Solutions

Notes on the Thermodynamics of Solids J.W. Morris, Jr.
; Fall, 2008
Chapter 18: Solutions

Chapter 18: Solutions.......................................................................................................396
18.1 Introduction .................................................................................................396
18.2 Ideal Solutions .............................................................................................397
18.2.1 A solution of ideal gases...............................................................397
18.2.2 The ideal solution..........................................................................400
18.3.3 The vapor pressure of a component in an ideal solution ...............401
18.3 Thermodynamics of Real Solutions.............................................................401
18.3.1 Excess thermodynamic quantities .................................................401
18.3.2 The activity and the activity coefficient .........................................403
18.4 Dilute Solutions ...........................................................................................404
18.4.1 The chemical potential in a dilute solution.....................................404
18.4.2 The fundamental equation of a dilute solution...............................407
18.4.3 Generalization to "semi-dilute" solutions ......................................408
18.5 Dilute Solutions: Applications.....................................................................409
18.5.1 Equilibrium of two solutions with the same solvent .....................409
18.5.2 Influence of a dilute solute on two-phase equilibrium...................410
18.5.3 The vapor pressure of a dilute solution: Raoult's Law ..................411
18.5.4 Osmotic pressure..........................................................................412
18.5.5 Dilute solutions with the same solute: Henry's Law .....................413
18.5.6 Solute-solvent equilibria between dilute solutions ........................414
18.5.7 The interference of solutes in a dilute ternary solution...................415
18.6 Behavior near a Critical Point ......................................................................416
18.7 The Simple Solution ....................................................................................419
18.7.1 The thermodynamics of the simple solution..................................419
18.7.2 Decomposition and ordering in the simple solution......................421
18.8 The Phase Diagram of a Binary Solution.....................................................422
18.8.1 Special points in the T-x diagram..................................................422
18.8.2 Binary phase diagrams..................................................................425
18.8.3 Solid solution diagrams ................................................................425
18.8.4 Low-temperature behavior of a solid solution...............................427
18.8.5 Phase diagrams with eutectic or peritectic reactions ......................430
18.8.6 Structural transformations in the solid state ..................................433
18.8.7 Systems that form compounds......................................................435
18.8.8 Mutation lines in binary phase diagrams.......................................441
18.8.9 Miscibility gap in the liquid ..........................................................442
18.1 INTRODUCTION
This chapter treats multicomponent fluid phases (solutions) that are sufficiently
simple that their thermodynamic behavior can be studied in some detail. We are, of course,
particularly interested in solid solutions, which obey the thermodynamics of fluids if the
stress is hydrostatic. The theory developed in this chapter includes that part of the
Page 396
Notes on the Thermodynamics of Solids J.W. Morris, Jr.; Fall, 2008
thermodynamics of solid solutions that is independent of the details of the atom

arrangements.
We begin with a discussion of the one completely solvable case: a solution of ideal
gases. We shall then use classical thermodynamics to generalize this result to the simplest
model of a real solution, the ideal solution. While almost no real solutions (except the ideal
gases) are ideal solutions over the whole range of composition, we shall discover that every
solution behaves very nearly like an ideal solution in the limit of small solute concentration
(the dilute solution). This result, and its logical extension to higher solute concentrations
through an expansion of the free energy in powers of the concentration, is the basis for
most of the useful theory of solutions, and we shall explore its applications in some detail.
We shall then consider models that attempt a global representation of the fundamental equa-
tion of a solution. Finally, we shall discuss the phase diagrams that represent the equilib-
rium of binary solutions and offer a simple classification of the more important of these.
18.2 IDEAL SOLUTIONS
18.2.1 A solution of ideal gases
The fundamental equation of a mixture of ideal gases was developed as an exercise

earlier in the course. The classical derivation is based on Dalton's Law,
N kT
Pk = V 18.1
where Pk is the partial pressure of the kth specie, and the caloric equation of state
3
E = NCT = 2 NT 18.2
where N is the total mole number. From eq. 18.2 the energy can be written as the sum of
the energies of the individual species:
3
E = Ek = 2 NkT 18.3
k k
Given the additivity of the energy and the pressure,
E PV
S = T + T - i N i = S k 18.4
i k
where Sk is the entropy the kth specie would have if it filled the volume V, at temperature,
T, alone. It follows that a component in a solution of ideal gases has the entropy it would
have if it were present alone.
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The entropy of a one-component ideal gas can be found by integrating the thermal
and caloric equations of state, and is
3 E V
S(E,V,N) = 2 NlnN + NlnN + Ns 18.5
The entropic form of the fundamental equation of a mixture of ideal gases is, therefore,
S(E,V,{N}) = Ns(e,v,{x})
Ek V
= 3
NklnN + NklnN + Nksk
2 k k
k
3 E V
= 2 NlnN + NlnN - N xkln(xk) + N xksk 18.6
k k
Comparing eqs. 18.5 and 18.6, the major difference between the entropy functions of the
one-component and n-component ideal gas is the inclusion of the extra term
Smix = - N xkln(xk) 18.7

k
on the right-hand side of 18.6. This term is called the entropy of mixing, and plays a cen-
tral role in the thermodynamics of solutions. Note that the entropy of mixing is a straight-
forward consequence of Dalton's Law; it does not enter because the species interact, but
because they do not interact. Its appearance is a consequence of writing the entropy as a
function of the global content of the mixture (E,N) rather than the contents of the individual
species (Ek, Nk). Essentially, it results from the fact that the various species in the mixture
fill the same space at the same time.
The Helmholtz free energy can be found by expressing S as a function of T,V and
{N}, and can be written
F(T,V,{N}) = Nf(T,v,{x}) = VFv(T,{n})
3n
= - VT 2 ln(T) + n - nkln(nk) + nkfk
k k
3
= - NT2ln(T) + ln(v) + 1 - xkln(xk) + xkfk 18.8
k k
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The advantage of using the Helmholtz free energy is that it is easily computed from

statistical thermodynamics, which lets us evaluate the unknown constants, fk . The result is
3 mk
fk = 2 ln 18.9
2N02
where mk is the atomic mass of the kth specie, N0 is Avogadro's number, = h/2, h is
Planck's constant, and T is measured as RK, where R is the molar gas constant and K is the
temperature in degrees Kelvin. [I leave it as an exercise to confirm that, with this result, the
quantity in braces on the right-hand side of 18.8 is dimensionless.]
The form of the fundamental equation that is most commonly used in the study of
solutions is the Gibbs free energy. To find it we compute the chemical potentials of the
components as a function of T, P, and {x}. From equation 18.8,
F 3T Nk
k = N = - 2 ln(T) + T ln V - Tfk
k
5T
= T ln(Pk) - 2 ln(T) - Tfk 18.10
Equation 18.10 shows that the chemical potential of a component in a solution of ideal
gases is the chemical potential it would have if it were present by itself. Since Pk = xkP,
where xk is the atom fraction of the kth component,
5T
k = T ln(P) - 2 ln(T) - Tfk + T ln(xk)
0
= k(T,P) + T ln(xk) 18.11
0
where k(T,P) is the chemical potential of component k at temperature T and pressure P.
The Gibbs free energy per mole is, then,
0
g(T,P,{x}) = xkk(T,P) + T xk ln(xk) 18.12
k k
where the first term is the Gibbs free energy per mole when the components are separated
at constant P and T, and the second term (which is negative) is the free energy of mixing.
Note that the free energy of the mixing comes from the entropy of mixing; it does not rep-
resent any physical interaction between the species, but is due to the fact that they do not
interact, and can, hence, fill the same space at the same time.
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18.2.2 The ideal solution
The mixture of ideal gases is one example of an ideal solution, which is a solution
of atoms of species that have no preferential interaction with one another. The ideal solu-
tion is the simplest solvable model of a real solution. It is useful to define an ideal solution
by its Gibbs free energy:
an ideal solution is a solution that obeys a fundamental equation of the form

