thermo_bm_3
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In addition, considering P and T as the other two variables, the total number of unknowns = totally lost in the process of such accounting. Here, we first try to identify the unknowns We can write equations relating compositional variables in each phase as follows Equations potential, at equilibrium, chemical potentials of every component is the same in every phase Important feature of the Gibb’s phase rule is to remember that the phase rule is simply an Derivation of the Gibb’s phase ruleTRANSCRIPT
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The Schreinemakers Method B. Mishra
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PART – 3
THE SCHREINEMAKERS METHOD: A GEOMETRIC APPROACH FOR CONSTRUCTING PHASE EQUILIBRIA
Derivation of the Gibb’s phase rule
Important feature of the Gibb’s phase rule is to remember that the phase rule is simply an
accounting of the number of equations and unknowns and identities of the unknown are
totally lost in the process of such accounting. Here, we first try to identify the unknowns
(variables) and the equations, necessary for deriving the phase rule.
Unknowns
If we represent the compositions of all the phases in the system in theirs of mole fractions of
their components (x1, x2, ……. etc.), then there will a mole fraction term for each
component in every phase, so that there will be ‘cp’ compositional variable.
In addition, considering P and T as the other two variables, the total number of unknowns =
cp + 2.
Equations
We can write equations relating compositional variables in each phase as follows
11
=∑=
C
iiX (1)
For ‘p’ no. of phases, there will be ‘p’ equations of the above type. Furthermore, since
transfer of chemical components takes place in the direction of decreasing chemical
potential, at equilibrium, chemical potentials of every component is the same in every phase
in which it appears.
Thus, pii 1............... μμμ βα === (2)
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There can be (p–1) number of equations (of eqn. 2) for ‘p’ no. of phases, that is (p–1) equal
signs and considering ‘c’ no. of component, the no. of equations of the above kind will be
c(p–1)
∴Total no. of equations = p + c×(p–1) (3)
The number of degrees of freedom (f) or the variance of the system
f = no. of unknowns – no. of equations
= cp + 2 – [p + c×(p–1)]
= cp + 2 – p – cp + c
= c – p + 2 (4)
For a P-T diagram (see Fig. 1), the phase rule states that
• Invariant points (f = 0) occur at fixed P and T
• Univariant (f = 1) reaction lines occur over a range of P and T, i.e., one is free to
change either P or T, but once we do that, the value of the other is fixed, and we
remain on the line.
• Divariant (f = 2) fields between reactions have two degrees of freedom, i.e., both P and
T can be varied within limits.
Special case: If one (or more) of the reactions degenerate, the reaction will include
fewer than n + 1 phases and there will be fewer than (i) n + 2 reaction curves, and (ii)
than n + 2 divariant fields. Degenerate reactions are those that can be described with
Corollaries to the phase rule, for a n component
system (c = n)
If f = 0 ⇒ no. of phases = n +2
If f = 1 ⇒ no. of phases = n +1 ⇐ n + 2
univariant reactions.
If f = 2 ⇒ no. of phases = n ⇐ n + 2 divariant
reactions.
Fig. 1 P-T diagram showing asimple one-component system –the Al2SiO5 triple point.
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fewer components than the overall system. When they are involved at any invariant
point – it may appear that there are too few reaction curves because two or more curves
may (a) be collinear on the opposite side of the invariant point and thus appear to be
same curve, or (b) may be superimposed on top of each other, so a single curve may
represent reactions with two or more phases absent.
Degenerate reactions may or may not pass through an invariant point. As because
these reactions actually depict two or more phase-absent curves, they can be either (i)
stable-on-stable (two reactions are superposed on top of each other and terminate at the
invariant point, with two phases absent levels on the end of the curve) or, (ii) stable on
metastable (each reaction is superposed on the metastable reaction of the other) so the
appearance is that the reaction curve passes directly thus the invariant point, but are
designated with different absent phases at the end. (H2O)/(Prl) - stable on metastable
(see Fig. 2).
Multi-component system:
In multi-component systems when two univariant reactions in a given system intersect
they create an invariant point - provided the total number of phases does not exceed c +
2. Again, if two reactions belong to different systems, they may cross without creating
an invariant point.
Fig. 2 An example of degenerate reaction (H2O)/(Prl). Note that the absent phases (marked within parentheses) are different on the opposite sides of the invariant point.
