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1563900
1563900
LECTURE 7
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Igneous Petrology
LECTURE 7
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-).
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Igneous Petrology
LECTURE 7
degree of polymerisation are more compact and thus denser. The abundance of metal cations is also
important in controlling the density of a magma.
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Igneous Petrology
LECTURE 7
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Igneous Petrology
LECTURE 7
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).
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Igneous Petrology
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.
M. Genge (room 1.39, ext 46467, email: m.genge@ic.ac.uk)
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Igneous Petrology
LECTURE 7
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.
(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.
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