0
18.12, where k(T,P) is the chemical potential of a pure sample of the kth
component at temperature T and pressure P.
Equation 18.12 shows that the change in free energy on forming an ideal solution from the
pure components at (T,P) is always negative. Hence species that form ideal solutions are
miscible in any proportions.
The entropy of mixing of an ideal solution is the same as that of a mixture of ideal
gases (eq. 18.6). The chemical potential of the kth component of an ideal solution is given
by equation 18.11. The molar enthalpy of an ideal solution is
0 0
h = g + Ts = xkk(T,P) + Tsk(T,P)
k
0
= xkhk(T,P) 18.13
k
0
where sk(T,P) is the molar entropy of the kth component in its pure state at (T,P).
Equation 18.13 shows that the heat of mixing, h, is zero; the enthalpy of an ideal solution
is just the weighted average of the enthalpies of its pure components, so no heat evolves
when the solution forms. It follows as a corollary that the miscibility of the species that
form an ideal solution is due to the entropy of mixing.
The relative chemical potential of the kth component in an ideal solution is
g 0 0 xk
k(T,P,{x}) = x = k - n + T lnx
k n
0 xk
= k(T,P) + T lnx 18.14
n
0
where n designates the reference component, or solvent, and k(T,P) is the relative chemi-
cal potential of the pure solute. Note that k depends on the concentrations of the other
solutes only through their effect on xn, the mole fraction of the solvent. For a binary solu-
tion,
Page 400
0 x
k(T,P,x) = k(T,P) + T ln1 - x 18.15
where x is the mole fraction of solute.
18.3.3 The vapor pressure of a component in an ideal solution
One of the properties of an ideal solution that can be easily calculated is the equilib-
rium vapor pressures of its components. Let the ideal solution be a condensed phase in
equilibrium with a vapor that is a mixture of ideal gases (this is almost always a good ap-
proximation since the total vapor pressure of a condensed phase is usually very small). The
condition of chemical equilibrium requires that the chemical potential of every component
be the same in the solution and the vapor.
From equation 18.10 the chemical potential of the kth component in the vapor phase
is
k = k(T) + T ln(Pk) 18.16
where k(T) is a function of the temperature only and Pk is the partial pressure of the kth
component. The chemical potential in the solution is, from equation 18.11
0
k = k(T,P) + T ln(xk) 18.17
0
where k(T,P) is the chemical potential of the pure component in the condensed state at
(T,P), and is a weak function of P when P is small. Equating the chemical potentials yields
0 -
k k 0
Pk = xk exp T ~ xkPk(T) 18.18
0
where Pk(T) is the vapor pressure of the kth component in its pure form. It follows that
the vapor pressure of a component in an ideal solution depends only on its own atom frac-
tion. Conversely, the concentration of a component in an ideal solution in equilibrium with
a dilute vapor depends only on its partial pressure in the gas.
18.3 THERMODYNAMICS OF REAL SOLUTIONS
18.3.1 Excess thermodynamic quantities
There are two model systems that provide good reference states for the thermody-
namics of a real solution in the sense that their properties are well-defined and relatively
simple to measure experimentally. These are the mixture of pure components and the ideal
solution. If the solution were a simple mixture of the pure components at temperature, T,
and pressure, P, the molar density of the Gibbs free energy would be
Page 401
0
g(T,P,{x}) = xkk(T,P) 18.19
k
while if the solution were ideal its molar free energy would be
0
gi(T,P,{x}) = xkk(T,P) + T xk ln(xk) 18.20
k k
It is often useful to measure the thermodynamic content of the solution in terms of its de-
viation from one of these two reference values. The excess of the Gibbs free energy of a
multicomponent system over that of a simple mixture is called the excess free energy of
mixing,
g(T,P,{x}) = g - g
0 0
= xkk - k = xkk 18.21
k k
and is a measure of the tendency of a mixture of components to form a solution. The more
negative this quantity, the more reactive the mixture. The excess of the Gibbs free energy
of a solution over the value it would have if the solution were ideal is the excess free energy
of solution,
0
gi(T,P,{x}) = g - gi = xkk - T xk ln(xk)
k k
i
= xkk 18.22
k
i
where k is the non-ideal part of the chemical potential, defined by the relation
i 0
k = k - k + T ln(xk) 18.23
i
k measures the deviation of the kth component from ideal behavior.
It is sometimes informative to divide the excess free energy of solution into its en-
thalpic and entropic parts. Since the excess enthalpy of an ideal solution is zero, the excess
enthalpies of mixing and solution are the same, the heat of mixing,
g
h = h - h = - T2 T T
Page 402
0
k
= - T2 xk T T 18.24
k
The heat of solution is zero when the solution is ideal, that is, when the species in solution
do not interact preferentially with one another. The heat of solution is negative when the
species in the solution bond preferentially to one another. In this case they prefer one an-
other as neighbors; solid solutions with h < 0 tend to form ordered compounds at low
temperature. The heat of solution is positive when the species prefer neighbors of their
own kind. Solutions with h > 0 tend to decompose into pure components at low tem-
perature.
The excess entropy of solution is
i
gi k
si
= - T = - xk T 18.25
k
The excess entropy of solution is zero when the solution is ideal, and also vanishes when
the deviation from ideality is independent of the temperature. The latter condition is as-
sumed in many of the more useful models of solid solutions. When the excess entropy of
solution is not zero it is generally negative and is due to a preferential order or clustering
that reduces the degeneracy of the configuration.
18.3.2 The activity and the activity coefficient
The chemical potential of a real solution can always be written
0 i
k(T,P,{x}) = k(T,P) + k(T,P,{x}) + T ln(xk) 18.26
i
where k is a measure of the non-ideality of the kth component. To preserve the functional
form of the chemical potential of the ideal solution it is customary to define the activity, ak,
and the activity coefficient, k, by the relations
0
k = k(T,P) + T ln(ak)
0
= k(T,P) + T ln(kxk) 18.27
where the activity of the kth specie is
- 0
k k
ak(T,P,{x}) = exp T 18.28
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and the activity coefficient is
k
k(T,P,{x}) = (xk)-1exp T 18.29
The activity is a convenient measure of the contribution of the kth component to the
excess free energy of mixing, which can be written
g = T xk ln(ak) 18.30
k
In this notation the heat of mixing becomes
[ln(ak)]
h = - T2 xk T 18.31
k
which shows that h vanishes when the activity is independent of the temperature.
The activity coefficient is a convenient measure of the contribution of the kth com-
ponent to the excess free energy of solution, which can be written
gi = T xk ln(k) 18.32
k
Given the emphasis that is placed on the activity and activity coefficient in many
undergraduate texts that treat the thermodynamics of solutions, it is worth noting that these
quantities are not independent thermodynamic parameters in any sense. They are simply
ways of writing a part of the chemical potential in a form that is sometimes mathematically
convenient.
18.4 DILUTE SOLUTIONS

18.4.1 The chemical potential in a dilute solution
One of the most important results in the thermodynamics of solutions was the
demonstration, by Gibbs, that dilute solutions have a quasi-ideal behavior. This result es-
tablished two older "laws" in the chemistry of liquid solutions: Henry's Law, which states
that the vapor pressure of a solute above a dilute solution is proportional to its concentra-
tion, and Raoult's Law, which states that the vapor pressure of the solvent decreases in
proportion to the total concentration of solute. It also provided a very useful framework for
the analysis of phase equilibrium and phase diagrams in solid solutions, since most solid
phases accept only a small addition of solute before the solubility limit is exceeded.
Page 404
Consider a dilute binary solution, and let the molar density of the solute, n1, be
changed at constant values of T, P and n2. The Gibbs-Duhem equation requires that the
chemical potentials of the solute and solvent change in the relation
d1 d2
n1 dn + n2 dn = 0 18.33
1 1
where the total differential has been used since only the single variable, n1, is changed.
Equation 18.33 continues to hold in the limit n1 0. But since n2 is finite there, we must
have either
d2
=0 18.34
dn1
or
d1 A
= 18.35
dn1 n1
where A is a constant. Since equation 18.33 holds for arbitrary components and arbitrary
types of solutions, either 18.34 or 18.35 must hold in general.
However, equation 18.34 cannot hold in general. It is not true for solutions of ideal
gases, for which
d2
=- T 18.36
dn1 n2
in the limit of small values of n1. It is also untrue for common liquid and solid solutions.
We are, therefore, forced to choose equation 18.35. Equation 18.33 then shows that
d2
n2 dn = - A 18.37
1
where A is independent of n1 and n2. In the limit n2 0 the system behaves as an ideal
gas. Hence
A=T 18.38
We can now evaluate the chemical potential of the dilute solute from equation 18.35.
Setting A = T and dividing the denominator of both sides of the equation by n2 ~ n2 + n1 =
n, we have
d1 T
dx = x 18.39
Page 405
where x is the mole fraction of component 1. Equation 18.39 has the integral
d
1(T,P,x) = 1(T,P) + T ln(x) 18.40
Equation 18.40 is formally identical to the expression for the chemical potential for
d
the ideal solution with the difference that 1(T,P) is simply a constant of integration. There
d 0
is no a priori reason to believe that 1 has any simple relation to the chemical potential, 1 ,
of the pure component. Rewriting equation 18.40 in terms of the activity coefficient of the
solute gives the result
0
1 = 1 + T ln[1x1] 18.41
where 1 is a constant. Equation 18.41 confirms one form of Henry's Law: a dilute solute
has a constant activity coefficient.
The chemical potential of the solvent also has a simple behavior. Given equation
18.38, equation 18.37 can be written
d2
dx = - T 18.42
which has the integral
0
2 = 2(T,P) - Tx
0
~ 2(T,P) + T ln(1-x) 18.43
where the constant of integration is fixed by the fact that 2 reduces to its value in the pure
component when x 0. Equation 18.43 confirms one form of Raoult's Law: the solvent
of a dilute solution behaves as if the solution were ideal.
Equations 18.40 and 18.43 are readily generalized to solutions of an arbitrary num-
ber of components, provided that all except one, the solvent, are present in very dilute con-
centration. A dilute solution behaves as if it were ideal with the exception that the constant
d 0
potential of a dilute solute is k rather than k . We call these solutions quasi-ideal.
Two important features of the behavior of real solutions can be inferred from the
behavior of the relative chemical potential of the solute in the dilute limit. From equations
18.40 and 18.43, when x is small
d x
1(P,T,x) = 1(P,T) + T ln1-x 18.44
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where
d d 0
1 = 1 (P,T) - 1(P,T) 18.45
In the limit x 0 the relative chemical potential increases without bound. It follows that:
1. any chemical specie is at least slightly soluble in any other;
2. the function g(x) at constant (T,P) has infinite negative slope in the limits
x = 0 and x = 1.
More generally, since most real solid solutions are dilute, the theory of dilute solu-
tions is often sufficient to treat the equilibrium behavior of multicomponent solids. The
d
application of the theory involves only one unknown, the function 1 (P,T) , which can be
obtained experimentally. Where the dilute theory is inadequate it can be developed into a
series in powers of x, as we shall show below.
18.4.2 The fundamental equation of a dilute solution
The fundamental equation of a dilute solution is formally identical to that of an ideal

0
solution with the difference that the chemical potential k(T,P) is replaced by the asymp-
d
totic value, k(T,P) , for each of the solute species. It is, however, useful to write the fun-
damental equation in a form that makes its functional dependence on the concentration vari-
ables more explicit.
For a multicomponent fluid, equation 18.40 gives the chemical potential of the kth
dilute solute
d
k(T,P,{x}) = k(T,P) + T ln(xk) 18.46
while equation 18.43 can be generalized to give the chemical potential of the solvent in the
form
0
n(T,P,{x}) = n(T,P) - T xk 18.47
k
Hence the molar density of the Gibbs free energy is
n
g= xkk
k=1
Page 407
0 d
= xnn(T,P) - xnT xk + xkk(T,P) + Txkln(xk)
k k
0

d xk
~ n(T,P) + xkk(T,P) + Txkln e 18.48
k
where the unlabeled sum is taken over the (n-1) solute species and we have neglected terms
of order (xk)2. Equation 18.48 has the form
g = n +
kxk 18.49
k
where the relative chemical potential,
g d
k(T,P,{x}) = x = k(T,P) + Tln(xk) 18.50
k
is accurate to within terms of order xk.
18.4.3 Generalization to "semi-dilute" solutions
To generalize the fundamental equation to slightly higher concentrations note that

the function,
xk
g'(T,P,{x}) = g(T,P,{x}) - Txkln e 18.51
k
is well-behaved in the limit xk 0 and has well-behaved first derivatives there (unlike g,
whose partial derivatives with respect to the xk are singular when xk 0). Assuming that
its higher derivatives are well-behaved as well we can obtain the free energy at finite {x} by
expanding g'({x}) about {x} = {0}. To second order,
g 1 2g
g'({x}) ~ g'({0}) + x xi + 2 x x xixj
i {0} i j {0}
i ij
0 d 1
= n +
i xi + 2 ijxixj 18.52
i ij
where the second-order coefficient
2g
ij = x x 18.53
i j {0}
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Hence, to second order in the concentration,
0 d 1 xi
i xi + 2 ijxixj + Txiln e
g({x}) ~ n + 18.54
i ij i
where the coefficients are functions of T and P. The relative chemical potentials of the sol-
utes in the semi-dilute solution are
d
i ~ i + ijxj + Tln(xi) 18.55
j
The expansion can, of course, be continued to higher orders of {x}. However, the
second order expansion is sufficient to treat most of the solid solutions of interest in mate-
rials science, since most solid phases have a limited range of solubility. Note that the same
expansion applies to non-stochiometric compounds if the solvent is taken to be the sto-
chiometric compound and the solutes are the species that are present in excess. Equation
18.54 can be evaluated experimentally by measuring the values of the constant parameters
as functions of temperature (their pressure dependence is rarely of interest). Several ther-
modynamic data bases have been compiled that contain the coefficients (or others that are
equivalent to them) and can be used to compute the thermodynamic properties of solid
solutions.
18.5 DILUTE SOLUTIONS: APPLICATIONS
We include a series of examples here to illustrate the applications of the theory of

