Principles of Thermodynamic Modeling of Igneous Processes

Geology 531: Igneous Petrology Notes
PART 3: Principles of Thermodynamic Modeling of Igneous Processes
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PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES
Principles of Thermodynamic Modeling of Igneous Processes Introduction to the Concept of Chemical Equilibrium Thermodynamic systems can be described in two different ways. There is, first, the real collection of atoms, molecules, phases, and energy that constitutes the real world. Then there is the mathematical structure that represents the real world. The literature contains several definitions of equilibrium in thermodynamic systems. Some definitions are phrased in terms of the behavior of the real collection. Other definitions are mathematical statements. Prigogine and Defay (1954, p. 69, Equation 6.23) use the value of a linear combination of chemical potentials to describe the equilibrium condition:

i i
=0
(1)
where i is a stoichiometric coefficient and i is the chemical potential of the chemical entity i. Equation (1) represents the equilibrium for a chemical transformation that can be written:
x
i i
=0
(2)
where xi is a chemical formula and Equation (2) represents a balanced chemical transformation. Denbigh (1981) describes thermal equilibrium with his zeroth law: ..if bodies A and B are each in thermal equilibrium with a third body, they are also in thermal equilibrium with each other. In other words, bodies in equilibrium, at least bodies in thermal equilibrium, have the same temperature. Nordstrom and Munoz (1985) state that equilibrium occurs when the equality holds in the Clausius equation: dQ TdS 0 (3)
where Q is the heat gained by the system, T is the temperature in Kelvin, and S is entropy. Equality holds for reversible processes. In other words, equilibrium and reversibility are synonymous with this definition. Anderson and Crerar (1993) define equilibrium with two statements: 1
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A system at equilibrium has none of its properties changing with time, no matter how long it is observed. A system at equilibrium will return to that state after being disturbed, that is, after having one or more of its parameters slightly changed, [they will] then change back to the original values. Other statements of equilibrium postulate a minimum for thermodynamic potentials that depend on a particular set of variables. For example, equilibrium obtains if the Gibbs energy for a system is a minimum at some fixed values of pressure and temperature. All of these statements are correct in that, if the criteria hold, then the system is at equilibrium. Except for the definition by Prigogine and Defay (1954), however, the statements are sufficient rather than necessary criteria for equilibrium in chemical systems. In some systems, the other statements will be incorrect whereas the statement by Prigogine and Defay (1954) (hereafter termed the First Statement) will still be correct. If the other statements obtain then so does the First Statement. The converse is not true. The First Statement can obtain, although one or more of the others do not obtain. In summary the sufficient statements are: 1. Equilibrium systems do not change, no matter how long they are observed. 2. At equilibrium, the rate of the forward reaction equals the rate of the reverse reaction. 3. When infinitesimally perturbed, equilibrium systems return to their original equilibrium state. 4. A minimum in the value of a thermodynamic potential occurs at equilibrium. 5. Equilibrium systems are at constant temperature. Although many equilibrium thermodynamic systems cannot be realized in nature, they often provide adequate representations of reality. If even part of a natural system can be adequately approximated by an equilibrium system then significant, mathematical simplification over a dynamic model usually follows. Consequently, a precise definition of equilibrium leads to precise descriptions of representations of reality and a better understanding of processes that affect chemical systems.
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The trivial case of one phase: Suppose two grains of kyanite, a and b. Then
a b Al 2 SiO5 Al 2 SiO5 = 0
Equilibrium Systems Do Not Change, No Matter How Long They Are Observed As a counter example to this definition of equilibrium, consider a glass of water and ice in an environment at room temperature. The temperature in the glass is 0C. In fact, the glass contains an assemblage of phases that defines a point on the thermodynamic temperature scale. Yet, obviously the system is changing with time as the ice melts. Purists will protest that the temperature is not really 0C but it is slightly greater than that. However, as a representation of reality, the mathematical formulation is adequate. A temperature scale based on phase assemblages out of equilibrium would be inconvenient at best and unusable normally. Consequently, for the practical purpose of the temperature scale, a mixture of ice and water is an equilibrium system and the appropriate and adequate expression is:
Ice H 2 O Water = 0 H 2O
(4)
an example of the First Statement. At Equilibrium, the Rate of the Forward Reaction Equals the Rate of the Reverse Reaction Again, the mixture of ice and water example provides a counter example. The rate of melting is faster then freezing, yet, as shown above, the system can be represented as an equilibrium system. When Infinitesimally Perturbed, Equilibrium Systems Return to Their Original Equilibrium State Consider a large volume of water and ice into which a drop of hot water is added. The temperature quickly returns to 0C but the small amount of ice that melted to cool the drop does not freeze again. Unless the equilibrium state is defined by temperature alone, then the system of ice and water does not return to its original state when infinitesimally perturbed.
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A Minimum in the Value of a Thermodynamic Potential Occurs at Equilibrium A counter example to this condition is more difficult to contrive than the others. Consider a solid solution that can have a varying degree of order, for example, an ilmenite-hematite solid solution. Ghiorso (1990) derives an expression for the chemical potential of the hematite component: Hm = G y G s G s y y s (5)
where y is the mole fraction of Fe2O3 in solid solution and s describes the degree of ordering of Fe and Ti on the metal sites of the structure. Disordered FeTiO3 is characterized by s equal to zero whereas fully ordered FeTiO3 has a value of s equal to one. G is the Gibbs potential for the solution. In general, s is evaluated by setting the partial derivative of G with respect to s equal to zero (see, for example, Sack, 1980). This exercise is equivalent to minimizing the Gibbs potential for the solid solution with respect to diffusion. However, it may happen that a solid solution encounters an environment where it will react with another phase under conditions where rates of internal diffusion in the solid solution are too slow to alter the ordering state. Under such conditions, the chemical potential of Fe2O3 still exists [Equation. (5)] and could be used to describe an equilibrium change in a geochemical system with an expression of the form of Equation (1). In such a system, the Gibbs potential for the system will not be a minimum because the Gibbs potential for the solid solution will not be a minimum. Equilibrium Systems are at Constant Temperature A counter example to this statement can be constructed by recourse to that magical device, an adiabatic semi-permeable membrane. Suppose a solution on one side of the wall and a vapor consisting of the pure solvent on the other. The wall is assumed permeable to the solvent but impermeable to the solute. As an example, suppose the solvent is water and that the solution is ideal. The chemical potential for H2O in the solution is: Water = 68317 16.712 TW RTW ln x H 2O (6)
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R is the gas constant and TW is the temperature of the solution. The chemical potential of H2O as steam, assuming ideal gas behavior is:
Steam H 2 O = 5795 45 . 11 T S + RT S ln P
(7)
TS is the temperature of the vapor. If the chemical potentials in Equations (6) and (7) are set equal, an equations in four unknowns results, TW, TS, x, and P. It remains to show that the equation can be satisfied by values of the unknowns that are physically realizable: 0 < TW < TW < TS < 0<P< 0<x<1 inequalities in (8). Summary of Concepts of Chemical Equilibrium Both equilibrium and non-equilibrium combinations of chemical potentials can exist in the same situation. In the example where two parts of the system were at different temperatures, the chemical potentials of H2O in the two parts were equal but the chemical potentials of the solute were different. In the solution, the chemical potential of the solute is finite but in the vapor, where the solute is absent, the chemical potential is at minus infinity. Reiss (1964) defined a thermodynamic system as: "A thermodynamic system is an arbitrary geometrical portion of the universe with fixed or movable boundaries which may contain matter or energy or both." Such a definition requires a part of reality. Mathematical representations of thermodynamic systems may represent reality or they may represent ideas about reality that do not exist but may come into being through some process; a kind of virtual reality. Study of such systems can increase understanding of reality because one may find reasons that a particular mathematical representation has no real counterpart. (8)
Figure 1 shows an example for a set of parameters that satisfy Equations (6), (7), and the
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Representations of equilibrium by linear combinations chemical potentials equal to zero do in fact, provide convenient methods for defining equilibrium systems. Equilibrium systems are those parts of reality that can be adequately and appropriately represented by such linear combinations. The non-equilibrium parts must be represented by linear combinations of chemical potentials different from zero. Describing systems in terms of equality and inequality constraints puts the initial focus on whether or not that part of reality can be described in terms of equilibrium thermodynamics or whether the description must be a dynamic one. The causes for the differences can then be interpreted in terms of geometric walls, membranes and barriers to the transfer of matter and energy. As Reiss (1964) emphasizes, the behavior of thermodynamic systems is usually dictated by the nature of the constraints (wall, membranes, and barriers) on the thermodynamic system. Just as thermodynamics is independent of our understanding of the atomic nature of matter, the mathematical structure that represents reality can be constructed without recourse to the precise nature of the real parts of the universe. Often equilibrium systems are equated with parts of reality characterized by reversible reactions or changes. Although systems containing reversible processes are systems at equilibrium, the converse need not be true. Some systems containing irreversible processes can be analyzed and described with equilibrium statements. One such set of systems is the set that contains isenthalpic changes (see page 34). Examples include expansion of gases into a vacuum (the Joule-Thompson effect, see Lewis and Randall, 1961, p. 48), adiabatic decompression during uplift (Waldbaum, 1971), and rapid ascent of nephelinites (Nicholls, 1990; Trupia and Nicholls, 1996). Such systems should be distinguished from systems described by what are called irreversible thermodynamics (e.g. the Soret effect). In these systems, linear combinations of chemical potentials differ from zero. The study of such systems is better described as nonequilibrium thermodynamics rather than irreversible thermodynamics. Phase Rules and Duhem's Theorem This chapter is an outline of the thermodynamic basis for modeling crystal-melt equilibria. Because the purpose of the chapter is to illustrate the principles of thermodynamic modeling, rather than solve the problems associated with specific
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applications, numerical analysis will be kept to a minimum. The main consequence of keeping numerical analysis to a minimum is that all solutions will be treated as ideal, thus eliminating the effects of activity coefficients. Once the features of ideal systems are mastered, the principles involved in modeling real systems are easily followed. The first question to answer is: How much information must we bring to a problem in order to model a thermodynamic system? The answer is surprisingly simple, if we know the composition of the system, then we need only two other pieces of information. Duhem's theorem, a little known form of a phase rule can be stated: Given the composition of a chemical system, then two and only two independent variables need be fixed to determine the equilibrium state of the system. The more commonly known phase rule, the Gibbs phase rule, can be written: F=c+2 (9)
where F is the degrees of freedom or number of variables that must be fixed in order to define the equilibrium state of the system, c is the number of components in the system and is the number of phases in the system. The import of Duhem's theorem is that F is equal to 2 if we know the composition of the system. In chemical systems of interest to petrologists, the intensive variables include P, T and the compositions of all the phases present. In addition to P, T and phase compositions, igneous petrologists have traditionally been preoccupied with the modal abundances of the phases in the system. Modal amounts are not considered intensive variables in derivations of the Gibbs phase rule (e.g. Prigogine and Defay, 1954, p. 174175). They are, however, intensive variables because they are measured in relative units (e.g. volume percent, weight percent, etc.). The intensive variables describing the phase compositions are related to properties of the phases, such as volumes, by partial molar quantities: v = ivi xi (10)
where v is the molar volume of phase , vi is the partial molar volume of component i in phase , and xi is the mole fraction of component i in phase . The summation is over index i = 1..N, N being the number of components in phase .
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Whereas phase properties are related to partial molar quantities and compositions, properties of the chemical system are related to the phase properties and the modal amounts: V = z v (11)
where V is the molar volume of the chemical system, z is the molar concentration of phase in the system and v is the molar volume of phase . In Equation (11), the sum is over index = 1..M, M being the number of phases in the system. Consequently, we see that the relationship between the molar volume of the system and the molar phase volumes parallels that between the molar phase volumes and the partial molar volumes. Both the molar system properties defined in this way and the molar phase properties are intensive variables. A typical statement of Duhem's theorem is (Prigogine and Defay, 1954, p. 188): "Whatever the number of phases, of components or of chemical reactions, the equilibrium state of a closed system, for which we know the initial masses [of the constituents] is completely determined by two independent variables." Compared to the statement given earlier, this is a much more restrictive version. First, the initial masses can be more difficult to estimate than the composition of the system. For example, even if a particular pluton crystallized as a closed system, a questionable assumption, estimating the masses of the elements in the rock body might be impossible because of the inaccessibility of parts of the pluton. Second, the system need not remain closed after we calculate its equilibrium state; to apply Duhem's theorem, all we need is its composition in an equilibrium state. The two different statements can be reconciled (mass vs concentration) by realizing that for calculating the properties of the phases or of the system, the size of an equilibrium system can be arbitrarily set: Two systems differing in size but with the same composition and in the same equilibrium state will differ neither in P, T, phase compositions, nor in modal concentration of the phases. The difference in size can be accounted for by extensive variables that are related by a single scalar multiple.
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The equilibrium state of an igneous system is defined when numerical values for P, T, the phase compositions and the mode are available. Consequently, the variables are P, T, M values of z where M is the number of phases in the system, and M N values of xi where N is the number of components in the system. The total number of variables in a system of known composition is 2 + M(1 + N). With this many variables, only two of which can be arbitrarily changed, there must be some equations relating them. Given the composition of the system, we can always write down N mass balance constraints. Generally, the mass balance constraints are written in terms of extensive amounts of the phases and constituents:
m x1 = n1 m x2 = n2
.
(12)
xN = nN
where the summation index, , is over the number of phases in the system; = 1..M. The m and ni are number of moles in the system. These extensive variables can be converted to intensive ones by dividing by the size of the system, represented by: Sn = ini After the division, the mass balance equations are: (13)
z x1 = y1 z x2 = y2
.
(14)
xN = yN
where the z = m /Sn and yi = ni/Sn are the mole fractions of the phases in the system and the mole fractions of the components in the system, respectively. Subtracting the number of mass balance equations, N, from the number of variables leaves 2 + M + N(M 1). Duhem's theorem says only two of these can be independently varied. Consequently, there must be an additional M + N(M 1) equations we can write down. The additional equations are thermodynamic ones, reflecting the
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equilibrium conditions. The simplest and most general equations (see page 1) to follow are equations relating chemical potentials: i (P,T,xi ) = i (P,T,xi ) nonlinear equations are then solved for the remaining variables. Example of the Application of Duhem's Theorem As a simple example of the application of Duhem's theorem, consider a ternary chemical system consisting of a binary solid solution and a melt (Figure 2). The composition of the system is known and is expressed as the mole fractions of two components, C and B. The concentration of the third component, A, in the system is given by: yA = 1 yB yC (16)