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An example of two different chemical systems is shown in Fig. 3a, where the reactions
are
System CaO-Al2O3-SiO2: Ca3Al2Si3O12 + SiO2 = CaAl2Si2O8 + 2CaSiO3 (5)
System CaO-MgO-SiO2: 2CaSiO3 + MgSiO3 = Ca2MgSi2O7 + SiO2 (6)
Fig. 3b shows an example of pseudo-invariant point in the CaO-Al2O3-SiO2 system where
six (6) phases (An, Wo, Gr, Qtz, Gh, Ky) coexist, as against five (5) phases, necessary, for
an invariant point, in a 3-component system, as expected from the phase rule. The gehlenite
(Gh)-forming reaction in Fig. 3b is
2CaSiO3 + Al2SiO5 = Ca2Al2SiO7 + 2SiO2 (7) Wo Ky Gh
3-Component System (MgO-Al2O3-SiO2): There are n + 2 (= 5) univariant reactions and
they intersect at the invariant point, having 5 phases (En, Co, Fo, Crd, Spl). The reactions
are given below and their dispositions are shown in Figure 4.
a b
Fig. 3 Examples of pseudo-invariant points: different chemical systems (a) and less number of phases (b).
Fig. 4 An invariant point in the 3-component system MgO-Al2O3-SiO2, with five univariant reactions.
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(En) Mg2Al4Si5O18 + 8MgAl2O4 = 5Mg2SiO4 + 10Al2O3 (8) Crd Spl Fo Co
(Co) Mg2Al4Si5O18 + 5Mg2SiO4 = 10MgSiO3 + 2MgAl2O4 (9) Crd Fo En Spl
(Fo) Mg2Al4Si5O18 + 3MgAl2O4 = 5MgSiO3 + 5Al2O3 (10) Crd Spl En Co
(Crd) MgSiO3 + MgAl2O4 = Mg2SiO4 + Al2O3 (11) En Spl Fo Co
(Spl) Mg2Al4Si5O18 + 3Mg2SiO4 = 8MgSiO3 + 2Al2O3 (12) Crd Fo En Co
4 -Component System (CaO-Al2O3-SiO2-H2O): There are six (n + 2) univariant reactions.
Each reaction involve 5 (n + 1) phases, excepting two (Mrg = Dsp + Zo + Ky and Ky + H2O
= Prl+ Dsp) that contain 4 phases. There are 6 (n + 2) phases at the invariant point and 4 (=
n) phases are stable in the divariant fields. There are two degenerate reactions, each
containing 4 phases. These are the (i) near-vertical (Mrg)/(Zo) reaction, and (ii) near-
horizontal (H2O)/(Prl) reaction. Details of these two reactions are given below and their
dispositions are shown in Figure 5.
Fig. 5 An invariant point in the 4-component system CaO-Al2O3-SiO2-H2O, containing six phases including pyrophyllite (Prl), margarite (Mrg), kyanite (Ky), diaspore (Dsp), zoisite (Zo) and H2O. There are twodegenerate reactions, (H2O)/(Prl) and (Zo/Mrg).
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(Mrg)/(Zo) 4Al2SiO5 + 4H2O = Al2Si4O10(OH)2 + 6AlO(OH) (13) Ky Prl Dsp
(H2O)/(Prl) 2CaAl4Si2O10(OH)2 = 3AlO(OH) + Ca2Al3Si3O12(OH) + Al2SiO5 (14) Mrg Dsp Zo Ky
The other two reactions are:
(Ky) 8CaAl4Si2O10(OH)2 + 4H2O = Al2Si4O10(OH)2 + 18AlO(OH) + 4Ca2Al3Si3O12(OH)
Mrg Prl Dsp Zo (15)
and
(Dsp) 4CaAl4Si2O10(OH)2 + Al2Si4O10(OH)2 + 6Al2Si2O5 + 4H2O (16)
Mrg Prl Ky
5-Component System (CaO-MgO-SiO2-H2O-CO2): This is a different example, compared
to the previous two, since it is an isobaric (dP = 0) T-XCO2 diagram, for which the phase rule
becomes f = c – p + 1. However, H2O and CO2 are together counted as one fluid phase.
Hence, it actually becomes a 4-component system and a normal univariant reaction involves
5 (n + 1 = 4 + 1) phases. For example, the (Di) reaction involves four minerals and a fluid.
Invariant points involve 6 phases, and 4 phases are stable in each divariant field. The
(Tr)(Cc) reaction is degenerate. The reactions are shown in Fig. 6 and are listed bellow.
Fig. 6 T-XCO2 diagram in the CaO-MgO-SiO2-(H2O-CO2) system, showing an invariant point and one degenerate reaction, i.e., (Tr)(Cc).