dilute solutions. All except the last assume that the first-order expansion is sufficient.
18.5.1 Equilibrium of two solutions with the same solvent
Let two phases ( and ) be dilute solutions with the same solvent, and let them be
in equilibrium with one another. Let x and x be the solute concentrations in the two so-
solutions. The solutes need not be the same so long as they are dilute; in fact, either
"solute" may be a mixture of several solutes whose total content is small. The two phases
have the same temperature, but do not necessarily have the same pressure since they may be
separated by a membrane that restricts their mechanical interaction. The condition of
chemical equilibrium of the solvent specie is

n (T,P,x) = n(T,P,x) 18.56
Since the mole fraction of solute is small,
0
n (T,P,x) = n (T,P) - Tx 18.57
Page 409

and n obeys a similar equation.
Equations 18.56 and 18.57 are sufficient to solve three important problems: the
change in the temperature or pressure of two-phase equilibrium between and when a
solute is added, the influence of a solute on the vapor pressure of a dilute solution, and the
osmotic pressure across a semi-permeable membrane that is restrictive to the solute. We
solve these in turn.
18.5.2 Influence of a dilute solute on two-phase equilibrium
Let two phases of a pure material be in equilibrium at (T0, P0). Then
0 0
n (P0,T0) = n (P0,T0) 18.58
If a dilute solute is added to the two phases then the equilibrium temperature and pressure
change slightly to satisfy equation 18.56. Since the changes, T and P are small when x
is small, the chemical potential of at T0 + T, P0 + P can be found in terms of its value
at T0, P0:
0 0
0 0 n n
n (P0+P,T0+T) = n (P0,T0) + T T + P P
0
= n (P0,T0) - sT + vP 18.59
where s and v are the molar entropy and volume of the solvent in the phase. Writing
the same equation for the phase and equating the two chemical potentials to preserve
equilibrium yields the equation
(x - x)T0 ~ (v - v)P - (s - s)T
Q
~ (v - v)P - T T 18.60
0
where Q is the latent heat of the transformation , and we have neglected terms of
order xT and (T)2. Equation 18.60 determines the change in the temperature and pres-
sure of the transformation in terms of the properties of the pure phases and the solute con-
centrations.
First consider the effect on the transformation temperature at constant pres-

sure. Since P = 0,
T02
T = - Q (x - x) 18.61

Page 410
The sign of the temperature change is fixed by the product of the signs of the latent heat and
the composition difference. If is the high-temperature phase then the latent heat is posi-
tive; heat is released. The transformation temperature then decreases if is relatively rich
in solute, as it usually is since the high-temperature phase has higher entropy and can nor-
mally accept a greater concentration of the solute. If is relatively poor in solute the trans-
formation temperature rises.
A familiar example of this effect is the influence of dissolved salt on the boiling and
freezing points of water. Assuming that the solute is relatively insoluble in ice, as most
salts are, then x, the concentration in the low-temperature phase, is negligible. The freez-
ing point is depressed by an amount that is proportional to the concentration of the salt in
water:
xT02
T = - Q 18.62
where Q is the (positive) latent heat of freezing. One therefore spreads salt on highways in
wintertime to melt the ice. Now consider boiling a solution of salt in water. If the solute is
relatively non-volatile, as salt is, then equation 18.62 still holds, but is now the low-tem-
perature phase. The latent heat is negative and the boiling point is raised. One therefore
cooks with salty water to raise the boiling point and speed the process.
If the temperature is fixed then the transformation pressure is altered by the amount
T0(x - x)
P = 18.63
v - v
If is the high pressure phase then it has the lower molar volume and normally has a lower
solubility limit. Hence the transformation pressure is usually raised by adding a solute. An
exception is the freezing of water at temperatures near T0. Water has a lower molar volume
than ice, but a higher affinity for salt. Hence P is negative, and ice melts at lower pressure
when salt is added.
18.5.3 The vapor pressure of a dilute solution: Raoult's Law
The change in the vapor pressure of a condensed phase when a dilute solute is
added can be computed from equation 18.63. The pressure, P0, at which a condensed
phase is in equilibrium with its vapor at temperature T is the vapor pressure at that tempera-
ture. When a solute is added the total pressure of the vapor changes to P0 + P, where P
is given by equation 18.63. Neglecting the molar volume of the condensed phase () with
respect to that of the vapor (),
T(x - x)
P = = P(x - x) 18.64
v
Page 411
where we have assumed that the vapor is sufficiently dilute to behave as an ideal gas. Since

P = (Pn + Ps ) - P0 = Pn + xP 18.65

where Pn is the change in the vapor pressure of the solvent and Ps = xP is the vapor
pressure of the solute, then, to within a term of order xP,

Pn

P0 = - x 18.66
Equation 18.66 is Raoult's Law: the relative decrease in the vapor pressure of a
condensed phase on adding a dilute solute is equal to the molar concentration of the solute.
18.5.4 Osmotic pressure
Let two dilute solutions with the same solvent be separated by a membrane that is
permeable to the solvent but impermeable to the solute. The pressure differs on the two
sides of the membrane. The condition for chemical equilibrium of the solvent requires that
its chemical potential be the same on both sides. Since the solvent is in the same phase on
both sides,
0 0
n(P,T) - xT = n(P,T) - xT 18.67
where and now refer to the two different sides of the membrane. To within a term of
the order T(P - P)2,
0 0
n(P,T) = n(P,T) + v(P - P) 18.68
where v is the molar volume of the solvent at P, T. It follows that the pressure difference
across the membrane is
T
P = (P - P) = v (x - x) 18.69
When the solute is present only on one side,
Tx
P = v 18.70
where x is the solute concentration and the pressure is greater on the solute side. Equation
18.70 is known as van't Hoff's Law.
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When the solvent is a condensed phase, v is small and equations 18.69-70 hold for
large P since the compressibility is small. It follows from equation 18.70 that a dilute
solute concentration can generate a substantial pressure. The most familiar example occurs
in the supply of water to plants. By absorbing water through an organic membrane that is
impermeable to the salts that are added to the water on the inside, a plant can create a pres-
sure differential that helps to raise the water to branches and leaves far above the ground.
18.5.5 Dilute solutions with the same solute: Henry's Law
Let two dilute solutions with the same solute be in equilibrium with one another.
The condition of chemical equilibrium for the solute is

1 (T,P,x) = 1(T,P,x) 18.71
where and are the two phases, the subscript 1 designates the solute, and x is the con-
centration of solute. Since both solutions are dilute
d d
1 (T,P) + T ln[x] = 1 (T,P) + T ln[x] 18.72
Hence the ratio of the solute concentrations in the two solutions is
d - d
x 1 1
= exp =
18.73
x T
where is the value of the activity coefficient of the solute in the dilute solution limit.
A common example of the equilibrium of two solutions with the same solute is the
equilibrium of a dilute solution in a condensed phase with its vapor. If phase () is the

vapor and P1 is the vapor pressure of the solute, then, approximating the vapor as an ideal
gas, equation 18.72 can be written
d
1 (T,P) + T ln[x] = T lnP1 + (T) 18.74
where (T) is a function of the temperature only. Equation 18.74 has the solution

P1 = K(P,T)x 18.75
where K(P,T) is independent of the composition. Equation 18.74 is Henry's Law:
the partial pressure of a solute above a dilute solution is linearly proportional

to the concentration of the solute.
Page 413
A second example, which is more important in materials science, is the equilibrium

of liquid and solid or two solid phases in a binary system near x = 0. Let T0 be the tem-
perature at which phases and are in equilibrium in the pure solvent at reference pres-
sure, P. Equation 18.73 then determines the equilibrium concentrations in the two phases
as a function of x when a dilute solute is added. This equation hence determines the shape
of the two-phase region in the T-x diagram of the binary solution near the x = 0 axis. The
ratio x/x is called the separation coefficient, and is often approximated as the constant,
k.
18.5.6 Solute-solvent equilibria between dilute solutions
Let two phases, and , be in equilibrium. Let component (1) be a dilute solute in
phase and the solvent in phase . Hence the activity coefficient of species (1) is a con-

stant, 1 , in phase and is unity in phase . The condition of equilibrium is

T ln1 x = T ln[x] 18.76
which shows that the ratio of the concentrations in the two phases is
x -1
= 1 18.77
x
In order for equation 18.77 to be consistent with the problem as it was set we must
have

1 >> 1 18.78
so that x << x. If this is not the case the dilute solution of component 1 cannot be in
equilibrium with a phase in which it is the solvent. From the definition of the activity
coefficient, equation 18.29, as it applies to the dilute solution,
d - 0
1 1
1 = exp T 18.79
Equation 18.78 is always satisfied at sufficiently low temperature if
d 0
1 > 1 18.80
Hence the equilibrium is always possible if the chemical potential of component 1 in phase
in the limit of zero concentration is greater than its chemical potential in the pure state.
Since the few atoms of species 1 that are present in phase in the limit of zero concentra-
tion are surrounded by atoms of the solute, equation 18.80 is the formal expression of the
Page 414
familiar statement that if species 1 bonds to itself in preference to the solvent the solution
will decompose at low temperature.
Note that, given equation 18.80, the activity coefficient of species 1 in the dilute
solution increases without bound as the temperature approaches zero. It follows that
the concentration of a component in a dilute solution that is in equilibrium

with a phase in which it is the solvent vanishes as the temperature ap-
proaches zero.
It follows that the dilute solution behaves according to the Third Law in the sense its equi-
librium concentration approaches zero with the temperature.
As a simple extrapolation, consider the behavior of a binary system that decom-

poses into two dilute solutions at low temperature. Each component is then present in a
solution in which it is dilute in equilibrium with a second in which it is the solvent. Both
obey equations of the form 18.77. It follows that the equilibrium state of the binary system
approaches a mixture of two pure phases as T 0. Moreover, since the chemical poten-
tials become independent of temperature in the limit of zero temperature, the solute concen-
tration in each phase approaches zero exponentially, according to the relation
K
x = exp- T 18.81
where x is the solute concentration in the th phase and K is a positive constant.
18.5.7 The interference of solutes in a dilute ternary solution
The governing equations of the "semi-dilute" solution, equations 18.54 and 18.55,
are useful to treat the mutual interaction of multiple solutes in a dilute solution. One simple
example is the influence of a ternary addition on the solubility of one specie in another.
The solubility limit of a binary solution is defined in practice as the maximum

amount of the solute specie that can be added, and is, hence, determined by the two-phase
equilibrium line in the binary phase diagram. The two-phase equilibrium depends on the
properties of both phases, which are ordinarily solutions themselves. When a ternary
species is added in dilute concentration its effect on the solubility limit depends on its influ-
ence on both of the phases in two-phase equilibrium.
To simplify the problem somewhat, let a binary system contain two phases, and
, that are in equilibrium, where is a dilute solution of component (1) in component (n).
Now let a small quantity of a second component, (2), be introduced into (), but not into
(). This condition is satisfied to a good approximation when the activity coefficient of (2)
in is much larger than it is in . It is exact when (2) is introduced into and and are
separated by a membrane that is impermeable to (2); a situation that is encountered in prac-
tice when the diffusivity of (2) in is much larger than its diffusivity in . If is large
Page 415
enough to act as a reservoir the relative chemical potential of (1) in is unchanged by the
addition of component (2). Hence

