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Igneous Petrology

LECTURE 7

The Structure of Magmas


Understanding the atomic structure of magmas is important since it allows us to predict their
physical (rheological) and chemical behaviour. Most magmas on Earth are silicate melts and these
have structures similar to silicate minerals except they are more disordered and undergo continual
rearrangement.

1. Revision of Atomic Bonding


Understanding atomic bonding is important if we are to get to grips with atomic structures. There are
two main types of atomic bond. (1) Ionic bonds in which atoms are held together by their mutual
electrostatic attraction. The negative electrons of one atom attract the positive nucleus of another
atom and vice a versa. (2) Covalent bonds in which atoms share electrons in order to become more
stable. Generally covalent bonds are directional and much stronger than ionic bonds.

2. Silicate Mineral Structures


The structures of silicate minerals are based around the
silica tetrahedra which consists of one Si atom surrounded
by 4 oxygens. The tetrahedra has the shape of a three
sided pyramid in which all the faces are equilateral
triangles.
The Si-O bonds in the silica tetrahedra are covalent. These
are strong and directional. The tetrahedra, therefore,
behaves as a rigid unit in silicate structures. Because the
silicon atom has a charge of 4+ and each of the 4 oxygens has a charge of 2-, the net electronic
charge of the tetrahedra is 4-. This is written as SiO44-.
The huge variety of silicate minerals arises because the oxygen in the silica tetrahedra are able to
form covalent bonds and link tetrahedra together. The tetrahedra share oxygens to form chains,
rings, sheets and 3D
networks. Different atoms
in silicate minerals play
different roles in the
structure. Silicon is the
basis of the tetrahedra on
which the network is
formed and is, known as a
network former. Oxygen
is present in two forms in
silicate minerals. Where it
links tetrahedra together
it is known as bridging
oxygen. Oxygen atoms
that are not shared
between tetrahedra are
known as non-bridging
oxygens. Electropositive
atoms (positively charged
since they have more
positive protons in their
nucleus than electrons in
their electron shell) hold
chains, rings and sheets
together through ionic
bonds. However, they
also influence the shape
of the network structure
they are known as
network modifiers.

M. Genge (room 1.39, ext 46467, email: m.genge@ic.ac.uk)

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The electronic charge of oxygen also changes depending on its role in the structure. Free oxygen,
which is not involved in silica tetrahedra, has a charge of 2- (O 2-), non-bridging oxygen has a charge
of 1- (O-) and bridging oxygen has a charge of zero (O0). The electronic charge depends on the
number of electrons that the oxygen is sharing in covalent bonds. Non-bridging oxygen shares one of
its two additional electrons with one silicon atom. Bridging oxygen shares both its two extra electrons
with two silicon atoms. The net charge of a single isolated tetrahedra is thus 4- (SiO 44-). The net
charge of two tetrahedra with a shared (bridging oxygen) is 6- (Si 2O76-).

Silicate Melt Structures


The structure of a silicate melt, like that of a silicate
mineral, is formed by a 3D network of linked silica
tetrahedra. In silicate melts, however, the structure
is more disordered, is flexible and can rearrange
itself through the random motions of atoms and
molecules. The network in the melt contains many
irregular rings and chains.
Atoms in the structure play the same roles as in
silicate minerals. There are network formers (Si),
bridging oxygens (O0) and non-bridging oxygens
(O-) making up the tetrahedra network, free
oxygens (O2-) that are not part of tetrahedra, and
network modifiers that support and change the shape of the silicate network.
2.1. Making the Network: Polymerisation.
To construct the silicate network we must add
silica tetrahedra to the framework, turning nonbridging oxygens into bridging oxygens. This
process of building a larger molecule by the
repeated addition of smaller molecules is known
as polymerisation and the network itself is a
polymer. Most hydrocarbons and complex organic
molecules such as DNA and proteins are also
polymers.
In the figure opposite we can see that increasing
the size of the network by adding tetrahedra leads
to molecules with the formulae SiO44-, Si2O76-,
Si3O108-, Si4O1310- - note that the ratio of oxygen to
Si decreases because some oxygens are shared between the tetrahedra as bridging oxygens. We can
use the ratio of the number of non-bridging oxygens (NBOs) to the number of tetrahedra (T) as a
measure of the degree of polymerisation. Note that NBO/T=4 for isolated tetrahedra and it decreases
to 0 for a structure where all the oxygens are bridging and shared between tetrahedra. NBO/T thus
decreases with increasing polymerisation.
We can write polymerisation as a reaction:
SiO44- + SiO44- Si2O76- + O2- (reaction 1)
Notice that polymerisation also produces free oxygen and that, like any reaction at equilibrium it
proceeds both ways at the same rate (i.e. it is balanced). In a liquid this is particularly true since the
structure is forever being constructed and deconstructed even though the total degree of
polymerisation stays the same. The processes by which the framework decreases in size is known as
depolymerisation.
3.2. The Physical Properties of Magma and Polymerisation
A more polymerised magma (i.e. lower NBO/T) will have a higher viscosity than a less polymerised
magma. This is because the silicate network, although flexible, consists of strong directional covalent
bonds that resist deformation. Viscosity is simply a measure of the resistance of a liquid to flow, and
flow requires the structure to deform and move. The more polymerised the magma the less easily it
can deform and the higher its viscosity.
Density, to a lesser extent, is also dependent on the degree of polymerisation. Magmas with large
polymers tend to be less dense since their silicate network contains open rings. Magmas with a low
M. Genge (room 1.39, ext 46467, email: m.genge@ic.ac.uk)