(15)
Generally, petrologic modeling has been done with P and T fixed arbitrarily; the set of
The variables describing the equilibrium state of the system are T, P, the composition of the solid, x, the composition of the melt, yB and yC, and the fractions of each phase, solid and melt, in the system, zS and zL, a total of seven. Relating these variables are three mass or materials balance equations: (1 x) zS + (1 yB yC) zL = 1 yB yC x z + yB z = yB yC z L = y C and two thermodynamic ones: AS(P,T,x) = AL(P,T,yB,yC) BS(P,T,x) = BL(P,T,yB,yC) two variables in order to calculate the others. The two variables that are most commonly fixed in thermodynamic modeling of igneous processes are P and T. Any two of the seven listed variables could be fixed, however, and the remaining ones calculated. In addition, variables that are functions of the seven listed could also be fixed. For example, the volume of the system is given by (20) (21)
S L
(17) (18) (19)
for a total of five equations in seven variables. As Duhem's theorem states, we must fix
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the appropriate modification of Equation (11): V = vS z S + v L z L (22) If the molar volume of the system, V, is known, this last equation provides a relationship between P, T, and the compositional variables because vS and vL are functions of P, T and phase composition. Consequently, with V fixed, P or T and the compositional variables can be calculated from the sets of Equations (17)-(19), (20)-(21) and (22)). The simplest and crudest approximation to the thermodynamic equations [Equations (20) and (21)] is to use distributions coefficients and assume they are approximately constant: x/yB = Kd1 (1 x)/(1 yB yC) = Kd2 (23) (24)
The distribution coefficients are either experimentally determined (e.g. Roeder and Emslie, 1970) or derived from thermodynamic data sets that are, in turn, constructed from experimental data (Ghiorso, et al., 1983; Nielsen and Dungan, 1983; Berman, 1988). Distribution coefficients are seldom, if ever, constants and to make reasonably accurate models one must use a thermodynamic data set to evaluate the thermodynamic equations. The sets of equations that must be solved for the remaining variables, after fixing two, are nonlinear. Nonlinear equations always create numerical and calculation problems. Consequently, there is a considerable literature on how to solve the equilibrium problem. The most efficient way is not to solve the set of nonlinear equations; rather, the preferred method is to minimize the Gibbs energy, G, or some other thermodynamic potential for the system (see, for example, Ghiorso, 1987). The numerical consequences of the different approaches to this problem are significant (Press et al., 1986, p. 269-272). The preferred method, however, does not guarantee that all physical-chemical configurations can be modeled in this way. If the degrees of freedom calculated with the Gibbs phase rule are zero or one (i.e. if the system is invariant or univariant) then the two independent variables cannot be arbitrarily chosen; rather, the independent variables must be system variables. Both must
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be system variables if the system is invariant; one must be a system variable if the system is univariant. Under any set of constraints, invariant, univariant, bivariant, or more, the independent variables may be system variables. The restriction is on the number of nonsystem variables, ones that are commonly called intensive variables. For example, suppose the system consists of two polymorphs, A and B. Then there are no chemical unknowns, both phases have the same composition, that of the system itself. The unknowns are P, T, and the fractions of the two phases, zA and zB. One equation relating the variables is an expression of thermodynamic equilibrium between the two phases: G(P,T) = 0 (25)
where G(P,T) is the Gibbs energy change for the transformation of A to B. This equation is a function of P and T only because the phases have the same composition and is independent of the concentrations of the phases in the system, zA and zB. Consequently, it provides no information about the amounts of the phases in the system. Given P we can calculate T and vice-versa. Consequently, we cannot arbitrarily fix both P and T and we cannot calculate zA and zB. In order to calculate zA and zB we require a relationship that depends on how much of each phase is present. Variables which depend on the amounts of the phases present are system variables such as density, heat content and heat capacity. Others are refractive index, compressibility, thermal expansion and functions of these variables such as the difference between the sound velocities in the system: Vp2 - (4/3) Vs2 = cp/[( cp - T v 2)] (26)
where Vp and Vs are the acoustic (seismic) wave velocities, cp is the molar heat capacity of the system at constant pressure, is the density of the system, v is the specific volume of the system, and and are the thermal expansion and compressibility of the system: = (v/T)P/v = (v/P)T/v (27) (28)
Suppose we select density as an independent variable and that we want to know the state of the system at some fixed density. The reciprocal of the density is the specific
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volume of the system. The coefficient of thermal expansion for a phase, k, in the system is given by: k = (vk/T)P/vk (29)
where vk is the specific volume of phase k and has units of m3/kg. Coefficients of thermal expansion are often approximately constant over temperature ranges of a few hundred degrees. Over a limited temperature range then, we can integrate Equation (29) to get: vk = vok exp(kT) volume at any T in the limited temperature range and at P = 0. The compressibility of a phase, k, in the system is defined as: k = (vk/P)T/vk (31) (30)
where vok is the specific volume of phase k at T = 0 and at P = 0. vk is then the specific
Like the coefficient of thermal expansion, compressibility is approximately constant over a limited range of the controlling variable, pressure. If compressibility is approximately constant, then Equation (31) can be integrated: vk = C(T) exp(kP) gives the specific volume of phase k at any P and T: vk = vok exp(kT kP) page 7, Equation (10): v = zA voA exp(AT AP) + (1 zA) voB exp(BT BP) where zk is the weight fraction of phase k in the system. This last equation is a function of P, T, and the concentration of phase A in the system. The concentration of B is one minus the concentration of A. By fixing either P or T, we can calculate the other with the equilibrium relation [Equation (25)]. By fixing density, we fix the specific volume of the system. Consequently, the weight fractions of the phases can be calculated with Equation (34). (34) (33) (32)
where C(T) is the volume of phase k at zero pressure. Combining with Equation (30)
The specific volume of the system will be a linear combination of the phase volumes (see
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Mathematical and Thermodynamic Preliminaries Reactions between solid and melt are written in the following pages as crystallization reactions. If component A enters the solid from the melt then the reaction is written: Am = As The equilibrium condition for this reaction is: As Am = A = 0 (35)
where the subscripts designate the components and the superscripts designate the phase. The standard states are the pure components in the solid or melt state. The thermodynamic condition for the crystallization of the pure component is written: A A* = A* (36)
where the superscripts and * indicate standard states for the solid and melt of component A, respectively. We assume the Gibbs energies for the standard state crystallization reactions are linear functions of temperature. This assumption is equivalent to assuming there is no heat capacity change for the crystallization reaction. Thermodynamics requires that: i* = Hi* T Si* (37)
Because of our assumption, the heats of crystallization (Hi*) and entropies of crystallization (Si*) must be constants. A melt is more disordered than a solid of the same composition and, therefore, has a larger entropy (remember entropies are positive). Consequently, the sign of Si* for the crystallization reaction will be negative. At the fusion temperature, i* is zero and, because T is always positive, we see that Hi* must be negative also. This conclusion is consistent with the fact that heat is liberated when substances freeze (latent heat of crystallization). If the solid and melt solutions are ideal, the equilibrium condition for component A can be written: A + RT ln xA A* RT ln yA = 0 (38)
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where xA and yA are the mole fractions of component A in the solid and melt, respectively. We will consistently use xi as a label for the concentration of a component in a solid and yi as a label for the concentration of a component in the melt. The particular component will be indicated by the subscript i. Equation (38) can be rearranged into a frequently used form: xA = yA exp( A*/RT) We will often use the abbreviation: fA = exp( A*/RT) and zoning profiles expected during crystallization. Its derivative is: dfA/dT = fA HA*/RT2 We will use the abbreviation: hA = HA*/RT2 (42) (41) (40) (39)
The derivative of Equation (40) is required when analyzing crystallization paths
The reader should note that Equation (41) is completely general in that it does not depend upon i* being a linear function of temperature [See a thermodynamics text, for example, Denbigh, 1981;, p. 90]. Hence, even in real systems, the derivative of fi is easily calculated if the enthalpy of crystallization is known. Writing Equation (40) in the form: fi = exp( Hi*/RT + Si*/R) (43)
provides a convenient way to examine its properties. The function, fi, is always positive because the exponential function is positive and the slope of Equation (43) is always negative because the sign of dfi/dT [Equation (41)] is determined by the sign of Hi*, which is negative. At high temperatures, the argument of the exponential function in Equation (43) is dominated by Si*/R. Because Si* is less than zero, the function becomes asymptotic to a horizontal line which has an intercept less than one. The argument to the exponential function is zero at the fusion temperature, Tif, of component i and there the value of fi is equal to one. At temperatures less than Tif the value of fi is greater than one and the steepness of the slope is proportional to Hi*.
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A schematic diagram illustrating these properties is shown on Figure 3. Liquidus Surfaces and Fractionation Curves This section illustrates the calculation of isotherms, cotectic curves, and fractionation curves in a simple ternary system. Suppose a ternary system, ABC. C crystallizes in the system only as a pure solid whereas A and B form a complete series of solid solutions. No other solid phases form in the system. Both the melt and the solid solutions are ideal. The standard state Gibbs energies for the crystallization reactions of the pure end members are: A: A* = 45000 + 45 T B: B* = 60000 + 50 T C: C* = 30000 + 20 T The units are Joules, moles and Kelvins. Plots of the Gibbs energies of crystallization are shown on Figure 4. The problem is to construct a phase diagram for this system showing the following features: 1. 2. The cotectic between melt, solid C and AxB(1 x) solid solutions. Isotherms on the liquidus surface.
In addition, we want to extract as much information as possible about crystallization paths. Consequently, we illustrate the following: 3. Equilibrium crystallization paths for the following bulk compositions: 1. 40% A, 45% B, 15% C. 2. 10% A, 85% B, 5% C. 4. Perfect fractionation curves that pass through the following bulk compositions: 3. 4. 40% A, 45% B, 15% C. 10% A, 85% B, 5% C.
Construction of the Phase Diagram The first step in the construction of a phase diagram is to find the fusion temperatures for the end members of the solid phases that form in the chemical system represented on the phase diagram. Equilibria between pure solid and pure liquid end
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member compositions occur at the fusion temperatures. At the fusion temperature, the Gibbs energy for the crystallization reaction must be zero; hence, i* is zero for the crystallization reaction at the fusion temperature for each end member: A: B: C: 45000 + 45 T = 0; 60000 + 50 T = 0; 30000 + 20 T = 0; TA,f = 1000 K TB,f = 1200 K TC,f = 1500 K
Next, calculate liquidus temperatures for the A-C and B-C binary edges of the diagram. Because no solid solution occurs in compositions on these edges, they can be represented by simple eutectic diagrams. Along the A-C edge there are the following exchange reactions: A = A Melt Solid C = C Melt Solid Because the solids are pure in our binary eutectic system, iS = i. The melt, on the other hand, is an ideal solution. Consequently: iL = i* + RT ln yi
S L
(44)
where yi is the mole fraction of component i in the melt. By setting i i = 0, we get the following equilibrium relations representing the crystallization reactions for the two end members, A and C [See Equation (39), Page15]. yA = exp(A*/RT) yA = 1 exp(C*/RT) where yA is the mole fraction of component A in the melt. The easiest way to find the liquidus compositions is to enter several values of T into the Equations (45) and (46) and calculate the corresponding values of yA and yC. Some results are shown in Table 1 and the A-C binary diagram is shown on Figure 5. Notice that at 950 K the mole fraction of component A in the melt is the same for both equations (0.752). This is the eutectic composition and 950 K is the eutectic temperature on the A-C binary side of the ternary system. (45) (46)
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An alternative method of solving Equations (45) and (46) is to substitute the expression for yA from Equation (45) into Equation (46) and rearrange it in the form: 1 exp(A*/RT) exp(C*/RT) = 0 special techniques are required to solve it. Table 1: Liquidus melt compositions on the A-C side of the ternary phase diagram. TK 1500 1400 1300 1200 1100 1000 950 900 800 A similar procedure yA Equation (45) yA Equation (46) 0.000 0.158 0.309 0.452 0.583 1.000 0.700 0.752 0.752 0.550 0.800 0.260 0.880 with the B-C binary returns a eutectic temperature of 1101 K and a (47)
This form is an implicit function of a single variable, T. It is, however, nonlinear and
mole fraction of B in the eutectic melt of 0.582. Slope of the Liquidus Curve Not often considered in the experimental and theoretical construction of a phase diagram are thermodynamic constraints on the slope of the liquidus curve or surface in temperature-composition space. Van Laar (1936, see Prigogine and Defay, 1954, p. 361) showed that in a binary system with a compound showing no solid solution, the liquidus surface near the compound's composition can have either a positive or negative curvature. To repeat Van Laar's demonstration we start with Equation (45): y = exp(*/RT) where we have temporarily dropped the subscript A in favor of a concise notation. To study the nature of the curvature of the liquidus curve on the binary temperature-composition diagram we need the slope (dT/dy) and the curvature (d2T/dy2). Solving Equation (45) for T, assuming H* and S* are constants, gives: T = (H*/R)/(ln y + S*/R) (49) (48)
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By differentiating Equation (49) and then back substituting from Equation (49) we get: dT/dy = - T/[y(ln y + S*/R)] d2T/dy2 = [R2T3/ (y H*)2](ln y + S*/R + 2) (50) (51)
The sign of the curvature will obviously depend on the sign of the last term in Equation (51) because the first term, in square brackets, is positive. We are considering a crystallization reaction, consequently, both H* and S* must be negative. Also, we are interested in the slope and curvature at y = 1 where the temperature is the fusion temperature for the pure component. At y = 1, then: If S*/R + 2 > 0, the curvature is positive. If S*/R + 2 < 0, the curvature is negative. Table 2: Liquidus slopes near the melting points of some silicate phases. The -quartz melting point is metastable with respect to the melting point of cristobalite. Phase Cristobalite -quartz Fayalite Forsterite Consequently, in S* - 4.091 - 28.934 - 61.860 - 78.668 order for the Tf y' T' 1996 0.221 491 1740 Metastable 1490 2163 slope of the liquidus curve to be concave upwards
on a temperature-composition plot near the composition of the pure phase, S* must lie between 0 and -16.6286 J/mole K (- 2 R). In addition, by setting the curvature, d2T/dy2, to zero we can find the coordinates of the inflection point where the curvature changes from negative to positive with increasing y: y' = exp(- S*/R - 2) T' = - H*/(2 R) where T' and y' are the temperature-composition coordinates of the inflection point. Some results for end members of petrologic interest are shown in Table 2 and Figure 6. Cristobalite obviously has a small enough entropy of crystallization for a concave upward liquidus curve. Other phases have entropies of crystallization of the order of the olivine end members. Consequently, we expect most phase diagrams to have liquidus curves with negative curvature, as commonly drawn. However, phase diagrams (52) (53)
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with cristobalite on the liquidus should have concave upward liquidus curves. This feature is present on diagrams for Na2OSiO2 and K2OSiO2 [See Morey, 1964]. Calculation of the Binary Loop The next problem is to calculate the binary loop for the A-B edge of the ternary system. If we let: xA = mole fraction of A in the solid yA = mole fraction of A in the liquid then the equilibrium relations for the components A and B are: yA = xA exp(A*/RT) 1 yA = (1 xA) exp(B*/RT) the ternary phase diagram. TK 1200 1150 1100 1050 1000 Solving for xA: yA 0.000 0.371 0.652 0.857 1.000 xA 0.000 0.183 0.399 0.662 1.000 (56) (54) (55)
Table 3: Temperature - composition coordinates of the binary loop along the A-B side of
xA = [1 exp(B*/RT)]/[exp(A*/RT) exp(B*/RT)]
Equation (56) is easiest to evaluate if xA is calculated at several temperatures between the fusion temperatures of the end members. The mole fraction of A in the melt is then calculated with Equation (54) or Equation (55). The results are shown on Figure 7 and in Table 3. Liquidus Slopes on Binary Loops The slope of the liquidus curve on a binary loop can be extracted from Equations (54) and (55) by eliminating x and solving for yA: yA = (1 f2)/(f1 f2) where: (57)