1 (x1 ) = 1 (x1 + x1 , x2 ) 18.82

where x1 is the change in the solubility of (1) due to the addition of (2). The right-hand

side of equation 18.82 can be evaluated by expanding about x2 = 0. To first order in the
concentration variation

1 1
0 = x x1 + x x2
1 0 2 0
T
= + 11 x1 + 12x2 18.83
x1

where the ij are the expansion coefficients that appear in equation 18.55. Since x1 is
small we neglect 11 with respect to the first term in the bracket. The fractional change in
the solubility of (1) is, hence,

x1 12
= - x 18.84
T 2
x1
Since 12 = 21, to the accuracy of equation 18.55 the influence of component (1)
on the solubility of (2) is the same as the influence of (2) on the solubility of (1). It follows

that if components (1) and (2) have limited solubilities, x1 and x2 , in phase , the maxi-
mum solubilities in a dilute ternary solution that includes both (1) and (2) differ from these
by the amounts
12
x1 ~ - T x2 x1 ~ x2 18.85
Since the coefficient, 12, can have either sign the addition of a second element may either
increase or decrease the solubility.
18.6 BEHAVIOR NEAR A CRITICAL POINT
The preceding sections have described the evaluation of the fundamental equation of
a solution by expanding it in powers of the concentration, x, of the solute added to a pure
component. The pure component may be a monatomic material, a stoichiometric com-
pound; in either case the addition of a second atomic species or compound creates a dilute
solution whose fundamental equation can be estimated. In the present section we consider
a second case in which the fundamental equation can be evaluated by expansion, when the
Page 416
state of the solution is very close to the critical state at the top of a miscibility gap. The
method of expansion in this case is very nearly the same as that used near the critical point
of a one-component fluid in Chapter 17.
A critical point in the concentration of a binary solution occurs where two distinct
solutions that are in equilibrium with one another become indistinguishable. The critical
point lies at the top of a miscibility gap in the T-x phase diagram, and is located at the tem-
perature, Tc, and composition, xc. Above Tc a system with the critical concentration, xc, is
a homogeneous solid solution. Below Tc the homogeneous solution decomposes into two
solutions with different compositions. In order for a miscibility gap to appear in the phase
diagram of a binary solution the two phases must differ only in composition; they must,
therefore, have the same symmetry. Miscibility gaps can divide liquid solutions or solid
solutions that are based on the same crystal structure, but evidently cannot separate a liquid
solution into a solid and a liquid, or a solid solution into two solutions with different crystal
structures.
It follows from the phase rule that a critical state in a binary solution has one degree
of freedom. The critical state is a point in a T-x diagram, but a line in the three-dimensional
T-x-P diagram. The general thermodynamic criteria for a critical state in a binary solution
follow from the general theory given in Chapter 16, and can be written

x TP = 0 18.86
2

x2 TP = 0 18.87
3

x3 TP > 0 18.88
Since a stable solution must satisfy the condition
2g
=
x2 x TP 0 18.89
the critical point is a stability limit for the homogeneous solution.
The fundamental equation for the critical point can be developed just as in the case
of the critical point in the one-component fluid. Let
x = x - xc 18.90
T = T - Tc 18.91
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Then the compositional derivative of the relative chemical potential can be written, to lowest
order,

2
x TP = 1(T) + 2(x) 18.92
where 1 and 2 are constant coefficients. It follows from equations 18.88-89 that both 1
and 2 are positive. Integrating equation 18.92 gives the relative chemical potential near the
critical point
1
(T,x) = (Tc,xc) + 1(Tx) + 3 2(x)3 18.93
The stability of the solution near the critical point can be found from equation 18.92.
Since the equation is quadratic in x, there are two solutions to the homogeneous equation

x TP = 0 18.94
When T > 0 both solutions are imaginary; the binary solution is stable for all concentra-
tions near xc. When T < 0 instabilities occur at
- 1T
xi = 2 18.95
which shows that the system must separate into two distinct phases. The compositions of
the two phases that are in equilibrium at T < 0 (call them ' and ") are fixed by the con-
dition
(x') = (x") 18.96
which has the solution
- 31T
x' = - x" = 2 18.97
It follows that the miscibility gap has a parabolic shape near the critical point, and
that a parabolic instability or spinodal curve lies within the miscibility gap and converges at
the critical point. If a solution is varied in composition at a fixed temperature, T < 0, it is
stable in phase ' until the composition reaches the value x' given by equation 18.97.
The solution then enters a region of two-phase equilibrium in which ' and " coexist. If
the nucleation of " is prevented then ' is preserved until the composition reaches the in-
stability at x = - xi. At this point the solution is unstable with respect to transformation
into a mixture of ' and ".
Page 418
The fundamental equation of the binary solution near the critical point can be found
by integrating equation 18.93 with respect to x at constant T. The result is
1
2
g(T,x) = n(T,xc) + (Tc,xc)x + 2 Tx2 + x4 18.98
12
where n is the chemical potential of the solvent. This function has a positive curvature
when T > Tc. When T < Tc the function has positive curvature to the left of - xi and to the
right of xi, but has negative curvature between the two spinodal limits.
18.7 THE SIMPLE SOLUTION
It is useful to have a model of a binary solution that yields a simple fundamental

equation at all compositions, but can generate binary phase diagrams that have the geomet-
ric features most commonly observed in real systems. Such a solution must, of course,
have the same symmetry at all compositions, otherwise its fundamental equation could not
be continuous for all x.
The simplest possible model solution is the ideal solution. However, the ideal so-
lution does not represent the behavior of typical real solutions in several respects. It has
zero heat of mixing, does not exhibit a miscibility gap, and has non-vanishing entropy in
the limit T 0. We therefore seek the simplest model of a real solution by perturbing the
ideal solution. We require that, like the ideal solution, the Gibbs free energy of a binary
solution reduce to the free energies of the pure components when x is zero or one, and yield
chemical potentials that have the correct form when either component is dilute. We also
require that the enthalpy of mixing be non-zero.
18.7.1 The thermodynamics of the simple solution
The simplest realistic model of the binary solution that has these properties has a
fundamental equation of the form
0 0
g(T,P,x) = x1 + (1-x)2 + h0[x(1-x)] + Tx ln(x) + T(1-x) ln(1-x) 18.99
where x is the mole fraction of component 1,
0 i 1
k = k + 2 vkk 18.100
is the chemical potential of the pure component, k, in the mean field approximation, and
1
h0 = v12 - 2 (v11 + v22) 18.101
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is a constant if the mean interaction potentials, vij , are. We shall call a binary solution that
obeys equation 18.99 a simple solution. It is a special case of the regular solution defined
by Fowler and Guggenheim (Statistical Thermodynamics).
The relative chemical potential of the simple solution is
0 0 x
= 1 - 2 + h0(1-2x) + T ln1-x 18.102
.
The chemical potential of the solvent can be found from the relation
0
2 = g - x = 2 + h0x2 + T ln(1-x) 18.103
while the chemical potential of the solute is
0
1 = + 2 = 1 + h0(1-x)2 + T ln(x) 18.104
The chemical potentials have the correct behavior in the dilute solution limit. When x is
small,
0 d
1 = (1 + h0 ) + T ln(x) = 1 + T ln(x)
0 0
2 = 2 + T ln(1-x) = 2 - Tx 18.105
The chemical potentials in the limit x 1 are obtained from these by interchanging the in-
dices 1 and 2. Since the first correction term is quadratic in x (or (1-x)) the simple solution
remains dilute in the thermodynamic sense for a reasonable range of concentrations near x
= 0 or 1.
The heat of mixing is equal to the change in the enthalpy on making the solution
g0
h0 = - T2T T = x(1-x)h0 18.106
Px
which vanishes only if h0 does, that is, if the solution is ideal. The enthalpy of mixing has
the sign of h0. We discussed previously that a negative heat of mixing suggests that the
species in solution prefer to bond to one another and hence promotes the formation of solu-
tions at high temperature and ordered compounds at low temperature. This qualitative
result is consistent with equation 18.101, which shows that h0 is negative when the mean
potential of the interaction between the different atoms is less than the average of the inter-
action between atoms of the same kind. When h0 is positive the species have an energetic
preference to separate, and we should expect the phase diagram of the solution to exhibit a
miscibility gap at low temperature.
Page 420
18.7.2 Decomposition and ordering in the simple solution
To determine the existence of a miscibility gap in the simple solution we compute

the second compositional derivative of the free energy, which is
T
gxx = x(1-x) - 2h0 18.107
The second derivative vanishes (that is, the solution reaches a stability limit) when
T
2h0 = x(1-x) 18.108
When h0 < 0 equation 18.108 has no solutions for positive values of x; the solution is sta-
ble for all x and T. When h0 > 0, however, equation 18.106 has the two solutions x = x0
and x = (1-x0), where
T
x0(1-x0) = 18.109
2h0
These solutions define a spinodal gap that is symmetric about x = 0.5. However, the value
of the left-hand side of 18.109 has a maximum at x0 = 0.5, at which point the two branches
of the instability curve converge. When T > h0/2 the solutions to 18.109 are imaginary. It
follows that the top of the miscibility gap falls at the critical point located at
h0
Tc = 2
xc = 0.5 18.110
As T 0 the instability points approach x0 = 0 and 1. Since the equilibrium concentra-