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degree of polymerisation are more compact and thus denser. The abundance of metal cations is also
important in controlling the density of a magma.

M. Genge (room 1.39, ext 46467, email: m.genge@ic.ac.uk)

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2.2. The Effects of Temperature and Pressure


Increasing temperature results in depolymerisation of the silicate network of a magma because the
increased kinetic energy of atoms makes it easier for bonds to be broken. Since the magma becomes
more depolymerised it, therefore, becomes less viscous (density usually still decreases, however,
due to expansion of the melt). Decreasing temperature causes an increase in polymerisation for the
opposite reason and increases the viscosity.
Increasing pressure results in polymerisation of the silicate network of a magma because the
structure is compressed and new bonds between tetrahedra form. Increasing pressure causes
increases in viscosity and density of the magma.
2.3. The Effects of Composition on Polymerisation
By considering the degree of polymerisation we can predict changes in the physical (and chemical)
properties of the magma with changes in composition.
3.3.a Silica Content
Increases in the SiO2 content of a magma produces large increases in the degree of
polymerisation since there are more SiO44- tetrahedra available to construct the network. Silica-rich
(acid) magmas are, therefore, much more viscous and have a lower density than silica-poor (basic)
magmas. The addition of any network former will cause an increase in polymerisation.
3.3.b. Metal abundances
The abundance of metal atoms other than Si changes the degree of polymerisation due to charge
balancing. The diagram below shows that we need to balance the negative net electronic charge of
the silicate network with positively charged metal atoms (cations). The number of cations per
tetrahedra in the network needed to balance the
excess negative charge is shown in the diagram
as M/T for divalent (2+) cations. Note that the
larger the network the fewer cations are needed
to balance the charge. Network modifiers,
therefore, not only help support the network (i.e.
keeping rings open) they also balance the
negative electronic charge of the network. The
total electronic charge MUST be zero.
If we added more divalent cations to a magma
you can see that it would have a positive total
electronic charge. This is not allowed and
depolymerisation would occur, making the
network more electronegative to charge balance
the cations.
Magmas richer in metals such as Fe2+ and Mg2+ relative to SiO2 are, therefore, less polymerised and
have lower viscosities. Note that monovalent cations
(charge 1+), such as Na and K, have a similar effect,
however, more of them are needed to charge balance the
network (as shown opposite). These cations have much
larger ionic radii than divalent cations such as Fe and Mg
and tend to make the network more open (i.e. they support
larger rings in the structure). Because the structure is more
open it is cannot be as highly polymerised. Magmas rich in
alkali metals (such as Na and K), therefore, tend to be less
polymerised and less viscous.
3.3.c. Aluminium and other network formers
Any atom that can substitute for silicon in the
silica tetrahedra can act as a network former.
Aluminum is the most important in natural
magmas and complicates the structure since
it has a lower electronic charge than Si of 3+.
If aluminium is present as a network former
(i.e. replacing Si) then the silicate network will
have a larger overall negative charge (i.e. it
will be more electronegative). More charge
balancing cations (network modifiers) will be needed to charge balance the aluminium-containing
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network. These can be trivalent (3+), divalent (2+) or monovalent (1+) cations. Even Al 3+ can be
present as a network modifier (i.e. outside the tetrahedra) to perform charge balancing. If there
arent enough charge balancing cations the network will depolymerise. If there are then Al will cause
polymerisation (because it helps build the network).