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PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES f1 = exp( A*/RT) f2 = exp( B*/RT)
Table 4: Fusion properties of some common rock-forming mineral end members. Units are K, Joules and moles. Tf H* S* Reference Anorthite 1830 135562 74.077 Weill, et al. (1980) Anorthite 1830 133000 72.678 Richet & Bottinga (1984b) Albite 1373 62800 45.739 Stebbins, et al. (1983) Albite 1373 64300 46.832 Richet & Bottinga (1984a) Sanidine 1473 57700 39.172 Stebbins, et al. (1984) Sanidine 1500 54000 36.000 Richet & Bottinga (1984a) Diopside 1670 137700 82.455 Richet & Bottinga (1984b) Enstatite 1834 77400 42.203 Stebbins, et al. (1984) Enstatite 1834 73200 39.913 Richet & Bottinga (1986) Titanite 1670 123805 77.134 King, et al. (1954) Fayalite 1490 89300 59.933 Stebbins & Carmichael (1983) Forsterite 2163 114000 52.705 Navrotsky, et al. (1989) Notice that on the binary AB edge of the ternary diagram, yA is equal to (1 yB). Differentiation of Equation (57) gives: dT/dyA = (f1 f2)2/[f2 h2(1 f1) f1 h1(1 f2)] where: hi = Hi*/RT2 The typical phase diagram has composition plotted on the x-axis and temperature on the y-axis. We look first for conditions where the liquidus is flat or vertical; in other words, where dT/dyA is zero or infinite. The slope is zero if the numerator of Equation (58) is zero or if f1 = f2. Generally, the fi for two compositions become equal only outside the temperature range of the binary T-x loop (Figure 8). Consequently, there is no likelihood of having a horizontal liquidus on a binary T-x loop. The second special case, a vertical slope, can occur if the denominator of Equation (58) is zero. The denominator can be written: (df2/dT)(1 f1) = (df1/dT)(1 f2) (See Equation (41), page 15). (59) (58)
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Our system was labeled such that component A melts at a lower temperature than component B. The temperature range accessible to liquidus conditions of such a binary loop is (TAf < T < TBf). Within this temperature range, (1 f2) is negative whereas (1 f1) is positive (Figure 9). Consequently, the distribution of signs on the factors in Equation (59) are: [()(+)] =? [()()] (60)
Clearly, this is an impossibility: the left-hand side will be negative whereas the right-hand side will be positive. A positive number cannot equal a negative number, hence we have shown there cannot be a vertical liquidus in a binary loop. A similar treatment of the solidus equation [Equation (56)] will show that it also cannot be flat or vertical in the temperature interval between the fusion temperatures of the end members. The liquidus curves of a binary loop can be either convex or concave upwards. Examples are shown on Figure 8. To determine the conditions for a convex or concave upward liquidus curve analytically is difficult because the second derivative with respect to yA is required for Equation (58). Equation (58) is an implicit representation of the liquidus curve; it is a function of T, not yA. Consequently, the chain rule would have to be used and the resulting expression is complex enough to almost defy analysis. Fortunately, there is a graphical method that works to some extent. The Gibbs energies of crystallization for the end members are linear functions of temperature in our simplified treatment. Consequently, graphs of the molar Gibbs energies of crystallization for the two end members of a binary loop can have only one of three configurations: The lines representing the changes on crystallization can intersect at temperatures greater than the fusion temperature of the more refractory end member; they can be parallel lines; or they can intersect at temperatures below the fusion temperature of the less refractory end member (Figure 8). Each configuration produces a unique shape for the liquidus and solidus. If the intersection of the curves representing the Gibbs energies of crystallization occurs at a temperature greater than the fusion temperature of the more refractory end member, then the liquidus curve is convex upwards. It is also true for the case where the entropies of 22
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crystallization are equal and the curves are parallel. On the other hand, the liquidus curve is concave upwards for the case where the lines representing the Gibbs energies of crystallization intersect below the lower fusion temperature (Figure 8). The heats of crystallization of several important end members are shown in Table 4. Solid solutions between albite and sanidine could have a configuration for a binary loop like the third case. However, the nonideal behavior required by the azeotrope and the incongruent melting of sanidine may make such a configuration difficult to detect. The olivines could also have a configuration like that predicted by case three. Again, there may be complications because the intersection of the lines representing the Gibbs energies of crystallization is at negative temperatures (K). Consequently, the linear approximation for the Gibbs energies of crystallization is invalid and one would have to investigate the effects of heat capacity terms on the slopes of the liquidus and solidus. Location of the Ternary Cotectic The location of the ternary cotectic (the line representing compositions in equilibrium with pure C and A-B solid solutions) can be calculated next. There are now three simultaneous equations, one for each component: A: yA = xA exp(A*/RT) B: yB = (1 xA) exp(B*/RT) C: yC = exp(C*/RT) In addition, we require that the sum of the mole fractions in the melt equal one: yA + y B + y C = 1 Solving Equations (61)(64) for xA gives: xA = [1 exp(B*/RT) exp(C*/RT)]/[exp(A*/RT) exp(B*/RT)] (65) (64) (61) (62) (63)
The ternary cotectic curve runs between the binary eutectic temperatures calculated earlier. The easiest method for locating the curve is to calculate xA at a series of temperatures between the binary eutectic temperatures with Equation (65). Then use these values of xA and the chosen temperatures to calculate yA and yB with Equations (61) and (62). The last mole fraction, yC, can be calculated with Equation (64). Some results are shown in Table 5.
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Calculation of the Isotherms Equations representing the isotherms in this system are particularly easy to find. In the primary phase field of component C, the equilibrium relation can be written: T = 30000/(20 R ln yC) (66)
At constant values of the mole fraction in the melt of component C, the right hand side of Equation (66) is a constant. Consequently, in the primary phase field of C, the isotherms are parallel to lines of constant mole fraction. To find the equations representing isotherms in the primary phase field of the A-B solid solutions, Equations (61), (62), and (64) can be combined in the form: yC = [(f1 f2)/f2] yA + (f2 1)/f2 where: f1 = exp( A*/RT) f2 = exp( B*/RT) If the temperature is constant, as it is on an isotherm, then Equation (67) has the form of a straight line, yC = a yA + b. Consequently, isotherms in the primary phase field of A-B solid solutions will be straight lines. These equations complete the description of the phase diagram. We know the compositions and temperatures of the eutectics, the liquidus and solidus of the binary solid solution diagram, the temperature and composition coordinates of the cotectic and the equations for the isotherms. The completed phase diagram is shown on Figure 9. Table 5: Composition and temperature coordinates of the ternary cotectic. TK xA yA yC 1100 0.0000 0.0000 0.4169 1075 0.1213 0.1770 0.3864 1050 0.2525 0.3267 0.3567 1025 0.4008 0.4574 0.3280 1000 0.5707 0.5707 0.3004 975 0.7676 0.6682 0.2738 950 1.0000 0.7514 0.2485 Linear isotherms are a consequence of the ideality assumption we are making and the absence of intermediate compounds in the system. They do not result from the linear form of the standard state Gibbs energies of crystallization. Rather they occur because T (67)
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and composition do not occur as products or quotients in the equations describing ideal solutions of compounds that are also components. Because the isotherms are linear in simple ideal systems, the liquidus surfaces are cylindrical surfaces with generators parallel to the isotherms. Calculation of Crystallization Paths. A crystallization path on a ternary diagram consists of a set of compositional coordinates. This is true whether the path is one of perfect fractional crystallization or perfect equilibrium crystallization. However, there are also the conditions, pressure and temperature, to contend with. Generally, phase diagrams are isobaric, polythermal ones when applied to petrological problems. Consequently, we actually need to construct a crystallization path in temperature-composition space. The first step, then, is to find the saturation temperature of the crystallizing assemblage. At this point, it is an advantage to take stock of the number of equations and the number of unknowns in those equations that we can put together. We assume the composition of the initial melt on the crystallization curve is known. Consequently, the mole fractions of the components in the melt are known. However, the composition of the saturating solid and the temperature of saturation are both unknown. If the solid is pure, then there is one equilibrium relation [Equation (63), for example]. The only remaining unknown is temperature, which can be calculated with the aid of Equation (63). If the solid is binary, then there are two equilibrium relations, [for example Equations (61) and (62)]. There is only one compositional variable in a binary solution, however, because the mole fractions of the two components must sum to one. Consequently, we can use the two equilibrium relations to calculate temperature and the composition of the solid solution. It is easy to demonstrate that for any solid solution of N components we can write equilibrium relations for each component. But the number of independent compositional variables in the solid solution is N 1 because the sum of the mole fractions must equal one. Consequently, we can always calculate the saturation temperature and composition of a phase, at a given pressure and melt composition.
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The discussion in the last paragraph provides us with a means for determining in which primary phase field a given composition falls: Calculate the saturation temperature for all possible phases. The primary phase field belongs to the solid with the highest saturation temperature. For example, composition A with 15% C saturates with C at approximately 839 K [Equation (63)] whereas the solid solution saturates at approximately 1104 K. If you have constructed the phase diagram as outlined above, you can determine from the isotherms that this last temperature is approximately correct. The determination of the saturation temperature for a solid solution requires some numerical analysis techniques because the equations are nonlinear. In our example, the equilibrium relations for components A and B can be written: xA = yA exp( A*/RT) xA = 1 yB exp( B*/RT) (68) (69)
Equations (68) and (69) are a simultaneous pair in two unknowns, T and xA (remember yA and yB are known). It is relatively easy to eliminate xA by setting the two equal to each other. However, solving the equations for T (or eliminating T, which is the same thing) is difficult because T occurs as part of the argument to the exponential function. Consequently, iterative methods of solutions of systems of nonlinear equations must be used to find xA and T. One can use these techniques to construct liquidus diagrams as functions of pressure and temperature. At several pressures, one calculates the saturation temperatures of the phases in the system. The points are plotted and connected with smooth curves. These are the saturation curves for the phases in P-T space. The curve that lies at the highest temperature at any pressure is the liquidus phase at that pressure. The metastable portions of the saturation curves can be plotted also. Where the curves are separated by small ranges in temperature, at the same pressure, the phase with the curve at a lower temperature than the saturation temperature of the liquidus phase will usually be the second phase to saturate at the pressure of interest. An example is shown in Figure 11.
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Perfect Equilibrium Paths The calculation of perfect equilibrium crystallization paths can be efficiently organized by invoking Duhem's theorem. Remember that this theorem states that if we know the bulk composition of an equilibrium system plus two other variables then all the equilibrium properties of the system are fixed (i.e. they can be calculated). The required compositional values for composition #1 are the percentages of A, B, and C (40%, 45%, and 15%) in the system. Let's call these values NA, NB and NC. If NM and NS represent the amounts of melt and solid solution in the system at some fixed pressure and temperature (the other two variables we must know to satisfy the conditions of Duhem's theorem) then conservation of mass requires that: xA NS + yA NM = NA (1 xA) NS + yB NM = NB yC NM = NC (70) (71) (72)
In addition to the equations representing conservation of matter, there are the equilibrium relations between components of the melt and solid solution. At constant pressure and temperature these can be written in the following form: yA = xA g1 yB = (1 xA) g2 where: g1 = exp(A*/RT) g2 = exp(B*/RT) In addition, we require that the sum of the mole fractions of the melt components equal 1: yA + yB + yC = 1 xA, yA, yB and yC. Some algebra can be used to eliminate all except xA to give: xA2 [(g1 g2)(NA + NB + NC)] xA [(NA + NC)(g1 g2) + (NA + NC)(1 g2)] + [NA(1 g2)] = 0 (75) (73) (74)
Equations (70)-(75) constitute a system of six equations in six unknowns, NS, NM,
(76)
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Table 6: Perfect equilibrium path for composition #1. Calculated with Equations (73), (74), (75) and (76). TK xA yA yC 1100 0.249 0.408 0.158 1080 0.292 0.436 0.201 1070 0.312 0.444 0.225 1060 0.329 0.447 0.250 1050 0.345 0.446 0.276 1040 0.359 0.442 0.304 1030 0.371 0.435 0.332 Equation (76) is a quadratic equation in xA which will provide two values on solution. Examination of the phase diagram (Figure 10) will show that the smaller value is correct. It is then a straightforward matter to back substitute into Equations (70)-(75) to calculate the remaining variables. Some results for composition #1 are listed in Table 6. The perfect equilibrium crystallization path for composition A is plotted on Figure 10, curve E. Perfect Fractionation Paths Although perfect fractionation can be approximated by a series of perfect equilibrium crystallization calculations, such a procedure does not provide a means for extrapolating to precursors of the present melt composition, assuming it was derived by perfect fractionation. The use of fractionation curves for determining more primitive melt compositions was described several years ago (Irvine, 1977; Pearce, 1978). At the time, the lack of knowledge of the temperature and compositional dependence of the distribution coefficients of components between crystal and melt precluded accurate calculations. Our first objective is to derive equations from which we can calculate the composition of the liquid and solids at any stage of the fractionation process. The fractionation curves of ternary phase diagrams are the geometric representation of the equations that provide the compositions of the melts. We will examine the case where the fractionating solid is a binary solution in components one and two. The mole fraction of component one in the solid will be labeled x. Consequently, the mole fraction of
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component two in the solid will be (1 x). Components in the melts, whether ternary or higher, will be labeled yi, i = 1,N. The mole fractions in the melt are related to the numbers of moles of the components in the melt by: y1 = n1/(n1 + n2 + sn) y2 = n2/(n1 + n2 + sn) where the ni are the number of moles of component i in the melt and sn is the sum: sn = ini, i = 3, N simply equal to n3. We will define: Sn = ini, i = 1, N The two sums, Sn and sn, are related by: Sn = n1 + n2 + sn one and two, sn is a constant. Therefore, the differentials of y1 and y2 are given by: dy1 = (1 y1) dn1/Sn y1 dn2/Sn dy2 = y2 dn1/Sn + (1 y2) dn2/Sn (82) (83) (81) (80) (79) (77) (78)
N is the number of components in the chemical system. If the system is ternary, then sn is
Note that because there is only one fractionating phase containing components
The definition of perfect fractionation requires that the change in melt composition equal that of the crystallizing solids. In our problem this means that the composition of the binary solution must be a function of the instantaneous changes of n1 and n2 in the melt: x = dn1/(dn1 + dn2) and (83), and eliminate dn1 from the resulting two equations: dy2/dy1 = (1 x y2)/(x y1) (85) (84)
The next step is to solve Equation (84) for dn2, substitute the result into Equations (82)
Equation (85) is our fundamental equation. It describes the effect of perfect fractionation of a binary solid solution on the composition of a melt. Notice that the expression is independent of the mole fractions of all components except those that enter the solid solution (i.e. the expression is independent of y3, y4,.....yN). 29
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Integration of Equation (85) will provide y2 as a function of y1. Consequently, if we know the initial composition of the fractionating system, we can plot the fractionation curve through the initial composition at all other values of y1. The integration cannot be carried out, however, until the relationship between x and y1 is specified. This relationship is necessarily a thermodynamic one and its exact nature will depend on the degree of non-ideality of the solid and liquid solutions. Equation (85) can also be derived from geometric arguments if the system is ternary. Such a derivation provides an illustration of the compositional meaning of the mathematical notation in Equation (85). A fundamental postulate of phase diagrams is that liquid compositions move directly away from the instantaneous composition of the crystallizing solid. The situation is shown on Figure 12. The solid composition lies on the line between pure component one and pure component two. Suppose the solid crystallizing has the composition of point S at coordinates (x,y2). However, the binary nature of the solid solution requires that: y2 = x + 1 (86)