tions of the two phases lie outside the spinodal lines it follows that the solution decomposes
into its two components as T 0, in agreement with the Third Law.
The simple solution model has two serious limitations in its ability to represent the
behavior of real solutions. First, it predicts a symmetric phase diagram with a miscibility
gap (if one exists) that is centered at x = 0.5, and predicts that the two species have the
same limiting potential in the dilute limit. This problem can be overcome in the model by
developing h0 as a power series in (x):
h0 = h0 + h1x + h2x2 + ... 18.111
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The second limitation concerns the low-temperature behavior of the solution when
h0 < 0. In this case there is no miscibility gap; the solution is retained to arbitrarily low
temperatures. But the entropy
g 0 0
s = - T = xs1 + (1-x)s2 - x ln(x) - (1-x) ln(1-x) 18.112
contains configurational terms that do not vanish in the T 0 limit for finite x. Hence the
simple solution does not obey the Third Law when h0 < 0. However, equation 18.101
shows that a negative value of h0 occurs in solutions whose species prefer to bond to one
another. It follows that a solution with h0 < 0 forms ordered compounds at low tempera-
ture. The free energy curves for the ordered phases fall below the free energy of the solu-
tion at low temperature, and the phase diagram near T = 0 contains only the pure compo-
nents and ordered compounds as stable states. It is straightforward to construct solution
models that predict ordering at low temperature, but it is simpler to write these for crystal
lattices, so we shall defer a discussion of them until we treat the solid state.
18.8 THE PHASE DIAGRAM OF A BINARY SOLUTION
The phase equilibria within a solution are given by the phase diagram, which is just
a map of the phase fields as a function of the values of the constitutive coordinates. While
most solutions of interest in materials science are, in fact, multicomponent solutions, we
shall restrict the discussion here to the phase diagrams of binary solutions, which are rela-
tively easy to visualize and interpret in terms of the simple solution model.
The value of the phase diagram is two-fold. First, it maps the equilibrium behavior
of the solution. Second, while it is extremely difficult to compute the fundamental equation
of a solution, the fundamental equation can always be found by expansion about a point
where its value is known. The fundamental equation is most easily found at special points
in the phase diagram where the fundamental equation must have a simple form or where the
fundamental equations of several phases must have equal value. We have already used this
principle to discuss the fundamental equation of a dilute solution and a solution near a criti-
cal point, and to study phase equilibrium near T = 0 and near a phase transformation point
of the pure solvent. In the following we first identify the special points, and then discuss
the form of the various possible phase diagrams of binary solutions.
18.8.1 Special points in the T-x diagram
A simple first- or second-order expansion is valid for at least some finite range of
values of the coordinates near the known point. The positions in the T-x phase diagram of
a binary solution where the thermodynamic potential is known, or can be found with rela-
tive ease, include the pure component lines at the boundary of the diagram, and particularly
the phase transformation points on the pure-component lines, the T = 0 line, where only
pure components and ordered compounds can be at equilibrium, and the isolated points that
represent critical phases, congruent phases and three-phase equilibria. As we have seen,
Page 422
the fundamental equation also has a relatively simple behavior near a limit of stability of the
solution which terminates a metastable region, but we shall defer a further discussion of
these limits until we treat the thermodynamics of order reactions.
The pure component lines lie at the boundaries, x = 0 and x = 1. The thermody-
namics of the solution near a pure-component line can be found from the dilute solution
model. If the thermodynamics of the pure component are known the fundamental equation
of the dilute solution contains only one unknown term: the activity coefficient of the solute.
Even at slightly higher concentrations the fundamental equation can be developed in a
power series so that only a few terms are required. The phase transformation points on the
pure-component lines are points from which two-phase regions emanate that represent di-
lute solutions in the two phases. The shape of the two-phase region near the transformation
point on the one-component line can be found from dilute solution theory as discussed in
Section 18.6.5.
The zero temperature line lies at the base of the phase diagram. According to the
Third Law the stable phases that fall on this line must be pure components or ordered com-
pounds. As we found in Section 18.6.6, both the pure-component phases and the ordered
compounds become dilute solutions at finite temperature with solute concentrations that in-
crease according to the Arrhenius equation that governs the activity. They are hence dilute
solutions over the whole equilibrium range for at least some range of finite temperatures.
Since many of the solutions that are important in materials science are effectively at low
temperature over the range of practical interest, they can be treated as dilute solutions over
the whole range of interest.
The critical points in the T-x diagram are the peaks of miscibility gaps, and are as-
sociated with the reaction
' + " 18.113
where ' and " differ from (and from one another) only through their compositions.
The fundamental equation of the solution near the critical point can be found by mathemati-
cal expansion as sown in Section 18.8.
The three-phase equilibrium points in the T-x diagram are isolated points in the T-
diagram of the solution where three two-phase equilibrium lines meet. In the T-x diagram
each of these equilibrium lines splits into a two-phase region with a finite extent. Since the
temperature of the three-phase equilibrium is fixed, the three two-phase equilibrium regions
meet at an isothermal line along which three phases are in equilibrium. There are three
three-phase reaction points on the three-phase line in the T-x diagram. Two of these are the
points at which the isothermal three-phase line terminates at a single-phase region, and are
the points where the reaction
++ 18.114
Page 423
occurs when the composition is varied at constant temperature. The third point lies at an
interior point of the three-phase line, and determines the reaction
+ 18.115
when the temperature is changed at constant composition.
Primarily for historical reasons four different terms are used to describe the three-
phase equilibrium lines in the T-x diagram. If in equation 18.115 is the high-temperature
phase, that is, if the arrow is in the direction of decreasing temperature, the special point is
called a eutectic point if is a liquid, and is called a eutectoid point if is a solid. If is
the low-temperature phase then the special point is called a peritectic point if either or is
a liquid, and is called a peritectoid point if both and are solid. Since the phase diagram
is morphologically identical at a eutectic and a eutectoid, and can be made identical at a
peritectic or peritectoid by simply reversing the sign of the temperature, the terminology can
be simplified substantially by referring to them as a eutectic and inverse eutectic, respec-
tively.
The three-phase equilibrium determines the compositions of the three phases. In the
T-x diagram, the compositions of the terminal solid solutions that lie at the ends of the
three-phase line are given by their intersection points, while the composition of the third
phase is given by its intersection with the three-phase line at the eutectic point. Since the
three two-phase regions are lines in the T- plot that split into bands in the T-x plot, all
three one-phase regions are cusped at their intersections with the three-phase line.
It is, of course, also possible to find a four-phase equilibrium in a T-x or T- dia-

gram. However, it is monumentally unlikely unless the pressure is very carefully selected,
since four-phase equilibria are isolated points in the three-dimensional P-T- diagram.
Since the chemical potentials of the two components are the same in all three phases
at a eutectic, it is possible to evaluate the fundamental equations and interpret the two-phase
equilibria near the eutectic by mathematical expansion about the three-phase equilibrium
point.
A congruent point in the T-x diagram of a binary system is a point where two solu-
tions transform into one another without changing composition. The reaction is
18.116
which occurs at constant composition. Hence the single-phase regions of and touch at
the congruent point. The phase transformations of the pure components are always con-
gruent. In order for and to have a congruent point at intermediate x there must be a
temperature at which the fundamental curves of the two phases touch without crossing (a
point at which two fundamental curves cross is always within a two-phase region by the
common tangent rule. To touch without crossing the two curves must be equal and tangent
Page 424
at the congruent point, but must have different curvature there. This leads to three mathe-
matical conditions:
g(T,P,x) = g(T,P,x) 18.117
g
(T,P,x) = x = (T,P,x) 18.118
2g

x = x2 > x 18.119
that ensure that the reaction occurs congruently on cooling at the composition, x. If
is the high-temperature phase the congruent point falls at a local minimum in the tempera-
ture at which it is stable. If is the low-temperature phase the congruent point falls at a lo-
cal maximum in the temperature of its one-phase field.
A mutation, such as the Curie point in iron, is a line in the T-x diagram. Mutations
of solutions are always congruent.
18.8.2 Binary phase diagrams
Many binary systems contain several solid phases, and hence have phase diagrams
with rather complicated forms. However, most of these diagrams can be simplified and
understood by breaking them into parts that involve the equilibrium of only a few phases.
In this section we consider possible binary phase diagrams for systems that contain one,
two or three solid phases, and also describe one common example of a phase diagram with
two liquid phases. Almost all binary phase diagrams can be divided into segments whose
behavior is like that of one of the diagrams listed below.
18.8.3 Solid solution diagrams
A x B
Fig. 18.1: The simplest phase diagram for the solid solution.
The systems that form solid solutions at all compositions (at least at intermediate
temperature) have one of three phase diagrams: the simple solution diagram discussed in
Page 425
Section 18.5, or a slight modification of it that has a congruent point either at the top or the
bottom of the two-phase (+L) region. Of course, solid solutions are only possible when
the two components have the same crystal structure in the solid state.
The simplest phase diagram for the solid solution is re-drawn in Fig. 18.1. This
diagram appears when the free energy curve of the solid solution first cuts the liquid free
energy curve at the higher of the two melting points of the pure components, and cuts it last
at the lower melting point, so there is no congruent point. Many binary systems have this
simple phase diagram, including Ag-Au, Ag-Pd, Au-Pd, Bi-Sb, Nb-Ti, Nb-W, Cd-Mg,
Cr-W, Cu-Ni, Cu-Pt, Cu-Pd, Hf-Zr, Mo-Ta, Mo-Ti, Mo-V, Mo-W, Ge-Si, Pd-Rh, Ta-Ti,
Ta-V, Ta-Zr, U-Zr, and V-W.
TB
T
TA
A B
x
...
Fig. 18.2: Solid solution with a high-temperature congruent point.
However, almost as many binary solutions have congruent points in their phase di-
agrams, which shows that the free energy curves of the liquid and the solid solution touch
before they cross at x = 0 or x = 1. If the first contact that happens between the liquid and
solid free energy curves on cooling falls at an intermediate composition then the system has
a elevated congruent point, as in Fig. 18.2. If the last contact on cooling falls at an inter-
mediate composition the system has a depressed congruent point, as in Fig. 18.3.
TB
L
TA
T
A B
x
Fig. 18.3: Solid solution with a low-temperature congruent point.
Page 426
There are very few binary systems with elevated congruent points; the Pb-rich so-
lution in the Pb-Tl system is one of the few examples. On the other hand, depressed con-
gruent points are common. Au-Cu, Au-Ni, Nb-Mo, Nb-Ni, Nb-V, Co-Pd, Cs-K, Fe-Ni,
Fe-Pd, Hf-Ta, Mn-Ni, Mn-Fe, Pu-U, Ti-V and Ti-Zr, show this behavior, among others.
Perhaps the strangest example is the behavior of the Ti-Zr system. The high temperature
solid structures of both components are BCC, and both transform to HCP on cooling. The
phase diagram contains two solid solutions, (BCC) at high temperature and (HCP) at
lower temperature. Both the liquid- equilibrium and the - equilibrium are separated by
two-phase regions with depressed congruent points like that shown in Fig. 18.3.
There is a simple thermodynamic reason for the preference for a low-temperature