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(Qtz) Ca2Mg5Si8O22(OH)2 + 3CaCO3 = CaMg(CO3)2 + 4CaMgSi2O6 + H2O + CO2 (17) Tr Cc Dol Di
(Dol) Ca2Mg5Si8O22(OH)2 + 2SiO2 + 3CaCO3 = 5 CaMgSi2O6 + H2O + 3CO2 (18) Tr Cc Di
(Di) 5CaMg(CO3)2 + 8SiO2 + H2O = Ca2Mg5Si8O22(OH)2 + 3CaCO3 + 7CO2 (19) Dol Tr Cc
(Tr)(Cc) CaMg(CO3)2 + 2SiO2 = CaMgSi2O6 + 2CO2 (20)
Dol Di
Compatibility Diagrams: e.g. system Al2O3-SiO2-H2O
The triangular compatibility diagrams contain reaction lines dividing them into further
triangular fields, each containing stable mineral assemblages. Since change in the mineral
assemblage takes when a reaction is crossed, the tie lines change as well. Crossing tie line
Fig.7 Invariant point in the Al2O3-SiO2-H2O system involving pyrophyllite, diaspore, kaolinite (Ka), quartz and H2O. Triangular compatibility diagrams show changes in mineral assemblages from one fieldto the next.
can be either because (i) a tie line flips
(e.g. Ka + Qtz = Prl + H2O) or (ii) of a
terminal reaction, i.e., a reaction that
has a single phase on one side (e.g. Prl
= Dsp + Qtz). Flipping-tie line
reactions results in one line on the
compatibility diagrams, disappearing
and being replaced by a different tie
line e.g., Ka + Qtz line disappearing
and being replaced by the Prl + H2O
line.
Al2Si2O5(OH)4 + 2SiO2= Ka Al2Si4O10(OH)2 + 2H2O (21) Prl
Crossing a terminal reaction results in a
phase disappearing completely and
involves several tie line disappearing.
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The following points have geometric rationale for depicting phase relations.
1. If a reaction is missing a particular phase, that phase is present on the opposite side of all
other reactions. For example, since the (Dsp) reaction is at the bottom of the diagram (Fig.
7) and Dsp is stable on the top side of all other reactions.
2. The metastable extension of any reaction (the dashed part) occurs in the divariant field
bounded by the univariant curves that have the absent phases facing each other. For
Fig. 8 The (Qz), (Dsp) and (Prl) reactions are all stable on one side of the invariant point only. This diagram, however, shows metastable extensions of those reactions into divariant fields. Consider the (Qtz) reaction: it cannot be stable up and to the left of the invariant point because the reaction involves pyrophyllite, andpyrophyllite is not stable to the left of the (Ka)(H2O) reaction. Note that the degenerate (Ka)(H2O) reaction passes through the invariant point. Degenerate reaction often, but not always, are stable on both sides of an invariant point.
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example, the metastable extension of the (Qtz) reaction extends into the divariant field
bounded by Dsp + Qtz + H2O and Dsp + Qtz (see Fig. 8).
4. The Morey-Schreinemakers (180°) Rule states that no sector (the wedge between two
reaction curves) around the invariant point, in any divariant field, can go more than 180°. In
other words, a divariant assemblage always occurs in a sector that makes an angle ≤ 180°
about the invariant point. For example, Ka + Qtz = 120o and Prl enjoys the full 180o
stability, i.e., three right lower sectors (see Fig. 8)
5. As we move around the invariant point, 2-phase assemblage breaks down before either
the phase (in the assemblage) breaks down itself. Similarly, a 3-phase assemblage breaks
down, before any 2-phase assemblage (containing two of the original three phases). In the
above example (Fig. 8), the (Qtz) reaction limits the assemblage Prl + Dsp + H2O. Moving
clockwise, the (Dsp) reaction limits Prl + H2O. Then the (Ka)(H2O) reaction limits Prl. Here,
we must have a word of caution. It does NOT mean that the sequence 3-phase, 2-phase, 1-
phase is followed for all assemblages. It just states that if 3-, 2-, and 1-phase reactions (that
involve the same phases) are present, then they always follow in order. For complex
systems, other reactions may interfere, but the order must be followed.
Practical Steps for Creating Schreinemakers 'Bundles' Let us recall the corollaries of the phase rule. For an n-component system, (i) if there are n +
2 phases, an invariant point is generated, and (ii) there are n + 2 univariant curves that
radiate from this point, unless one or more of the reactions degenerate. The first task is to
make a list of all possible reactions. The best way to do this is to think about the phases
NOT involved (absent phases), systematically make a list of reactions and label them by the
absent phases, as shown below.
Let us consider the CaO-MgO-SiO2 system as an example, and the phases are wollastonite
(Wo), quartz (Qtz), diopside (Di), enstatite (En), and akermanite (Ak). A 3-component
system means that there are four phases in each potential reaction and five possible reactions
in all. These are (Wo), (Qtz), (Di), (En), (Ak), with one that degenerates, leaving:
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A. (Wo) 2Di = Ak+Qtz+En
B. (Di) Ak+Qtz=2Wo+En
C. (En) Ak+Qtz=Di+Wo
D. (Qtz)(Ak) Di=Wo+En
In principle, while creating a Schreinemakers bundle, it does not matter which two
curves we start with, or which sides we label (as reactants and products) of the reactions.