The liquid composition, L, with coordinates (y1, y2), lies on the fractionation curve (labeled F on Figure 10). The straight line connecting L and S is, by definition (see above), tangent to the fractionation curve. The derivative of y2 with respect to y1 gives the instantaneous slope of the fractionation curve. We need only equate the derivative with the slope of the straight line between L and S to get: dy2/dy1 = (y2 y2)/(x y1) earlier: dy2/dy1 = (1 x y2)/(x y1) (88) (87)
Substitution of the value of y2 from Equation (86) gives the result obtained
The second equation that describes the state of a system during a perfect fractionation process is one from which we can calculate the amount of uncrystallized melt. As in most petrological calculations, we are not after the absolute amount of melt but rather the fraction of the original melt that has not crystallized. This fraction, F, is defined by:
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PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES F = Sn/Sn (89)
where Sn is the number of moles of components 1, 2,....,N originally present in the magma before fractionation. Equation (89) is a definition rather than a practical recipe for calculating F. However, the definitions of y1, y2, sn and Sn [Equations (77) (80)] can be combined to give: F = (1 y1 y2)/(1 y1 y2) fractionation. Equations (85) and (90) are our main weapons for calculating more primitive melt compositions. Before delving into the calculations a description of the petrologic situation is in order. Suppose we have a lava or, better yet, a glass composition and associated with this lava or glass is an olivine that is too Mgrich in its core to be in equilibrium with the melt. If we call Mg2SiO4 component A (or 1) and Fe2SiO4 component B (or 2) then one way we can recognize this fact is to calculate an equilibrium olivine composition with Equations (68) and (69). If the calculated value of the equilibrium olivine differs significantly from the composition of the cores of the olivine phenocrysts then presumably the crystals and melt were not in equilibrium. Consequently, the olivine is perhaps a cognate xenocryst that formed during an earlier stage in the evolution of the lava which then fractionated olivine to achieve its present state. What we want to do is calculate the composition of a melt that satisfies two criteria: (1) (2) The calculated melt is in equilibrium with the Mg-rich olivine. The observed composition of the lava or glass lies on a fractionation curve (90)
where the superscript, , indicates the values of the mole fractions in the melt prior to
that passes through the calculated melt composition. Integral Form of Fractionation Curves Our desired position is an integrated form of Equation (85). Only under special circumstances, however, can an integrated form of Equation (85) be found with the result expressed in elementary functions. In order to integrate Equation (85), xA has to be
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eliminated, say with Equation (68). This elimination introduces T which can, in theory be eliminated with Equation (69). In other words, we would have to eliminate T between Equations (68) and (69), solve the result explicitly for xA, and substitute into Equation (85). If the distributions of components A and B were independent of T so that: xA = Kd1 yA 1 xA = Kd2 yB Then under these circumstances Equation (88) becomes: dyB/dyA = (Kd2 1) yB/[(Kd1 1) yA] Integration gives: yB/yB' = (yA/yA')K where K = (Kd2 1)/(Kd1 1). We know, however, that Kdi is equal to: Kdi = exp(Gi*/RT) = exp[(Hf* T Sf*)/RT] (95) (94) (91) (92) (93)
In order for Kdi to be constant, the argument in the exponential function must be constant. The only way this can happen is if the temperature is constant, an impossibility if crystallization is constrained to fall on a fractionation curve. Consequently, this integrated form can, at best, be only an approximation over a small temperature range and we might as well go to numerical integration methods directly. Numerical Integration of Fractionation Slopes Our starting point is with Equations (68) and (69). These two equations contain the composition of the olivine, x, temperature, T, and the mole fractions of components one and two in the melt, y1 and y2, as potential unknowns. Because the composition of a melt on the fractionation curve is, by hypothesis, the composition of the rock or glass, we can determine y1 and y2. Equations (68) and (69) can be solved for x and T, the remaining variables. The next step is to calculate the composition of a melt slightly displaced in composition from the original but up in temperature along the fractionation curve. To do this we slightly increase the value of y1 (the Mg-component of the melt) and call this increment dy1. Because the Mg-component has a very much higher fusion temperature than the Fe-component, increasing y1 will usually guarantee we are moving up the
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fractionation curve (for an exception to this statement see Ghiorso, et al., 1983, p. 125). We next calculate the increment in y2, dy2, with Equation (88). The mole fractions of y1' and y2' in the new melt are then given by: y1' = y1 + dy1 y2' = y2 + dy2 (96) (97)
The remaining mole fractions in the new melt are easily calculated with the aid of the definition of the fractionation stage F [Equation (89)]. The mole fraction of component j, a component that remains in the melt during fractionation is given by: yj' = nj/Sn Substitution for Sn from the defining equation for F gives: yj' = nj/(F Sn) original, consequently, the original mole fraction of component j is given by: yj = nj/Sn component that remains in the melt and is not fractionated into the solids: yj' = yj/F, j = 3,...,N (101) (100) (99) (98)
However, the number of moles of component j is the same in the new melt as in the
Combining the last two equations gives the expression for the mole fraction of a
The mole fractions of all the components in the melt on the fractionation curve, which is the precursor to the melt represented by the lava or glass, can be calculated with Equations (96), (97), and (101). One then begins the process anew: first, calculate an olivine composition and equilibrium temperature for the new melt with Equations (68) and (69) then find another melt composition on the fractionation curve by incrementally increasing y1 and y2. The process is repeated until the calculated composition of the olivine in equilibrium with the primitive melt matches that of the Mg-rich core of the olivine found in the rock. The values of y1 and y2 that result in this olivine composition also determine the primitive melt composition when substituted into Equations (90) and (101) and the calculations are complete. To apply this discussion to our current problem, we first make a small change in notation to Equation (88):
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PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES dyB/dyA = (1 xA yB)/(xA yA) (102)
The first step of the calculations has already been done. From the calculation of the saturation temperature and composition of the solid solution we know xA. The original composition of the system provides yA and yB. Substitution into Equation (102) gives us the slope of the fractionation curve at the composition of the original melt (dyB/dyA = 1.94). Next pick a fractionation step by choosing a value for dyA. This is possibly the most critical step. If you choose too large a step, then the fractionation path will be imprecisely located; if the step is too small, at best you will spend a lot of time and effort calculating the path. In addition, if the calculation is part of a computer program, round off error may cause the calculations to be wrong. Because the purpose of the problem is to provide an idea of the concepts of calculating phase diagrams, let's choose a fairly large step, say 0.1, for the change in yA. Then dyB can be obtained from Equation (102) as 0.194. Adjusting the values of the mole fractions and ensuring that the sum of the mole fractions of the melt components is one gives: yA = 0.500 yB = 0.256 yC = 0.244 When the new melt composition is plotted on Figure 10, it falls very close to the 1050 K isotherm. This value can be substituted into Equation (68) or Equation (69) and a new value of xA calculated. The slope is again evaluated and another step along the fractionation path is calculated. The result is shown on Figure 10 (Curve F). One can also change the sign of the fractionation step, dyA, and calculate the fractionation path to higher (that is, more primitive compositions). This part of the curve is labeled F' Figure 10. Polybaric Fractionation Curves To calculate isobaric fractionation curves, we need only vary one melt component to step along the curve. Given an initial composition, there is only one fractionation path that can be calculated. If a polybaric fractionation curve is required however, the system of equations will have two independently variable compositional components and the
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path will not be unique for a given starting composition. If another thermodynamic property of the melt can be set, then the pressure need not be fixed and there will be only one independently variable compositional component. A unique polybaric fractionation path can then be calculated which will reflect the constraint provided by the additional thermodynamic variable. A tractable path to calculate is one in which there is no heat lost from the melt; the only heat extracted from the magma would be that carried by the fractionating solids. Only the melt is on the isenthalpic path; fractionated solids are removed from the system on crystallization. The derivation is for a system fractionating a single binary solid solution. The differentials of H and S as functions of P, T, V, S and number of moles in the melt are given by: dH = V dP + T dS + i dni and: dS = (Cp/T) dT + (S/P)T,n dP + (S/ni)T,P dni where the summation index, i, runs from 1 to N. In order to find dH as a function of P and T, we need to substitute for dS (as a function of P, T and the ni) in Equation (103). In order to do this, we need to find an expression for the coefficient of dP in Equation (104) in terms of melt properties (V, Cp, etc.). The differential of the Gibbs function is given by: dG = V dP S dT + i dni Applying Maxwell's relations gives: (S/P)T,n = (V/T)P,n with respect to temperature by: (V/T)P,n = V Substituting into Equation (104) gives: dS = (Cp /T) dT V dP + (S/ni)T,P dni (108) (107) (106) (105) (104) (103)
The coefficient of thermal expansion, , is related to the partial derivative of the volume
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A further substitution of this last equation into Equation (103) gives: dH = V(1 T) dP + Cp dT + T (S/ni)T,P dni + i dni (109)
The coefficients of dni can be combined by noting that the partial derivatives of S with respect to ni are partial molar entropies and are related to the partial molar enthalpies, hi, by: i + T (S/ni)T,P = hi following equation: dH = V(1 T) dP + Cp dT + hi dni (111) (110)
The general equation for changes in H due to changes in P, T and ni is given by the
The next step is to introduce the constraints generated by a single, fractionating, binary solid. The mole fraction of component 1 in the solid will be represented by x and the corresponding mole fraction in the melt will be represented by y1. The mole fraction of component 2 in the solid is (1 x) and is y2 in the melt. The size of the system is the sum of the moles of each component and is given by: Sn = ni Divide Equation (111) by Sn: dH/Sn = (V/Sn)(1 T) dP + (Cp /Sn) dT + hi dni/Sn Introduce molar quantities: v = V/Sn; cp = Cp /Sn to get: dH/Sn = v(1 T) dP + cp dT + hi dni/Sn becomes: dH/Sn = v(1 T) dP + cp dT + h1 dn1/Sn + h2 dn2/Sn The composition of the fractionating solid is given by: x = dn1/(dn1 + dn2) Substituting this last equation into the penultimate one gives: dH/Sn = v(1 T) dP + cp dT + [x h1 + (1 x) h2](dn1 + dn2)/Sn (118) (117) (116) (115) (114) (113) (112)
If only components 1 and 2 are crystallizing as a solid solution then Equation (115)
36
GLGY 431
If only a binary solid composed of components 1 and 2 is fractionating, then the change in the size of the system is given by: dSn = dn1 + dn2 The mole fraction of component 1 in the melt is given by: y1 = n1/Sn Its differential is given by: dy1 = dn1/Sn y1 dSn/Sn An analogous expression can be written for y2: dy2 = dn2/Sn y2 dSn/Sn Adding Equations (121) and (122) gives: (dn1 + dn2)/Sn = (dy1 + dy2)/(1 y1 y2) Substituting the result into Equation (118) gives: dH/Sn = v(1 T) dP + cp dT + [x h1 + (1 x) h2](dy1 + dy2)/(1 y1 y2) Under conditions of constant H, Equation (124) can be written: (1 y1 y2)[v(1 T) dP/dT + cp] = [x h1 + (1 x) h2](dy1/dT + dy2/dT) independent, but are related by: dy2/dT = [(1 x y2)/(x y1)] dy1/dT Combining these last two equations gives: (x y1)[v(1 T) dP/dT + cp] = [x h1 + (1 x) h2] dy1/dT An example may make the use of Equation (127) easier to follow. To minimize numerical problems, and cp will be set to zero in the following illustration. Generally, is of the order 1 10-9 and T is of the order 1000. Consequently, T is considerably less than one and the assumption of equal to zero is a reasonable one. The molar heat capacity, cp, however is not zero and would need to be included in a real calculation. With these stipulations, Equation (127) becomes: dP = - [x h1 + (1 - x) h2] dy1/[v(x - y1)] (128) (127) (126) (125) (124) (123) (122) (121) (120) (119)
In a fractionating system, the derivatives of the mole fractions in the melt are not
37
GLGY 431
where hi is the standard state enthalpy of component i. The standard state molar enthalpies can be used in place of the partial molar enthalpies because of the assumption of ideal melt solutions. Given an initial melt composition and an initial pressure, the calculation of the fractionation path begins with solving the pair of equations: 1s(T, P, x) = 1m(P, T, yi) 2 (T, P, x) = 2 (P, T, yi) calculated with: dy2 = (1 - x - y2) dy1/(x - y1) repeated. An example is shown on Figure 13. As expected, the polybaric, isenthalpic path diverges from the isobaric path. As a result, the solid compositions fractionating from derivative melts will be different along the two paths, even though the initial melt composition and conditions were identical. The isobaric perfect fractionation path is reversible. By changing the sign of dy1 at any stage of fractionation one reproduces points on the path above the fractionation stage where the sign change was made. In contrast, the polybaric, isenthalpic path is not reversible. The isenthalpic path shown on Figure 13 was calculated from high pressure to low starting with a composition where the two paths, isobaric and isenthalpic, diverge on the left-hand diagram (40% A, 45% B). Again change the sign of dy1 and starting at the low pressure end of the original isenthalpic path (32.6% A, 5.5% B) calculate a path under isenthalpic conditions; it does not exactly coincide with the original. This is more apparent on the plot of melt mole fraction y1 vs solid mole fraction, x, [Figure 13(b)] where the compositions near the maximum on the fractionation paths are distinct. Isenthalpic paths are not reversible paths [See, for example, Waldbaum, 1971; Lewis and Randall, 1961, p. 46-51) whereas isentropic paths are. (131)
s m
(129) (130)
for x and T. A value for dy1 is selected and the change in concentration of component 2 is
The pressure change is calculated from Equation (128) and the cycle of calculations
38
GLGY 431
Example from Yukon Territory The lava flows from Volcano Mountain form one of the few reported occurrences of Recent nephelinites in the Canadian Cordillera (Francis and Ludden, 1990; Fiesinger and Nicholls, 1977; Nicholls, et al. 1982). They contain olivine phenocrysts, clinopyroxene microphenocrysts, and olivine, pyroxene, microlitic nepheline and leucite in the groundmass, and host ultramafic xenoliths (spinel lherzolites) and olivine xenocrysts. The curve labeled olivine on Figure 14 is the saturation curve for olivine in a melt with the composition of a Yukon nephelinite. An isenthalpic fractionation curve (Nicholls 1990) starting at the olivine saturation temperature at 2 GPa is shown with a dashed line. The curve labeled clinopyroxene connects points where olivine and clinopyroxene coexist with melts that formed by perfect fractionation of olivine under isobaric conditions. The numbers on the points designated with plus signs are the calculated olivine compositions that fractionated along the isenthalpic curve on ascent to the surface. The numbers in italics on the points shown with open squares are the calculated olivine compositions that coexist with clinopyroxene and melts derived by isobaric fractionation. Observed olivine compositions in the phenocryst cores and groundmass are indicated with bold numbers. If the magma that formed this nephelinite had ascended along the isenthalpic path shown with a dashed line on Figure 14, the expected product, according to the model, would be a rock with a monomineralic olivine phenocryst assemblage and a glassy or finely crystalline groundmass, as the isenthalpic decompression path never crosses the clinopyroxene saturation curve. Introducing a small amount of heat loss, (i.e., deviating slightly from a perfectly isenthalpic crystallization path) would produce microphenocrysts of clinopyroxene. The observed textures in the nephelinites show a monomineralic phenocryst assemblage with small modal amounts of pyroxene microphenocrysts. Furthermore, the expected compositions of the phenocrysts under isobaric crystallization conditions at the pressures and temperatures modeled do not match the observed values but they nearly match those predicted to form on an isenthalpic fractionation path (Figure 14). These
39
GLGY 431
observations suggest that the modeled nephelinite in particular and the other nephelinites from Volcano Mountain crystallized under polybaric conditions and that loss of heat from the magma during ascent was small. This interpretation of the crystallization path is consistent the fact that lava flows usually erupt rapidly with little heat loss during transport.
40
1.0
0.8
0.6
Tw = 300 K Ts = 500 K
x
0.4
0.2
0.0
P (bars)
10
15
20
25
Figure 1: Diagram representing the equality of chemical potentials of H2O in steam and an ideal solution. The two phases are at different temperatures.
Mass Balance Equations (1 - x) zS + (1 - y B - yC) zL = 1 - y - y B C