congruent point. The high-temperature phase is the more disordered one, and generally has
a higher entropy of mixing. As a consequence its free energy curve tends to have a deeper
trough at intermediate composition, so that the liquid and solid free energy curves contact at
intermediate composition at a temperature below the melting points of the pure components.
18.8.4 Low-temperature behavior of a solid solution
One of the fundamental laws of thermodynamics is the Third Law, which asserts
that the entropy of an equilibrium phase vanishes in the limit T 0. The Third Law has
the consequence that the equilibrium state cannot be a solid solution in the limit of zero
temperature. If a solid solution is cooled sufficiently its equilibrium state must be a per-
fectly ordered phase or a simple mixture of perfectly ordered phases. This criterion can be
satisfied in two simple ways: the solid solution can decompose into two terminal solutions
at low temperature or the system can rearrange itself into an ordered compound or mixture
of ordered compounds.
In many real systems this low-temperature behavior intrudes at temperatures so low

that it is never observed; such systems are solid solutions for all practical purposes.
However, in other cases complete solubility is lost at moderate temperature through the
formation of either a miscibility gap or an ordered phase. We consider the two possibilities
in turn.
Phase diagrams containing a miscibility gap
A possible binary phase diagram that contains a miscibility gap is shown in Fig.
18.4. The system freezes into a solid solution () at all compositions. However, at lower
temperature the solid solution spontaneously decomposes into two solid solutions, ' and
'', that have the same structure but different compositions. The two-phase, ' + '' region
within the miscibility gap contains the same information as any other two-phase region in a
binary phase diagram. The compositions of the two phases, ' and '', are determined as a
function of temperature by the isothermal tie-lines. The phase fractions are determined
from the tie-line by the lever rule. As T 0 the compositions of the terminal solid
solutions approach x = 0 and x = 1 to satisfy the Third Law.
Page 427
As suggested by the simple solution model, a miscibility gap is due to a preference

for bonds between atoms of like kind, with the consequence that the energy is lowered
when the system segregates into A-rich and B-rich solutions. At higher temperature the en-
ergetic preference for decomposition is outweighed by the entropic preference for the solid
solution.
' ''
A B
x
...
Fig. 18.4: The phase diagram of a binary system that contains a miscibility
gap in a homogeneous solid solution. The two-phase regions
are shown shaded; the horizontal lines are the tie-lines.
The binary systems whose components are mutually soluble at intermediate tem-
perature, but become immiscible at lower temperature include Au-Ni, Au-Pt, Cr-Mo, Cr-W,
Cu-Ni, Cu-Rh, Ir-Pa, Ir-Pt and Ta-Zr. Ceramic systems such as NiO-CaO also form solid
solutions with low-temperature miscibility gaps. According to the Third Law, the
miscibility gap must extend to the pure component lines at T = 0, as drawn in Fig. 18.4.
Not all of the diagrams that appear in compilations of binary phase diagrams are drawn this
way since decomposition is kinetically slow and difficult to observe at low temperature.
Phase diagrams with low-temperature ordered phases
The phase diagram of a binary system that forms an ordered phase at low tempera-
ture is shown in Fig. 18.5. The single-phase region of the ordered phase is closed at a
congruent point at its top (T0) and asymptotes to a point in the limit T 0, to satisfy the
Third Law. The conditions at the two limiting temperatures have the consequence that the
ordered phase field has a shape something like that of an inverted teardrop. At finite tem-
peratures the ordered phase has at least a slight solubility for the species A and B, and is in
equilibrium over a range of compositions about its stoichiometric value. The single-phase
field is bounded by two-phase (+) fields that separate it from the single-phase field on
either side. If only one ordered phase is present, then the two-phase regions that bound it
must spread across the phase diagram in the limit T 0 so that the equilibrium phases at T
= 0 are the stoichiometric ordered phase and the phase at x = 0 or x = 1, in agreement
with the Third Law. In many systems that order, several ordered phases are present.
Page 428
A B
x
...
Fig. 18.5: Phase diagram of a binary system that has an ordered phase ()
at low temperature. The two-phase regions are shaded with
horizontal tie-lines.
The free energy relations that give rise to a phase diagram like that in Fig. 18.5 are
illustrated in Fig. 18.6. The free energy curve of the ordered compound lies above that of
the solid solution when T > T0 and passes through it to create a congruent point at T =
T0. The free energy curve of the ordered phase has a strong minimum at its stoichiomet-
ric composition. When T < T0 the free energy curve of the phase lies below that of the
solid solution only at compositions near the stoichiometric value. Hence there are common
tangents between the and free energy curves on both sides of the curve. The phase
is the equilibrium phase at compositions near the stoichiometric value; the phase is at
equilibrium at compositions that deviate significantly from the stoichiometric value to either
side.

g g
14A

+ +

A B A B
x x
...
Fig. 18.6: Free energy relations leading to the appearance of an ordered
compound: (a) T > Tc; (b) T < Tc.
Many binary systems whose components have complete or extensive solid solubil-
ity at intermediate temperature are known to order into one or more stoichiometric com-
Page 429
pounds at lower temperature. Examples include Au-Cu, Cu-Pt, Cd-Mg, Co-Pt, Cu-Pd, Fe-
Ni, Fe-Pt, Fe-V, Mn-Ni, Ni-Pt, and Ta-V.
18.8.5 Phase diagrams with eutectic or peritectic reactions
Binary systems that have two distinct phases in the solid state often have phase dia-
grams of the simple eutectic or peritectic (inverted eutectic) form.
The eutectic diagram
The simple eutectic diagram is drawn in Fig. 18.7. It takes its name from the
eutectic reaction which occurs at the minimum point of the liquid phase field.
A B
x
...
Fig. 18.7: A binary system with a simple eutectic diagram. The two-
phase regions are shown shaded with horizontal tie-lines.
A system that has a eutectic phase diagram is usually one whose components have
different crystal structures in the pure form. Since components with different structures
cannot form a continuous range of solid solutions, there are always at least two phases in
the solid state and the eutectic diagram is one of the simplest the system can have. Among
the systems with simple eutectic diagrams are Ag-Bi, Al-Ge, Al-Si, Al-Sn, Au-Co, Au-Si,
Bi-Cu, Bi-Cd, Bi-Sn, Cd-Pb, Cu-Li, In-Zn, Pb-Sb, Pb-Sn, Si-Zn and Sn-Zn. Ceramic
systems with simple eutectic diagrams include MgO-CaO, among others. All of these sys-
tems have components with different crystal structures, and are sufficiently different
chemically that it is plausible that they form no stable compounds.
However, there are also systems that have simple eutectic phase diagrams even
though their components have the same crystal structure. Examples include Ag-Cu, in
which both components are FCC, Cd-Zn, both components HCP, and Na-Rb, both com-
ponents BCC.
The most plausible interpretation of the eutectic behavior in this case is that the two
terminal solutions have a miscibility gap at a temperature so high that the liquid phase is re-
tained to temperatures well below Tc. The relations between the free energy curves that
Page 430
lead to a eutectic diagram in a system whose solid phases have a miscibility gap is dia-
grammed in Fig. 18.8. Fig. 18.8a diagrams a situation in which a solid phase has decom-
posed into two solutions with the same structure, and , at a temperature at which the
liquid is still stable. As the temperature decreases the solid free energy curve drops with
respect to the liquid, and leads to a eutectic diagram. Fig. 18.8b shows the situation just
above the eutectic point where all three phases appear. Fig. 18.8c shows the situation just
below the eutectic point where only and solid solutions appear at equilibrium.
L

g
L
L +L L +L +
A x B A x BA x B
...
Fig. 18.8: Free energy relations leading to a eutectic diagram for a system
whose components have a miscibility gap at high temperature.
(a) Liquid phase stable; (b) three phases appear at lower T; (c)
two solid phase appear below the eutectic point.
The peritectic diagram
The classic peritectic phase diagram is drawn in Fig. 18.9. It is characterized by the
appearance of a peritectic reaction of the form
+L 18.150
that appears at the top of the field.
A B
x
...
Fig. 18.9: A simple peritectic phase diagram in a binary system.
Page 431
The peritectic reaction is, essentially, an inverse eutectic. The classic eutectic reac-
tion occurs when the free energy curve of the liquid cuts through a common tangent to the
curves of two solid phases on heating. The peritectic occurs when the free energy curve of
a solid phase cuts through a common tangent to the curves of liquid and solid phases on
cooling. The relations between the free energy curves just above and just below the peri-
tectic point are illustrated in Fig. 18.10. Just above the peritectic the common tangent to the
L and phases lies below the free energy curve, as in Fig. 18.10a. At the peritectic the
free energy curve contacts that common tangent, and drops below it as the system is cooled
further to create the configuration shown in Fig. 18.10b.
L L
g g
L
L L+ +

L+
A B A B
x x
...
Fig. 18.10: Free energy relations leading to a peritectic phase diagram. (a)
T just above the peritectic temperature; (b) T just below.

