Energetics of crystalline solutions

B. Mishra

PART 2

ENERGETICS OF CRYSTALLINE SOLUTIONS

In the previous section (Part-1), dealing with pure crystalline phases, we derived an
expression for G = G (P, T). However, most of the rock forming minerals (silicates) and
those constitute ore deposits (sulfides) occur as solid solutions of two or more end
member components. Hence, it is appropriate to bring in the compositional variable for
deducing the free energy of formation of a phase, i.e., G = G (P, T, X). Accordingly, in
this section, we deal with energetics (total change in Gibbs free energy), pertaining to
formation binary crystalline solution phases.

The activity of a pure phase component (i) is related to free energy through the relation

Gi

P ,T

Gi

where Gi

Gi

0 , P ,T

, P ,T

(1)

is the free energy of component i in phase at P, T.

P ,T

0 , P ,T

RT ln ai

is the free energy of component i if it were a pure phase at P, T

(as derived in eqn. (24) in Part 1)

ai

, P ,T

is the activity of the component i in phase at P, T.

Also,

ai

, P ,T

X i . i

, P ,T

(2)

where X i = mole fraction of component i on phase

and, i

, P ,T

= activity coefficient of i in phase

Energetics of crystalline solutions

B. Mishra

In pure phases

X i = 1.0, i = 1.0

ai = 1 and Gi

P ,T

= Gi

0 , P ,T

[from eqn. (1)]

In solid solution phases with ideal mixing (Fig. 1)

i = 1.0, hence ai = X i
and Gi

P ,T

Gi

0 , P ,T

RT ln X i

(3)

Fig.1
Activity-composition
relationship of a binary solid
solution showing ideal (ai =
Xi) and non-ideal (ai >Xi and
ai < Xi) behaviors.

Gi Gi RT ln X i
id

In solid solutions phases with non-ideal mixing (Fig. 1)

i 1.0 ai X i
if i > 1.0, positive deviation from ideality.
if i < 1.0, negative deviation from ideality.
At any known P and T, the free energy of a mechanical mixture (G MM ) of A and B should
0

lie on a straight line joining G A and G B , in the G-X space as shown below.

Energetics of crystalline solutions

Hence, G MM = X A G A X B G B
0

B. Mishra

(4)

where G MM =free energy of mechanical mixture of A and B at P, T

0

G A , G B = free energy of pure phases A and B at P and T

X A , X B = mole fractions of A an B in the mechanical mixture

But for solid solution of components A and B forming a homogenous crystalline solution
AB, the G of Thus for a point (X) in the G-X plot, G SS can be expressed in terms of G MM
and g mix as
G SS = X A G A X B G B + g mix
0

(5)

Fig.2 GX plot for a model binary solid

solution AB showing the variation in
Gibbs free energy of the mechanical
mixture (Gmm) and solid solution (Gss).
Note the shift in free energy of mixing
(gmix) as consequence of change in the
composition of the solid solution.

X1

X2

Alternatively, a tangent can be drawn to the G SS -X curve at (X), as shown in Fig.2 and
extrapolated to intersect the G-X curve at X A 1.0 and X B 1.0 .The points of
intersections are labeled as G A and G B that are free energies of components A and B for
a specific composition (X1 or X2). But it is important to note that if (X) is shifted along
the G SS curve (say from X1 to X2), the slope of the tangent changes and so does its
intersections at X A 1.0 and X B 1.0 . Hence, G A and G B are functions of the
composition of solid solution (AB) at the given P-T.

Energetics of crystalline solutions

B. Mishra

Now, G SS at (any X value) can be represented as

G SS = X A G A X B G B

(6)

From eqns. (5) and (6) we may write

X A G A X B G B = X A G A X B G B + g mix
0

g mix X A (G A G A ) X B (G B G B )
0

(7)

Eqn. (7) can be written as

g mix = X A Gm , A X B Gm , B

where Gm, A G A G A RT ln a A (see eqn. 1)

0

Gm , B G B G B RT ln a B (see eqn. 1)
0

For a general case

Gi Gi RT ln ai
0

(8)