Thermodynamic Equations S L mA = mA
C z = dS/ (dS + dL) L z = dL/(dS + d ) L
S
L dS dL A
Known Values y: Mole fraction component C in system. C y: Mole fraction component B in system. B
System Composition
B S Mole Fraction, x
Variables 1. x: Mole fraction component B in binary solid. 2. yB: Mole fraction component B in melt. 3. yC: Mole fraction component C in melt. 4. zL: Fraction of melt in system. S 5. z : Fraction of solid in system. 6. T: Temperature. 7. P: Pressure.
Unknown Variables - Number of Equations = 2

Figure 2: Example of the application of Duhem's theorem. Given the initial composition of the chemical system, yB and yC, and the values of two other variables, T and P, there are five equations to be solved for the remaining variables; three mass balance equations and two thermodynamic ones. The remaining variables are the composition of the melt (yB, yC), the composition of the solid (x, 0) and the fractions of each phase, zS and zL.
TA,f TB,f f2
f1
3
df2/dT = f2DHB/RT2 < 0
fi
2
f2 > 1 (1 - f 2) < 0
1
f1 <1 (1 - f 1) > 0
df1/dT = f1DHA/RT < 0
500
1000
TK
1500
2000
Figure 3: Diagram showing the properties and relationships for two curves of fi vs T [fi = exp(mi */RT)]. In one instance, the parameters are: HA* = 45000, SA* = 45. For the other curve, the parameters are: HB* = 60000, SB* = 50. Slopes are shown at T equal 1100.
25 20 15 10 5 A B C
Dm* i
0 -5 -10 -15 -20 800 900 1000 1100 1200 1300 1400 1500
T
Figure 4: Plot of Dmi* for the three end members of the ternary system discussed in the text. The crystallization (or fusion) temperatures of the end members are given by the intersection of the curves and the line where Dmi* = 0 (1000 for A, 1200 for B, and 1500 for C).
1500
1300
T
1100 Te 900 0.0 0.2 0.4 0.6 ye 0.8 1.0
yA
Figure 5: The phase diagram for the AC binary side of the ternary diagram discussed in the text. The eutectic temperature, Te, and composition, ye, are marked. The liquidus curves are dashed where metastable below the eutectic temperature.
2000
b-Quartz
Cristobalite
1500
TK
1000
500
Inflection point
0 0.0
0.2
0.4
0.6
0.8
1.0
Mole Fraction SiO2 in Ideal Melt