L

g
L
L +L L +
A x B A x BA x B
...
Fig. 18.11: A peritectic reaction in a system with a high-temperature misci-
bility gap. (a) The liquid phase is stable at a high temperature
below the miscibility gap in the solid; (b) two-phase equilib-
rium just above the peritectic; (c) two-phase equilibrium below
the peritectic temperature.
Simple peritectic diagrams are much less common that simple eutectic ones. The
thermodynamic reason is apparent from Fig. 18.10. To create a peritectic point the free en-
ergy curve of the solid must cut that of the liquid at finite x, that is, at a composition away
from the axis. For that to happen the free energy of the solid phase must decrease more
quickly than that of the liquid at small x. Since the liquid has higher entropy, this is only
Page 432
likely to happen when the enthalpy of the solid phase drops rapidly with the solute content,
that is, when there is a strong preferential bonding between the two components in the
phase. But this is precisely the situation that leads to the formation of stable compounds
between the two components. A system that has a simple peritectic diagram is, therefore,
likely to be one that also forms stable compounds.
There is at least one example, Ag-Pt (FCC), in which two components with the
same crystal structure have a peritectic phase diagram. As in the case of a eutectic diagram
between elements with the same structure, this suggests that the components have a high-
temperature miscibility gap, leading to free energy relations like those shown in Fig. 18.11.
The condition is that the second solid phase that intersects the liquid curve ( in the case
shown) makes its first appearance as a stable phase by cutting the tie-line between the liquid
and the solid solution.
18.8.6 Structural transformations in the solid state
When one of the components of a binary system undergoes a structural transforma-

tion on cooling, not only is a new structure introduced into the binary phase diagram, but
new two-phase equilibria appear. Since the phases that are connected by the structural
transformation are different, they respond differently to the introduction of the solute. The
result is a two-phase equilibrium field between them. Figs. 18.12 and 18.13 show the com-
mon forms of the binary phase diagram of a system in which one component (A) under-
goes a structural transformation ( ) as the temperature is lowered. The configurations
at the solid-solid transformation are geometrically identical to those at the eutectic and peri-
tectic points of the liquid-solid transformation.
If is the low-temperature phase of a component (A) that also has a high-tempera-

ture phase, , then the free energy of falls below that of as the temperature is lowered.
On the x=0 axis (where the system has only one component) the two free energies cross at
the transition, which happens at a particular temperature. However, since the two phases
are distinct they respond differently to the solute, and hence have different free energy
curves at finite x. As these curves pass through one another they generate a two-phase re-
gion, just as in the liquid-solid case. The shape of the two-phase (+) region depends on
where the free energy curve first contacts the curve as the temperature is lowered. If
the first contact is between the and curves rather than between the curve and the -
common tangent then the behavior is just like that near a eutectic point in the liquid-solid
case; the high-temperature phase field () extends to a temperature minimum at finite x, as
shown in Fig. 18.42. The reaction at the bottom of the field is
+ 18.151
This reaction is called a eutectoid reaction since it is eutectic-like, but involves only solid
phases.
Page 433
L
+L +L
T
+

+
A B
x
...
Fig. 18.12: A binary system with a eutectic reaction at the bottom of the
liquid phase field and a eutectoid reaction at the bottom of the
phase field of the high-temperature () phase. The two-phase
fields are shaded with isothermal tie-lines.
In a system that has a eutectoid reaction the first contact between and is ordinar-
ily at x = 0, in which case the phase diagram near the reaction looks like that shown in Fig.
18.18. However, it is also possible that the first contact occurs slightly off the x-axis at fi-
nite composition. In this case the field has a maximum at a congruent point between
and , while the field has a minimum at a eutectic point at slightly higher composition.
We shall not illustrate this case.
Eutectoid reactions are common in binary systems that include a component that
transforms in the solid state. The most familiar example is the transformation in Fe-
Fe3C phase diagram that is the basic phase diagram of carbon steel. Other examples in-
clude the transformation of Ti in Ti-Cr and Ti-W, the transformation in Mn in
Ni-Mn, and the transformation in Th in Th-U and Th-Zr. Eutectoid reactions also
occur in the transformations of many intermetallic and oxide compounds.
The second possibility is that the free energy curve cuts the - common tangent
as the system is cooled before it contacts the free energy curve outside the common tan-
gent. Then the situation near the transition temperature is like that illustrated for the peri-
tectic transition in the liquid-solid case. The phase field extends to a temperature maxi-
mum at finite x, and the configuration near the transition has a shape like that drawn in Fig.
18.18. The reaction at the maximum point of the field is
+ 18.152
and is called a peritectoid reaction.
Peritectoid reactions are reasonably common. Examples include the transition

of Fe in Fe-Nb and Fe-Ta, the transition of Co in Co-Cr and Co-W, and the
Page 434
transition of Mn in Mn-Cr. Peritectic reactions are also found in a number of intermetallic

and oxide compounds.
A B
x
...
Fig. 18.13: A binary system with a eutectic reaction at the bottom of the
liquid phase field and a peritectoid reaction at the top of the
phase field of the low-temperature () phase. The two-phase
fields are shaded with isothermal tie-lines.
18.8.7 Systems that form compounds
A substantial fraction of all binary systems form ordered compounds in the solid
state. In fact, it is common for several compounds to appear in the phase diagram. To ex-
plore the influence of ordered compounds on the shape of the phase diagram we consider
systems that contain a single one. Fig. 18.15 illustrates the phase field of a compound that
emerges directly from a solid solution. We now consider compounds in systems that con-
tain two terminal solid solutions. Four cases are reasonably common: (1) a compound first
appears at a congruent point in the liquid; (2) a compound first appears at a peritectic point
in a two-phase region (+L); (3) a high-temperature compound disappears at a eutectoid;
(4) a low-temperature first appears at a peritectoid. Finally, we consider the equilibrium
phase fields near a structural transformation of an ordered compound.
Compounds that form directly from the liquid
Many binary systems have stable compounds that can be formed directly from the
liquid at a congruent point. The simplest phase diagram for a system of this type is shown
in Fig. 18.14. The compound essentially divides the phase diagram into two eutectic dia-
grams between the compound and the terminal solid solutions.
Phase diagrams like that shown in Fig. 18.14 govern a large number of binary sys-
tems, including Al-Sb, Al-Ca, Al-Au, As-In, As-Pb, Ca-Mg, Nb-Cr, Cd-Sb, Cd-Te, Cr-
Ta, Cr-Zr, Ga-Sb, Hf-V, In-Sb, Mg-Pb, Mg-Si, Mg-Sn, Mo-Pt, Pb-Te, Sn-Te, and Zn-Te,
among others. Note that phase diagrams of this form are particularly common in the III-V
and II-VI systems. In these cases the stable compounds are the semiconducting III-V and
II-VI compounds.
Page 435
A B
x
...
Fig. 18.14: The phase diagram of a system that forms a stable compound
at an intermediate composition.
The reaction at the congruent point in Fig. 18.14 is L , where is the com-
pound. Compounds of this type are particularly easy to make since they can be gotten by
direct solidification (casting or crystal growth) from a liquid of appropriate composition.
Phase diagrams of this type are basic to a number of technologically important processes.
Perhaps the most important is the growth of large crystals of III-V and II-VI semiconduct-
ing compounds from the melt, which is only possible when the compound has a congruent
point with the liquid.
Compounds that form through a peritectic reaction
If a binary system contains a single compound () whose free energy curve is such
that its first appearance breaks a solid-liquid (+L) tie-line then the compound is derived
from a peritectic reaction ( + L ) and the simplest phase diagram is like that shown in
Fig. 18.15.
L

T
A B
x
...
Fig. 18.15: The phase diagram of a binary system with an intermediate
compound that forms by a peritectic reaction.
Page 436
Several binary systems that have phase diagrams that closely resemble Fig. 18.15,
including Bi-Pb, Cd-Sn, Hg-Pb, In-Pb, Hf-W, Mo-Zr, Ru-W and Sn-Tl. The phase dia-
grams of Mo-Hf and Sb-Sn differ from Fig. 18.15 only in that the phase at the far end of
the phase diagram has a peritectic rather than a eutectic relation to . The phase diagrams of
many binary systems that form multiple compounds are such that some of these com-
pounds form through peritectic reactions and have local phase relationships like those in the
left-hand side of Fig. 18.15.
Because the compound in Fig. 18.15 is the product of a peritectic reaction it can-
not be cast or grown directly from the melt. Moreover, many of the more useful com-
pounds of this type include elements that diffuse slowly in the solid state so that it is diffi-
cult to make the compound by holding the system at a point within equilibrium phase field.
Technologically important compounds that have this behavior include the A15 supercon-
ducting compounds such as Nb3Sn and Nb3Al, high-temperature intermetallic structural
materials like Ni3Al, and low-density intermetallics with potential high-temperature struc-
tural applications such as the Al-Ti intermetallics. Complex processing techniques such as
reaction from a ternary solution, vapor deposition, or powder processing are required to
synthesize these compounds.
Finally, note that a phase diagram like that shown in Fig. 18.15 has a eutectic reac-
tion, but the phases that border the eutectic include intermediate compounds ( in the fig-
ure). Nonetheless, a system that has the eutectic composition will solidify into a eutectic
microstructure. One or both of the interleaved phases are intermetallics rather than terminal
solid solutions.
Compounds that disappear at a eutectoid
Many binary phase diagrams contain ordered compounds that only appear at inter-
mediate temperature. They are stable at high temperature, but eventually disappear if the
system is cooled. For this to happen in a simple system that contains only one ordered
compound the common tangent to the free energy curves of the terminal solid solutions
must fall beneath the free energy curve of the compound at sufficiently low temperature.
This is more likely to happen if the terminal solution is more stable than the compound, and
is hence most often observed in systems whose compounds result from a peritectic reaction
like that shown in Fig. 18.15.
Fig. 18.16 contains a sketch of a simple phase diagram containing a single ordered
compound that is confined to intermediate temperature. The top of the phase field of the
compound is a peritectic point, +L . The phase field terminates in a eutectoid reaction,
+.
Several binary systems have phase diagrams that resemble Fig. 18.16 very closely,
including Bi-Pb, Cd-Sn and Ru-W. Many other systems contain compounds whose ther-
mal stability is limited by the intrusion of other ordered compounds.
Page 437
L

