Phase Diagrams

2004 GEOLOGY
INSET PROGRAMME
Supporting ESTA

(Earth Science Teachers Association)

Solid Solution Phase Diagrams

The solid solution phase diagram explains the behaviour of chemical solid solution series, such as the transition from high temperature, calcium-rich plagioclase to low temperature sodium-rich plagioclase, or the transition from high temperature magnesium-rich to low temperature ironrich crystals in ferromagnesium minerals (e.g. olivine, pyroxene). The example here is for the PLAGIOCLASE FELDSPARS.

Phase The following relates to the Diagrams behaviour of plagioclase under

complete equilibrium conditions during crystallization. The conventions for the phase diagram include the following: 1. Two components: high temperature CaAl2Si2O8 (anorthite) and low temperature NaAl2Si2O8 (albite) plotted along the horizontal axis. Low temperature, sodic plagioclase (Albite) is on the left; high temperature calcic plagioclase (anorthite) is on the right. Composition is in % anorthite. A 30% anorthite melt has 30% calcium and 70% sodium.

Phase As we expect from Bowen's Diagrams reaction series, Ca-rich anorthite

crystallizes at a much higher temperature than Na-rich albite. 2. One variable - Temperature is plotted along the vertical axis. 3. Pressure is held constant at 1 atmosphere. 4. Two phases: crystal and liquid melt. The diagram is divided into three fields, all liquid, liquid + crystal, all crystal. The liquidus line separates the all liquid phase from the liquid + crystal phase. The solidus line separates the liquid + crystal phase from the all crystal phase.

Phase The solidus and liquidusDiagrams lines are experimental; they have
been determined by melting and cooling many melts at different anothite percentages.
5. Complete miscibility (mixing) occurs in both liquid (magma) and crystal phases. The assumptions are: The system remains in equilibrium throughout its history so that all reactions can take place and everything can come to stability. Early formed crystals completely react back with the melt as temperature falls to produce the feldspar most stable at that temperature.

Phase USING THE GRAPH Diagrams (numbers on phase diagram

correspond with numbers below) 1. As an example, take a hot melt (over 1500 degrees) of 30% anorthite (70% Albite). 2. Cool melt to liquidus line. First crystal begins to form at about 1380o. 3. To determine the composition of the first crystal move horizontally across to the solidus line. The solidus always indicates crystal composition. 4. Then drop from the solidus straight down to the bottom scale. The first crystal is 72% anorthite (28% Albite). The diagram is always read in this manner, down-across-down regardless of starting composition. 2

Phase As the temperature drops Diagrams and

crystallization continues, Ca is removed from the melt faster than Na. (a 30% anorthite melt yields a first crystal with a composition ratio of 72% Ca:28% Na) Thus as crystallization proceeds the Na concentration of the melt increases and Ca gets lower.

Phase 5. Thus as the temperature Diagrams lowers the composition of the

melt migrates down the liquidus line. But at the same time the composition of the crystals forming are moving down the solidus line (that is, decreasing in Ca.) This is because the system cools slowly enough to stay in equilibrium at all times. The earlier formed crystals react with the melt, exchanging Ca for Na, to come to a composition in equilibrium with the temperature at the moment. The composition of the melt and crystals move down in tandem, exactly opposite each other along a horizontal line. 2

Phase Thus at any temperature the Diagrams combined composition of both

the crystals and melt must equal the original composition of the melt. QUESTIONS: (i) What will be the composition of the last drop of melt? (ii) At what temperature will it crystallise? (iii) What will be the composition of the last crystal from the melt? ANSWERS (i) The last drop will be about 3% anorthite (97% albite) (ii) At a temperature of about 1185o. (iii) The last crystal will be about 30% anorthite. 5 2

Phase EXPLANATION Diagrams

If the system stays in equilibrium at all times the final composition must end up where we started, 30% anorthite:70% albite. So, find the composition of the melt on the liquidus line which is opposite where the 30% line crosses the solidus line. This is the composition of the last drop of melt.

The temperature is read where this line intersects the temperature scale.

Zoned crystals
Ca-rich plagioclase
But what if crystallisation of the melt takes place too rapidly and the early formed crystals do not have time to react back fully with the melt? The early Ca-rich crystal will only partly react back with the melt and leave a crystal remnant behind. It is around this that a later crystal will grow which in turn will become surrounded by later forming crystals as temperature falls. In this way a ZONED CRYSTAL is formed with a central core of Carich anorthite surrounded by layers (zones) of increasingly Na-rich plagioclase.

Phase Diagrams

5cm

Na-rich plagioclase

The feldspar crystal illustrated is a phenocryst as it is surrounded by a finer grained groundmass of un-zoned plagioclase crystals that have cooled too quickly to form larger crystals - PORPHYRYTIC texture

Phase Diagrams

The End