Figure 6: Binary liquidus curves for cristobalite and b-quartz, assuming ideal solution behavior in the melt and Dcp = 0 for the fusion reaction. The large circle marks the inflection point on the liquidus curve for cristobalite.
1200
F(y, T)
TK
1100
F(x, T)
1000
B
0.0 0.2 0.4 0.6 0.8
A
1.0
y A, x A
Figure 7: The binary loop along the A-B side of the ternary diagram.
1600
40
1500
DHA = -30 kJ, DSA = -25 J/K DHB= -60 kJ, DSB = -40 J/K
20
1400
DG (kJ) xl
TfA
TK
1300
-20 -40
TfB
1200
-60
1600
40
1500
DHA = -30.0 kJ, DSA = -25 J/K DHB= -37.5 kJ, DSB = -25 J/K
20
1400
DG (kJ) xl
TfA
TK
1300
-20 -40
TfB
1200
-60
1100 1600
40
1500
DHA = -60 kJ, DSA = -50 J/K DHB= -30 kJ, DSB = -20 J/K
20
1400
DG (kJ) xl
TfA
TK
1300
-20 -40
TfB
1200
-60
1100
0.2
0.4
x, y
0.6
0.8
500
1000
1500
2000
TK
Figure 8: Diagram showing binary loop configurations and the corresponding arrangements of standard state Gibbs energy of crystallization curves.
TA,f TB,f f2
f1
3
df2/dT = f2DHB/RT2 < 0
fi
2
f2 > 1 (1 - f 2) < 0
1
f1 <1 (1 - f 1) > 0
df1/dT = f1DHA/RT < 0
500
1000
TK
1500
2000
Figure 9: Plot of f and their slopes vs T for components A and B.
C 1500
1400 1300 1200 1100 1000
1200
1000
C 1500
1400 1300 1200 1100
E F'
1200
F A
1000
Figure 10: Phase diagram for the system ABC. An example described in the text. Isotherms are shown with dashed lines. The ternary cotectic runs between the AC and BC edges of the diagram. The curve FF' is a fractionation curve through composition #1. Curve E is the perfect equilibrium path that originates at composition #1
1.0
0.8
BT1 Saturation Curves, Dry