However, some starting choices may make the analysis easier than others, so trial and error
may be involved. In general, it is best to begin with terminal reactions, if we have some. We
can draw the two reactions intersecting, and label them with products/reactants, and missing
phases. If portions of the reaction curves are clearly metastable, those portions can be
represented as dashed lines. Once we "fix" the positions of the first two curves, all the other
curves will fall into the appropriate sequence. If we find difficulty, we can try starting with
two different curves.
Two Solutions
(1) The Schreinemakers method produces bundles of reactions that are topologically correct.
Depending on how we orient, i.e., label reactants and products in the first two reactions, we
can get two different solutions that are mirror images of each other. In other words, if you go
around the invariant point clockwise for one solution, you will hit reactions in the same
order as going around the other solution counter-clockwise. The two possibilities are called
enantiomorphic projections or enantiomorphic pairs, and one way to think of them is that
there is a "right-handed" and a "left-handed" sequence of reactions.
(2) There is no priori way to determine which of the two the correct solution is. Deciding the
correct one requires some geologic intuition and knowledge of the types of reactions in
orienting the Schreinemakers bundles on a phase diagram. For example, in a P-T diagram,
(i) high density phases tend to be present on the high-P side of a reaction, (ii)
devolatilization reactions tend to have a steep, positive slope, and the volatiles are liberated
on the high-T side of the diagram. Additional in-depth understanding can be gained from
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thermodynamic principles. The slopes of individual reactions may be calculated using the
Clausius-Clapeyron equation ⎟⎠⎞
⎜⎝⎛
ΔΔ
=VS
dTdP .
Step 1: In our example, reactions (A) and (D) are terminal reactions. They are plotted in
Figure 9a. Their orientation and labels have been placed arbitrarily. The metastable parts are
shown dashed.
Now we can consider an additional reaction. With reference to the first two curves, we can
determine the quadrant in which the new reaction may be stable, draw the reaction in that
quadrant and continue it through the invariant point and make the line dashed where
metastable. We must label each curve with the absent phase, and also label curves with
reactants and products on the correct side of each reaction, strictly in accordance with the
180°-rule, and other hints in the points # 1 through 5, mentioned above (especially #5).
There is only one correct way to place the products and reactants. If we get them reversed,
we are asking for confusion and trouble.
Fig. 9 (a) Step 1: arbitrarily start with two terminal reactions [(Wo) and (Qtz)(Ak)]. (b) Step 2: addition of the third reaction (Di), which must lie in the lower right quadrant as it involves Ak-Qtz-Wo-En, and those phases can only be stable together in that quadrant because of the first two reactions. "Wo+En" is placed on the right (high-T) side of the (Di) reaction becausethere is another reaction limiting Wo+En. The two must "face" each other, so that the anglebetween them cannot exceed 180°.
a: Step 1 b: Step 2
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Step 2: For our example, we will now plot reaction (b) (Fig. 9b). This reaction includes Ak,
Qtz, En, and Wo. Hence, if it is stable, it can only be stable in the bottom right quadrant. We
plot it there and extend it (metastably) through the invariant point. We then label the right
hand side "Wo+En" because the (Qtz)(Ak) reaction also limits Wo+En, and Wo+En- sector
can not be stable more than 180°. Note that, as expected, the metastable part of this reaction
(Di) lies between two curves that eliminate Di.
This way, we can continue to position all additional curves around the invariant point
using the conventions above, label each curve with the absent-phase, and also label curves
with reactants and products on the correct side of each reaction, with some guess. However,
in the extreme case, if we guess wrong, we will end up finding that most of the reactions
turn out to be metastable and we do not have a reasonable invariant point.
Step 3: We add the last reaction (c) in Fig.10. Here
we note that it contains Di, which means that it
must lie in the upper left quadrant, if it is stable
(since two other reactions limit Di to that
quadrant). We plot it there and extend it through
the invariant point. We label the left hand side
"Ak+Qtz" because the (Di) reaction also limits
Ak+Qtz, and again that assemblage cannot be
stable more than 180°. Finally, we complete the
diagram, by adding chemographic drawings
showing mineral assemblages in each of the
divariant fields.
Fig. 10 The invariant point with all four reactions plotted.
Step 3
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Step 4: We now appropriately eliminate the metastable reaction extensions (Fig. 11a).
Step 5: Finally, we add the triangular diagrams depicting stable mineral assemblages (Fig.
11b).
Fig. 11 Step 4: Eliminating the metastable extensions in Figure 10 (a) and Step 5: Construction of the Schreinemakers P-T bundles for the CaO-Mgo-SiO2 system with triangular diagrams showing stable assemblages in each field.
a b
P
T