(1) Calculate the distribution of the normative components in the silica-rich part

of the system Na
2
O-SiO
2
.
(2) Calculate the activity coefficient (Na
2
O) ate 1400 C for x(SiO
2
) = 0.7.
Compare the result to the experimental data given below.
Exercise:
0.0 0.2 0.4 0.6 0.8 1.0
-10
-8
-6
-4
-2
0
non-linear approach
log f(SiO
2
),
1400 C
log f(Na
2
O)
1000 C
1200 C
1400 C
l
o
g

(
a
c
t
i
v
i
t
y

c
o
e
f
f
i
c
i
e
n
t
)
molar fraction of SiO
2
(1) Calculate the distribution of the normative components in the silica-rich part
of the system Na
2
O-SiO
2
.
(2) Calculate the activity coefficient (Na
2
O) ate 1400 C for x(SiO
2
) = 0.7.
Compare the result to the experimental data given below.
Exercise:
0.0 0.2 0.4 0.6 0.8 1.0
-10
-8
-6
-4
-2
0
non-linear approach
log f(SiO
2
),
1400 C
log f(Na
2
O)
1000 C
1200 C
1400 C
l
o
g

(
a
c
t
i
v
i
t
y

c
o
e
f
f
i
c
i
e
n
t
)
molar fraction of SiO
2
Set up a coefficient matrix like this: . Let .
|
|

\
|
1 0
2 1

2
2
2
O Na
SiO
NS S

30 . 0
70 . 0
2
2
|
|

\
|
=
|
|

\
|
O Na
SiO
( )
|
|

\
|
|
|

\
|
= =
|
|

\
|
=
) (
) (

1 0
2 1
) (
) (
2 2
2
NS n
S n
k
O Na n
SiO n
j
jk
r
r

The relation between oxides and compounds reads:

( )
jk
=
The equation is resolved for the vector of coumpounds:
( ) ( )
|
|

\
|
= =
|
|

\
|
=

) (
) (

) (
) (
2
2 1 1
2
O Na n
SiO n
j
NS n
S n
k
jk jk

r
r
( ) ( )
kj
T
jk
A
u u
u u
=
|
|

\
|

=
|
|

\
|
+
+
=
|
|

\
|
=

1 0
2 1

1 0
2 1
22 21
12 11
1
1

The coefficient matrix

jk
is inverted like this (better use a computer!):
Now we start with the inverted matrix .
( ) ( )
kj jk
A = =
1

|
|

\
|

1 0
2 1

2
2 2
NS
S
O Na SiO
( )
|
|

\
|

=
|
|

\
|

|
|

\
|

= =
|
|

\
|
=
) (
) ( 2 ) (
) (
) (
1 0
2 1

) (
) (
2
2 2
2
2
2
O Na n
O Na n SiO n
O Na n
SiO n
j A
NS n
S n
k
kj
r
r
and calculate
Normalization to n
S
+ n
NS2
= n
SiO2
- 2n
Na2O
+ n
Na2O
= n
SiO2
- n
Na2O
yields
Thus, x
S
= 0.25, x
NS2
= 0.75.
|
|

\
|
=
|
|
|
|

\
|

=
|
|
|
|

\
|

=
|
|
|
|

\
|

=
|
|

\
|
4 / 3
4 / 1
1 7 . 0 2
7 . 0 1
1 7 . 0 2
2 7 . 0 3
1 2
1
1 2
2 3
) ( ) (
) (
) ( ) (
) ( 2 ) (

2
2
2
2
2 2
2
2 2
2 2
2
SiO
SiO
SiO
SiO
NS
S
x
x
x
x
O Na n SiO n
O Na n
O Na n SiO n
O Na n SiO n
x
x
) 0 , (
) 2 1 (
1

2 1

) , (
1

1 3

) , (
) 1 (
1

1
1 2

) , 1 (
) 1 2 (
1

1 2
2 3

/ 1
3
1
2
2
2 2
2
2 2
3
1
2
1
2
2
2 2
2
2
2
1
3
2
2
2
2 2
2
2 2
3
2
2
2
2 2
2
2
2

