Gibbs-Thomson equation

Figure 1
( ) ( ) ( )
0
x
G
G P G x x x
x
o
| o |
o
'
| | c
' ' = = +
|
c
\ .


( ) ( ) ( )
x
G
G P P G x x x
x
o
| | o |
o
''
| | c
'' '' = = +
|
c
\ .


( ) ( ) ( ) ( ) ( ) ( )
m
0
x x
P V
G G
G P P G P G x x x G x x x
x x
| |
o o
| | | o | o |
o o
'' '
| | | | c c
'' '' ' ' = = = +
| |
c c
\ . \ .

(1)
Let us use our favourite ultimate weapon by decomposing G
o
in the Taylors series in the
vicinity of x' :

( ) ( ) ( ) ( )
( )
x x
G G
G x x x G x x x
x x
G x
o o
o | o |
o o
'' '
o
| | | | c c
'' '' ' ' +
| |
c c
\ . \ .
' = ( ) ( ) ( )
x x
G G
x x x x G x
x x
o o
| o
o o
' ''
| | | | c c
'' ' '' ' + +
| |
c c
\ . \ .
( )
x
x
G
x x
x
G
x x
x
o
|
o
'
o
o
'
| | c
'
|
c
\ .
| | c
'' ' =
|
c
\ .
x x
|
' +
( ) ( )
x
G
x x
x
o
|
o
''
| | c
'' +
|
c
\ .

1
Now let us employ it again by decomposing G x
o o
c c in the Taylors series in the vicinity of x' :

( ) ( ) ( ) ( )
( )
x x
x
G G
G x x x G x x x
x x
G
x x
x
o o
o | o |
o o
'' '
o
|
o
'
| | | | c c
'' '' ' ' +
| |
c c
\ . \ .
| | c
'' =
|
c
\ .
( )
x
G
x x
x
o
|
o
'
| | c
'' +
|
c
\ .
( )
( )
( )
2
2
x
G
x x x
x
o
|
o
'
| |
c
|
x '' '' ' +
|
c
\ .
(2)
Since x'' does not differ dramatically from x' , (2) can be written as:
( ) ( ) ( ) ( )

( )
( )
2
2
x x
x x
x
G G
G x x x G x x x x x x
x x
x
o o
o | o | o |
o o
o
'' '
'' '
G
o
'
| |
| | | | c c
|
'' '' ' ' ' + ~ A
| |
| c c
\ . \ . c
\ .
c

By taking (1) into account, one immediately arrives at:

( )
( )
2
m 2
x
G
x x x P V
x
o
o | | |
o
'
| |
c
|
' A =
|
c
\ .
(3)
By rearranging (3), the following expression, in which x' is replaced with x
o
for the sake of
clarity, can be obtained:

( ) ( )
m
2
2
P V
x
x x G x
| |
o
| o o o
A =
c c
(4)
If the | phase exists as a spherical particle of radius , then: r

2
P
r

|
= (5)
By combining (4) and (5), one gets:

( ) ( )
m
2
2
2 V
x
r x x G x

|
o
| o o o
A =
c c
(6)
Although (6) looks great, it is not quite clear what to do with the partial derivative in its
denominator. Let us consider a simple case when o is the regular solution:

( ) ( ) ( )
ref
a linear function
with respect to
1 ln 1 ln 1
x
G G RT x x x x x e
o
o o o o o o o
(
= A + + +

x
o


( )
( )
( )
( )
2
2
2 1
2
1 1
RT x x
G RT
x x x x
x
e
e
o o
o
o o o o
o

c
= =

c
(7)
2
Substitution of (7) in (6) yields:

( )
( ) ( ( ) )
m
1
2
2 1
x x
V
x
r
x x RT x x

e
o o
|
o
| o o o

A =

(8)
(8) is known as an extended form of the Gibbs-Thomson equation.
For large x
o
A
2 1
, an integration should be carried out. The calculations become straightforward if
is a dilute solution of the second component in the first component. In this case, o
( )
RT x e
o
x >>
o
, which allows the following simplification of (8):

