneous or metamorphic rocks surviving on the Earth’s
surface. The study of the rates and mechanisms (pathways) of reactions belong to the field of
kinetics.
Chemical equilibrium (Law of Mass Action – equilibrium constant (Keq)
Suppose, we mix two substances X and Y in a closed container and at some appropriate temperature so
that they would chemically react to form two other substances C and D.
The forward reaction X + Y → C + D will result in complete conversion of X and Y into C and D.
Thermodynamic systems
The system we define can be as small as a rock chip or as large as the entire earth.
The rest of the universe beyond the chosen system constitutes the surroundings.
The matter contained in a system can be described completely in terms of phases
and components. A phase is defined as a physically distinct, homogeneous body
of matter that is, at least in principle, mechanically separable from the rest of the
system. Each mineral in a rock is a single phase even if it is dispersed in
homogeneously throughout the system. A mixture of gases, on the other hand, is
one phase because gases are miscible in all proportions. A mixture of miscible
liquids is also one phase, but immiscible liquids, such as water and oil, must be
counted as separate phases. A system consisting of a single phase is called
homogeneous; a system consisting of more than one phase is called
heterogeneous.
Kinds of thermodynamic systems and processes Thermodynamic systems are classified into
various kinds depending on the exchange of energy (in the form of heat or work) and matter
between the system and the surroundings:
Isolated system – a system that permits no exchange of either matter or energy (in the form
of heat or its mechanical equivalent, work) with the surroundings; such a system maintains a
constant mass, a constant bulk chemical composition, and a constant level of energy.
Closed system – a system that permits exchange of energy with the surroundings but not
matter; such a system has a constant mass and a constant bulk chemical composition but
variable energy levels.
Open system – a system that permits exchange of both matter and energy with the
surroundings; such a system has variable mass, bulk chemical composition, and energy
levels.
Most geological systems are open, but some may be treated as closed because of very slow
rate of mass exchange with the surroundings. Isolated systems do not exist in nature. In
addition to reversible and irreversible processes defined earlier, a system may undergo change
by special processes that are named according to the constraint imposed on the system:
isothermal (constant temperature); isobaric (constant pressure); isochoric (constant volume);
and adiabatic (constant heat content, although the system can exchange energy with the
surroundings in the form of work).
Metastability
Metastability refers to the persistence of a mineral or a mineral assemblage in a pressure–
temperature environment where thermodynamically it is not stable. A familiar example of
metastability is diamond. Diamond is stable only under the high pressure–temperature
conditions of the mantle, yet it occurs at or near the Earth’s surface in kimberlites and placers
instead of being oxidized to CO2 by atmospheric oxygen:
C (diamond) + O2(g) ⇒ CO2(g), ΔG1 r, 298 = −394 kJ mol−1 (4.97)
Another example is the metastable occurrence of the mineral olivine in rocks exposed at the
Earth’s surface. It is well known that olivine typically occurs in mafic and ultramafic igneous
rocks and is a mineral that crystallizes from magmas at relatively high temperatures. It is,
therefore, very susceptible to chemical weathering when such rocks are exposed on the
Earth’s surface. In the presence of water, olivine alters to serpentine, which may be
represented by the reaction
2Mg2SiO4 + 3H2O = Mg3Si2O5(OH)4 + Mg(OH)2
Computation of simple P–T phase diagrams
Phase diagrams depicting stability fields of minerals and mineral assemblages in P–T space is
widely used for predicting which mineral or mineral assemblage is stable at any particular T
and P. The preferred way to construct such phase diagrams is to conduct experiments under
controlled P–T conditions.
Subject to the availability of relevant thermodynamic data, simple phase diagrams can also be
constructed quite easily by application of the concepts and computational techniques
developed in the previous sections. The task involves computation of reaction boundaries that
delineate the stability fields of minerals and mineral assemblages of interest in P–T space.
Bowen's Reaction Series
Bowen's reaction series is a means of ranking common igneous silicate minerals by the
temperature at which they crystallize. Minerals at the top have a relatively high
crystallization temperature, which means that they will be the first minerals to crystallize
from a magma that is cooling. IF they are chemically compatible with the magma as
it continues to cool, they will grow larger by addition of external layers of additional
material. [They then can potentially become the phenocrysts in a porphyritic igneous
texture.] If they are chemically incompatible, they will react with the melt and recrystallize
into new minerals. What determines this chemical compatibility is in large part the
silica content of the melt.
Minerals on the left part of the "Y" of the diagram are what are called ferro
magnesian minerals, because they contain iron (Latin: ferrum) and magnesium in their
composition. This part of the series is referred to as the discontinuous series, since
these minerals, if chemically incompatible with the melt as it cools, will usually completely
react to form totally new minerals: an olivine crystallizing in a melt relatively high in silica
(e.g., 60%) will completely recrystallize into pyroxene, and that pyroxene may in part
or completely recrystallize into hornblende.
The minerals on the right arm of the "Y" are the plagioclase feldspars, which form a
continuous series from 100% Ca plagioclase (anorthite) with the highest melting point, to 100%
Na-plagioclase (albite) with the lowest melting point. The first crystals forming may only
partially re react with the melt, but without destroying the basic feldspar crystal structure.
Very often, large plagioclase crystals in an igneous rock will have cores that are more calcium rich
than the outer layers, and sometimes this layering (called zonation) can be clearly seen under the
microscope, or even with the naked eye for particularly large crystals.
In general, melts higher in silica are higher in sodium (Na) and lower in calcium (Ca).
The lower portion of Bowen's Re action Series is dictated more by chemistry than is the
upper part. Biotite, orthoclase feldspar and muscovite are the only minerals here that
contain large amounts of potassium; of these three, only biotite is found in volcanic rocks.
Orthoclase is a mineral found in plutonic rocks, those that crystallize entirely underground.
Its high temperature (1000°C melting point) volcanic equivalent with the same formula but
a different crystal structure is the mineral sanidine, which is common in high silica volcanic
rocks. Minerals near the bottom of the series also have much higher silica contents than the
minerals at the top (e.g., pure olivine is about 38% SiO2 , while pure sanidine is 65% SiO2). It is
this increase in silica content that lowers the melting point; note that quartz, at the bottom of the
series, is 100% SiO2 and has the lowest melting point (about 700°C)