Olivine Cpx
P(GPa)
0.6
Dashed where metastable
0.4 Plagioclase
0.2
1000
1050
1100
1150
1200
1250
TC
Figure 11: Saturation curves for olivine, plagioclase and clinopyroxene for a basalt from Craters of the Moon Lava Field, Idaho (Stout, et al., 1994). Curves calculated with data from thermodynamic data from Ghiorso, et al. (1983).
B
dyB/dyA = (yB - y ) / (yA - y) B A y = 1 - x, y = x B A dy B/dy A = (1 - x - y B)/(x - yA ) yB y B
yA
x, y A
Figure 12: Geometrical relationships between fractionation curves and binary solid solution composition in a ternary system. Mole fractions of melt components represented by y1 and y2. The mole fraction of component 1 in the solid is represented by x.
Isobaric Fractionation Curve Isenthalpic Fractionation Curve
(a)
B
1200
1100
1000 900
C
0.45
y1 - Mole Fraction in Melt
(b)
0.40
0.35
Down P Curve Up P Curve Isobaric Curve
0.30 0.3
0.4
0.5
0.6
0.7
x - Mole Fraction in Solid

Figure 13: Comparison of an isobaric perfect fractionation path and an isenthalpic fractionation path. Both are equilibrium paths in the sense that S L mi = mi holds for all components. The isenthalpic path, however, is not a reversible path whereas the isobaric path is. (a): Ternary system ABC. Dashed lines are zero pressure isotherms. (b): Melt and solid mole fractions for component 1.
1.0
VM01 Saturation Curves & Isenthalpic Fractionation Curve
xFo = 0.8983
0.91 Pheno Cores
0.8955
0.8
0.8925
Plag
P(GPa)
0.6
Cpx
0.8895
0.8862
0.4
0.8830
Olivine
0.2
0.8796
0.84 Gm 0.8739
0.0 1000
1100
1200
1300
1400
TC
Figure 14: Saturation curves and an isenthalpic path for a nephelinite from Volcano Mountain, Yukon Territory (Trupia, 1992; Trupia and Nicholls, 1996). Bold text indicates measured olivine compositions. Other numbers are calculated mole fractions of olivine in the isenthalpic fractionation model.