M. Genge (room 1.39, ext 46467, email: m.genge@ic.ac.uk)

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LECTURE 7

3.3.b. Volatiles
Volatiles are gaseous substances such as CO2 and H2O. They are very important in the behaviour of
magmas during eruption, they change the melting point of magmas and they change their physical
properties. Water and CO2, however, behave differently when incorporated into magmas.
Water
The diagram opposite shows the
reaction mechanism by which
water dissolves in a silicate
magma. The hydrogen of the
H2O molecule reacts with a
bridging oxygen of the silicate
network to form a hydroxyl (OH)
molecule which is hydrogen
bonded to a bridging oxygen.
The reaction of the H2O
molecule causes
depolymerisation. Adding water
to a silicate melt will, therefore,
decrease its viscosity. The
viscosity of polymerised melts,
such as acidic melts, decreases
more significantly with water content than less polymerised (basic) melts.
As a reaction this can be written as:
Si2O76- + H2O = 2SiO44- + 2HThe degree of polymerisation also controls the amount of water that can be dissolved in a magma.
Polymerised magmas (acidic) can dissolve large amounts of water since they have more bridging
oxygens. The solubility of water in magmas, therefore, decreases with SiO2 content due to the
decrease in polymerisation (i.e. acid magmas can contain more dissolved water than basic magmas).
With decreasing pressure the solubility of water in a magma decreases because of the decrease in
polymerisation. The explosive volcanism of acid magmas is a result of this behaviour since as they
rise through a conduit the pressure decreases until the water can no longer be dissolved in the
magma and exsolves as water vapour. The large expansion of the vapour causes the explosive
nature of the eruption.
Carbon Dioxide
Carbon dioxide (CO2) dissolves in a magma
by reacting with a non-bridging oxygen of
the silicate network to form a carbonate
molecule (CO32-). The removal of the nonbridging oxygen causes polymerisation of
the network as shown and thus increases
in viscosity. Because CO2 solubility is
dependent on non-bridging oxygens it is
higher in depolymerised magmas. The CO2
content of basic magmas is, therefore,
higher than acidic magmas.
As a reaction this can be written as:
Si2O76- + CO32- = 2SiO44- + CO2
A complication is in the presence of Al3+ as a network former (i.e. in the tetrahedra) since the
carbonate ion formed by the reaction of CO2 forms a complex with a divalent cation which can no
longer balance the charge of the Al in the network. In the case of Al-rich magmas CO 2 can cause
depolymerisation.
3.3.c. Oxygen
Oxygen is the most abundant element in igneous rocks and has important effects on the structure of
silicate magmas and the minerals that crystallise from them. Free oxygen is a powerful chemical
agent (because of its bonding capabilities) and its abundance is described by the oxygen
fugacity.The higher the abundance of free oxygen the higher the oxygen fugacity.
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To see the effects of oxygen fugacity on the structure of a silicate melt we can write reaction 1 just in
terms of bridging (O0), non-bridging (O-) and free (O2-) oxygen.
4O- + 4O- O0 + 6O- + O2- (reaction 2)
for any reaction at equilibrium its progress is constant (because its balanced) and can be described
by an equilibrium constant k where [O0] is the abundance of bridging oxygen. k is constant at
constant pressure and temperature.

[O 0 ].[O ]6 .[O 2 ] [O 0 ].[O 2 ]

(equation 1)
[O ] 4 .[O ] 4
[O ] 2

Because k is a constant if we increase the oxygen fugacity (i.e. increase [O 2-]) we must decrease the
number of bridging oxygens relative to non-bridging oxygens (i.e. [O 0]/[O-]). Increasing the oxygen
fugacity (the abundance of free oxygen), therefore, causes depolymerisation.

M. Genge (room 1.39, ext 46467, email: m.genge@ic.ac.uk)

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