T
A x B
...
Fig. 18.16: Phase diagram of a simple binary system that forms a com-
pound at intermediate temperature.
Compounds that form at a peritectoid
If an intermetallic compound first appears in the solid state then it intrudes either
into a single-phase region or a two-phase region. In the former case the maximum tempera-
ture of the equilibrium field of the compound is a congruent point, as in Fig. 18.5, where
the compound forms by a reaction of the type . In the latter case the maximum tem-
perature is the temperature at which the free energy curve of the compound cuts a two-
phase tangent line. The top of the field is a peritectoid point, and the compound forms by a
reaction of the type + .
A simple phase diagram for a binary system with a compound that forms by a peri-
tectoid reaction is shown in Fig. 18.18. Several binary systems have phase diagrams that
resemble this one, including Ru-Mo, Ru-Nb and Pd-V. In binary systems that contain
several compounds it is common that one or more appear at low temperature through peri-
tectic reactions.
A B
x
...
Fig. 18.17: Phase diagram of a simple system in which a compound ap-
pears through a low-temperature peritectoid reaction.
Page 438
Structural transformation of a compound
Compounds may undergo structural transformations just as pure phases do. In fact,
there is a richer set of possibilities for transformations in compounds, since compounds can
change in chemical order as well as in basic lattice structure.
A transformation occurs in a compound when there are two separate phases of es-
sentially the same compound (nearly the same stoichiometric composition) whose free en-
ergies become equal at some temperature and composition. If the high-temperature phase
of the compound were cooled to that temperature and composition it would transform ho-
mogeneously to the low-temperature phase. If the two phases are related by a first-order
transformation, that is, if they are distinct phases at the transformation point, then they are
represented by different free energy curves and their first contact on lowering the tempera-
ture is at an isolated point.
A compound differs from a pure component in that its composition can deviate
from stoichiometry in either the positive or the negative sense. At finite temperature the
free energy curve of a compound is continuous through its stoichiometric composition and
its chemical potential is not infinite there. This has the consequence that the free energy
curves of two phases of essentially the same compound (that is, compounds that have the
same stoichiometric composition in the limit T 0) may first touch one another on cooling
at a composition that is off-stoichiometric and possibly outside the equilibrium phase field
of the high-temperature phase.
+ + + +
A BA B
x x
...
Fig. 18.18: Possible shapes of the free energy curves near the transforma-
tion . (a) The free energy curve contacts within the
stability range. (b) The free energy curve contacts the -
common tangent.
The two possibilities are illustrated in Fig. 18.18, which shows free energy curves
at a temperature just above that at which a compound, , transforms to a second compound,
, in a system whose phase diagram is like that in Fig. 18.14 at temperatures above that
shown. In the left-hand figure the free energy curve of the phase contacts that of the
Page 439
phase within its region of stability. In the right-hand figure the free energy curve contacts
the common tangent between the phase and the primary solution.
A x B
...
Fig. 18.19: Phase diagram of a binary system in which a high-temperature
compound, , transforms to a low-temperature compound, , at
a congruent point, as in Fig. 18.48a.
The situation shown in Fig. 18.18a leads to a phase diagram like that shown in Fig.
18.19. The contact of the and free energy curves gives rise to a congruent point in the
phase field at which without change of composition. The congruent point is en-
closed by two-phase (+) fields that terminate at eutectic points for the reactions +
and +.
Structural transformations of compounds that lead to a phase relationship like that

drawn in Fig. 18.19 occur in a number of binary systems, including W-C, Ag-Ga, Ag-Li,
Au-Zn, Cu-In, Cu-Sn, Mo-C, Mn-Zn, Ni-S, Ni-Sn and Ni-Sb.
A x B
...
Fig. 18.20: Phase diagram for a system in which a compound transforms
through a peritectic reaction, as in Fig. 18.48b.
When the configuration of the free energy curves near the structural transformation
resembles that in Fig. 18.18b, the low-temperature phase, , first appears as the product of
Page 440
a peritectic reaction, + . The given fact that becomes stable means that the curve
is displaced downward relative to the free energy curve as the temperature decreases. The
form of the phase diagram near the peritectic can be approximated by translating the free
energy curve in 18.18b downwards as T decreases and constructing the successive
common tangents. The resulting phase diagram is drawn in Fig. 18.20. The and sta-
bility fields never touch; they are separated by a narrow two-phase region that terminates at
a eutectic point where the reaction is + .
Compound structural transformations of the type that appears in Fig. 18.20 are
found in many binary phase diagrams. Among the systems that have reactions of this type
are Ag-Cd, Ag-In, Bi-Mg, Co-Cr, Ge-Cu, Cu-Sn, Hf-Ir, Mn-Ni, Mn-Pt, Mn-Zn, Mo-Pt,
Ni-V, and Zn-Sb. As this extensive list suggests, the geometry of the transformation in
Fig. 18.20 is, in fact, more common than that the congruent geometry shown in Fig. 18.19.
Its prevalence reflects the narrow width of the equilibrium phase fields of most solid com-
pounds; a small difference in the relative composition dependence of the free energies of the
two phases can then shift the first intersection of the two curves out of the stability field of
the high-temperature phase.
18.8.8 Mutation lines in binary phase diagrams
In a mutation, one phase simply becomes another. There is no two-phase equilib-

rium and, hence, there are no two-phase regions associated with mutations.
'
A B
x
...
Fig. 18.21: A eutectic system with a mutation in the terminal solid solu-
tion, indicated by the dashed line.
However, in a binary system the critical temperature for a mutation can be a func-
tion of composition, and almost always is. Hence the mutation appears as a simple curve in
a pseudo-single phase region that contains both of the phases that are related by the mu-
tation. There is also no discontinuity in the boundary of the pseudo-single phase region
where the mutation line contacts it. The composition of the phase in equilibrium in a two-
phase region is fixed by temperature. Hence a mutation line is a horizontal isotherm
through a two-phase region that gives the temperature at which one phase mutates.
Page 441
T

'
A B
x
...
Fig. 18.22: A binary system with an intermediate compound that under-
goes a mutation, indicated by the dashed line.
Fig. 18.21 illustrates the appearance of a eutectic phase diagram with a mutation in
the -rich solid solution. The ferromagnetic transition in Fe and Ni and the rare earths
leads to phase relationships like those shown in Fig. 18.21. Fig. 18.22 illustrates the phase
relationships in a simple system with an intermediate ordered phase that mutates. Many
intermediate compounds undergo ordering reactions that are mutations. The classic exam-
ple is the ' transition in Cu-Zn.
18.8.9 Miscibility gap in the liquid
As a final example we consider a binary system in which a miscibility gap intrudes

in the liquid, as it does in many real systems. The simplest system of this type has only the
two terminal solid solutions in the solid state. The phase diagram is drawn in Fig. 18.23.
L1 L2
A B
x
...
Fig. 18.23: A possible phase diagram for a binary system with a miscibil-
ity gap in the liquid. The shaded region is an equilibrium be-
tween two liquid phases.
Page 442
A sequence of free energy relations that lead to a phase diagram like that shown in
Fig. 18.23 is drawn in Fig. 18.24. Fig. 18.24a pertains to a temperature just below the
melting point of the phase. The miscibility gap in the liquid is due to the inflection in its
free energy curve, which divides it into two stable phases with a common tangent. The
three phases , L1 and L2 appear in the section. Fig. 18.24b is drawn at a lower tempera-
ture at which the liquid phase L1 no longer appears. As shown in the diagram the free en-
ergy curve of the phase has dropped with respect to that of the liquid, with the conse-
quence that the lowest common tangent connects the and L2 free energy curves directly.
The free energy curve is everywhere above that of L2. As a consequence there are two
phases in the section, and L2. Fig. 18.24c illustrates behavior at a still lower temperature
where both the and free energy curves are well below that of the liquid. The lowest
common tangent in this case connects and directly; only these phases appear in an
isothermal section through the phase diagram.

g L' L" L' L" L' L"

+ L' L'+L" L" +L" L" +
L'
A x B A x B A x B
...
Fig. 18.24: Free energy relations at three temperatures in a system with the
phase diagram shown in Fig. 18.53: (a) just below the melting
point of ; (b) at a T where only and L2 appear; (c) at a T
where only and appear.
The binary systems that have phase diagrams that resemble Fig. 18.24 include Al-
Bi, Al-In, Bi-Zn, Cu-Cr, Cu-Pb, Cu-Tl, Ni-Pb, Pb-Zn and Th-U. These systems contain
species that are very different in their chemical behavior, which leads to the miscibility gap
in the liquid. A like behavior is seen on the silica-rich side of the SiO2-MgO diagram.
Similar phase relations are found at low temperature in the solid state in a number of
systems that form extensive solid solutions, including Al-Zn, Nb-Zr and Hf-Ta. Phase
fields like those in Fig. 18.23 result from a miscibility gap in the solid solution. In the case
of Al-Zn the miscibility gap has a bottom because of its interaction with the terminal Zn
solid solution. In Nb-Zr and Hf-Ta the bottom of the miscibility gap is due to interference
by the low-temperature phase of one of the components; both Hf and Zr have structural
transformations at low temperature.
Page 443

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Notes on the Thermodynamics of Solids J.W. Morris, Jr.

Chapter 18: Solutions

thermodynamics of solid solutions that is independent of the details of the atom

18.2 IDEAL SOLUTIONS

18.2.1 A solution of ideal gases

The fundamental equation of a mixture of ideal gases was developed as an exercise

Given the additivity of the energy and the pressure,

Smix = - N xkln(xk) 18.7

F(T,V,{N}) = Nf(T,v,{x}) = VFv(T,{n})

18.2.2 The ideal solution

an ideal solution is a solution that obeys a fundamental equation of the form

The relative chemical potential of the kth component in an ideal solution is

where x is the mole fraction of solute.

18.3.3 The vapor pressure of a component in an ideal solution

k = k(T) + T ln(Pk) 18.16

18.3 THERMODYNAMICS OF REAL SOLUTIONS

18.3.1 Excess thermodynamic quantities

The excess entropy of solution is

18.3.2 The activity and the activity coefficient

The chemical potential of a real solution can always be written

where the activity of the kth specie is

and the activity coefficient is

In this notation the heat of mixing becomes

18.4 DILUTE SOLUTIONS

which has the integral

1. any chemical specie is at least slightly soluble in any other;

18.4.2 The fundamental equation of a dilute solution

The fundamental equation of a dilute solution is formally identical to that of an ideal

Hence the molar density of the Gibbs free energy is

where the relative chemical potential,

is accurate to within terms of order xk.

18.4.3 Generalization to "semi-dilute" solutions

To generalize the fundamental equation to slightly higher concentrations note that

where the second-order coefficient

Hence, to second order in the concentration,

18.5 DILUTE SOLUTIONS: APPLICATIONS

We include a series of examples here to illustrate the applications of the theory of

18.5.1 Equilibrium of two solutions with the same solvent

Since the mole fraction of solute is small,

18.5.2 Influence of a dilute solute on two-phase equilibrium

Let two phases of a pure material be in equilibrium at (T0, P0). Then

(x - x)T0 ~ (v - v)P - (s - s)T

First consider the effect on the transformation temperature at constant pres-

18.5.3 The vapor pressure of a dilute solution: Raoult's Law

18.5.4 Osmotic pressure

When the solute is present only on one side,

18.5.5 Dilute solutions with the same solute: Henry's Law

Hence the ratio of the solute concentrations in the two solutions is

where K(P,T) is independent of the composition. Equation 18.74 is Henry's Law:

the partial pressure of a solute above a dilute solution is linearly proportional

A second example, which is more important in materials science, is the equilibrium

18.5.6 Solute-solvent equilibria between dilute solutions

Equation 18.78 is always satisfied at sufficiently low temperature if

the concentration of a component in a dilute solution that is in equilibrium

As a simple extrapolation, consider the behavior of a binary system that decom-

where x is the solute concentration in the th phase and K is a positive constant.

18.5.7 The interference of solutes in a dilute ternary solution

The solubility limit of a binary solution is defined in practice as the maximum

18.6 BEHAVIOR NEAR A CRITICAL POINT

Since a stable solution must satisfy the condition

the critical point is a stability limit for the homogeneous solution.

(x') = (x") 18.96

which has the solution

18.7 THE SIMPLE SOLUTION