Principles of Thermodynamic Modeling of Igneous Processes

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Geology 531: Igneous Petrology Notes

PART 3: Principles of Thermodynamic Modeling of Igneous Processes

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

(17) (18) (19)

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

The derivative of Equation (40) is required when analyzing crystallization paths

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES f1 = exp( A*/RT) f2 = exp( B*/RT)

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES F = Sn/Sn (89)

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES dyB/dyA = (1 xA yB)/(xA yA) (102)

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES

Mass Balance Equations (1 - x) zS + (1 - y B - yC) zL = 1 - y - y B C

Unknown Variables - Number of Equations = 2

df2/dT = f2DHB/RT2 < 0

df1/dT = f1DHA/RT < 0

Mole Fraction SiO2 in Ideal Melt

df2/dT = f2DHB/RT2 < 0

df1/dT = f1DHA/RT < 0

Figure 9: Plot of f and their slopes vs T for components A and B.

BT1 Saturation Curves, Dry

Dashed where metastable

Isobaric Fractionation Curve Isenthalpic Fractionation Curve

y1 - Mole Fraction in Melt

Down P Curve Up P Curve Isobaric Curve

x - Mole Fraction in Solid

0.91 Pheno Cores

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PRINCIPLES OF THERMODYNAMIC MODELING OF IGNEOUS PROCESSES f1 = exp( A/RT) f2 = exp( B/RT)