( )
m
d d V P x
x RT x x
| o
o | o
=

(9)
You should not be surprised that (9) does not contain 1 x
o
, which is seen in the numerator of
(8). Since the solution is dilute, , which means that 1 1 x
o
<< 1 x
o
~ .
If the difference x x
| o
is not markedly affected by pressure, then one has:

( )
( )
( )
atmospheric
atmospheric
m
d d
P
x P
x P
P
V P x
x RT x x
o
o
| o
o | o
=

(
(
(
(
]
]


( )
( ) ( )
(
m
atmospheric
atmospheric
ln
x P V
P P
x P RT x x
o
|
o | o
=

)
(10)
For the spherical particle of | , (10) can be written as:

( )
( ) ( )
m
atmospheric
2
ln
x P
V
x P rRT x x

o
|
o | o
=

Very nice, eh?
So far, only one phase, namely o, was allowed to change its composition. Another phase, | ,
was assumed to be a stoichiometric one. What if both phases may vary their compositions? Since
a general derivation will be torturously lengthy, let us restrict ourselves by the small changes
case. Take a look at Figure 2 and realize that:
( ) ( ) (
x
G
G y G x y x
x
o
| o
o
'
| | c
)
' ' = +
|
c
\ .
' ' (11)
3
( ) ( ) (
x
G
G y G x y x
x
o
| o
o
''
| | c
'' '' '' '' = +
|
c
\ .
) (12)
( ) ( )
m
G y G y P V
| |
'' ' ~
| |
(13)
Let us subtract (11) from (12):
( ) ( ) ( ) ( ) ( ) ( )
x x
G G
G y G y G x y x G x y x
x x
o o
| | o o
o o
'' '
| | | | c c
'' ' '' '' '' ' ' ' = +
| |
c c
\ . \ .

Let us decompose into the Taylors series in the vicinity of G
o
x' :

( ) ( ) ( ) G y G y G x
| | o
'' ' ' = ( ) ( ) ( )
x x
G G
x x y x G x
x x
o o
o
o o
' ''
| | | | c c
'' ' '' '' ' + +
| |
c c
\ . \ .
( )
x
x
G
y x
x
G
x x
x
o
o
'
o
o
'
| | c
' '
|
c
\ .
| | c
'' ' =
|
c
\ .
y x ' ' +
( )
( )
x
G
y x
x
o
o
''
| | c
'' '' +
|
c
\ .

Now let us decompose G x
o o
c c :

( ) ( ) ( ) ( )
( )
( )( )
2
2
x x
x
x
G G G
G y G y x y y x y x x x
x x
x x
G
x
x
o o o
| |
o o
o o
' '
'
o
o
'
| |
| | | | c c c
|
'' ' '' ' '' '' '' '' '' ' = + +
| |
| c c
\ . \ . c
\ .
| | c
'' =
|
c
\ .
y y x ' '' '' +
( )
( )
( )( )
2
2
0, because y y x
G
y x x x
x x
o
o o
'' ' ~ ~ '
| |
c
|
'' '' '' ' +
|
c
\ .

(14)
It is natural to name x x '' ' as x
o
A . Since we are considering the small changes scenario,
y x '' '' can be identified with x x
| o
. Consequently, (14) can be written as:
( ) ( )
( )
( )
2
2
x
G
G y G y x x x
x x
o
| | | o
o o
'
| |
c
|
'' ' = A
|
c
\ .
o

By making use of (13), one arrives at:

( ) ( )
( )
2
2
m
P V
x
x x G x x
| |
o
| o o o
A =
c c
o

It is clear that the equilibrium composition of the matrix phase depends on whether the
coexisting phase physically exists as a bulk piece or a small particle. Moreover, we know how to
quantify the effect. Can you derive an expression for x
|
A ? It is not tricky. Try!
4

Figure 2
5