In eqn. (8), by subtracting and adding Gi ,id one obtains

(Gi Gi ,id ) Gi ,id Gi0 RT ln ai RT ln X i RT ln i

RTln i

RTln X i

From eqn. (3),

Gi ,id Gi RT ln X i
0

G i G i , id RT ln

(9)
Since (Gi ,id Gi ) is the change in free energy of a solid solution due to ideal mixing.
0

Hence, (Gi Gi ,id ) in eqn. (9) refers to an excess free energy of mixing over and above
ideal mixing in a crystalline solid solution. If the excess free energy of mixing is
represented by g mex,i , then we can write

g mex,i RT ln i

(10)

Hence, the total free energy of excess mixing in a solid solution g mex, ss can be expressed as

Energetics of crystalline solutions

B. Mishra

g mex,ss X A g mex, A X B g mex, B

or , g mex,ss X A ( RT ln A ) X B ( RT ln B )
X A ln A X B ln B

g mex,ss
RT
(11)

Eqn. (11) can be written in the general form as

Y (1 X 2 ) y1 X 2 y 2
where Y

g mex,ss
RT

(12)

, y1 ln A , y 2 ln B , x1 X A , x2 xX B

From eqn. (12) we can write

dY
y1 y 2
dx 2
y1 y 2

dY
dx 2

Substituting y1 in eqn. (12)

Y (1 x2 )( y 2

dY
dY
) x2 y 2 (1 x2 ) y 2 (1 x2 )
x2 y 2
dx2
dx2

dY
dY
y 2 Y (1 x2 )

Y y 2 (1 x2 )
dx2
dx2
(13a)
g mex, ss

d
RT
g mex, ss

(1 X B )
ln B
dX B
RT
y1 y2

dY
dx2

dY dY

Y (1 x2 )
dx2 dx2

dY

y1 Y x2
dx2

(13b)

B. Mishra

Energetics of crystalline solutions

g mex, ss

d
RT
g mex, ss

ln A
xB
RT
dX B

From eqn. (13), we obtain

g mex, ss

RT
g mex, ss

ln B
1 X B
RT
dX B
(14a)
g mex, ss

d
RT
g mex, ss

ln A
XB
RT
dX B
(14b)

Symmetric mixing (Regular solution or one Margules parameter model)

In case of symmetric mixing g mex, ss can be expressed as

g mex,ss W AB . X A X B W AB (1 X B ) X B
or , g mex,ss W AB ( X B X B2 )
(15)

Where WAB is the interaction or interchange free energy that arises as a result of
molecular interaction between A and B, and has the same unit as gmix (joules or calories)
Significantly from eqn. (15) both at X B 1 or X A (1 x B ) 1.0, g mex, ss 0
Now, from eqn. (15), we can write
g mex, ss

RT

dxB

W X X B2
d AB B

RT

dxB

Energetics of crystalline solutions

g ex
d m ,ss
RT

dx B

B. Mishra

W
AB (1 2 x )
B
RT

Substituting in eqn. (14a)

ln B

W AB ( X B X B2 )
W
1 x B AB
RT
RT

W AB
x B x B2 1 2 x B x B 2 x B2
RT
W
W
2
AB x B2 2 x B 1 AB 1 x B
RT
RT
RT ln B W AB (1 X B ) 2

1 2 x B

(16a)

Again from eqn. (14b), we get

W AB ( X B X B2 )
W
X B AB 1 2 x B
RT
RT
W .X
AB B 1 X B 1 2 X B
RT
W X2
AB B
RT
RT ln A W AB X B2
ln A

(16b)

Thus for a binary symmetrical solid solution (AB)

G AP ,T G A0, P ,T RT ln X A RT ln A
or , G AP ,T G A0, P ,T RT ln X B W AB X B2

(17)

Similarly, G BP ,T GB0, P ,T RT ln X B W AB (1 X B ) 2

Energetics of crystalline solutions

B. Mishra

In eqn. (17) G AP ,T and G BP ,T can be determined at any temperature if

(i) G AP ,T and G BP ,T are estimated from known constants (eqn.24, in the first part).
(ii) X A and X B being intensive thermodynamic variables, can be estimated from
mineral-chemical data.
(iii) W AB is known, determined from solution chemistry.