=
=
SiO
SiO SiO
SiO
S N
SiO
SiO SiO
SiO
NS
SiO
SiO SiO
SiO
NS
SiO
SiO SiO
SiO
S
SiO B A B
x
x x
x
x N S N
x
x x
x
x S N NS
x
x x
x
x NS NS
x
x x
x
x NS S
x x x x A B range
We calculated the constitutional structure for range I. The results across the entire
compositional range are compiled below:
I.
II.
III.
IV.
0 20 40 60 80 100
0.0
0.2
0.4
0.6
0.8
1.0
SiO
2
Na
2
Si
2
O
5
Na
2
SiO
3
Na
4
SiO
4
Na
2
O
mol % SiO
2
f
r
a
c
t
i
o
n

o
f

s
p
e
c
i
e
s
The results for the constitutional structure across the entire compositional range are
shown. The calculated result for x
SiO2
= 0.70 is marked.
0 20 40 60 80 100
0.0
0.2
0.4
0.6
0.8
1.0
SiO
2
Na
2
Si
2
O
5
Na
2
SiO
3
Na
4
SiO
4
Na
2
O
mol % SiO
2
f
r
a
c
t
i
o
n

o
f

s
p
e
c
i
e
s
The results for the constitutional structure across the entire compositional range are
shown. The calculated result for x
SiO2
= 0.70 is marked.
Now we write down the Gibbs energy G of our mixture. It can be presented equally well
in terms of oxide components j or in terms of constitutional compounds k:
Since n
j
is replaced by (A
kj
)n
k
, we may write the sum term by term for each oxide j:
Resolving this equation for log
j
yields:
Note that the activity a
j
is given by
j
x
j
.
( )
( ) ( )
(
(

|
|

\
|
+ =
|
|

\
|
+ = +
+ = + =
+ =
+ =
+ =

j
j
k
k
k
kj j
k
k
k
kj j
j
k
k k j kj
k
k k k
j
j j j
k k k
j j j
x
RT
G
x
RT
G
A
x
RT
G
A a
RT
G
x RT G n A x RT G n
a RT G n G
x RT G G
a RT G G
ln ln
303 . 2
1
log
ln ln
ln ln
ln
ln
ln
(
(

|
|

\
|
+ =

j
j
k
k
k
kj j
x
RT
G
x
RT
G
A ln ln
303 . 2
1
log
When evaluating the equation
we need to employ the coefficients from the Na
2
O column of the matrix A
kj
:
This results in the following equation:
The following basic data are given for T = 1400 C:
G
SiO2
= G
S
= -1073.8 kJ/mol, G
NS2
= -3067.6 kJ/mol, G
Na2O
= -681.5 kJ/mol,
RT = 8.3141673.1510
-3
kJ/mol = 13.91 kJ/mol. We started with x
SiO2
= 0.7
x
Na2O
= 1 - x
SiO2
= 0.3 and calculated x
S
= 0.75. The result reads log
Na2O
= -6.8.
|
|

\
|

1 0
2 1

2
2 2
NS
S
O Na SiO
O Na NS S
O Na NS S
O Na
x x x
RT
G G G
2 2
2 2
2
log log 1 log 2
1 2
303 . 2
1
log +
(

+
=

0.0 0.2 0.4 0.6 0.8 1.0
-10
-8
-6
-4
-2
0
1000 C
1200 C
1400 C
log f(Na
2
O)
l
o
g

(
a
c
t
i
v
i
t
y

c
o
e
f
f
i
c
i
e
n
t
)
molar fraction of SiO
2
0.0 0.2 0.4 0.6 0.8 1.0
-10
-8
-6
-4
-2
0
1000 C
1200 C
1400 C
log f(Na
2
O)
l
o
g

(
a
c
t
i
v
i
t
y

c
o
e
f
f
i
c
i
e
n
t
)
molar fraction of SiO
2

] [ ] [ ] [ 1
] [ ] [ ] [ 1
] [ ] [ ] [ 1
] [ ] [
] [
;
] [ ] [
] [
;
] [ ] [
] [
1
4 4 2
2
2
1
3 2 2 2
1
5 2 2
2
2 2
2
2
2
4 4
3
2 2
3 2
2
2
2 2
5 2 2
1
2
2
2
2

=
=
=

= =

= =

= =
SiO Na SiO O Na K
SiO Na SiO O Na K
O Si Na SiO O Na K
SiO O Na
SiO Na
K K
SiO O Na
SiO Na
K K
SiO O Na
O Si Na
K K
S N
NS
NS
S N
NS
NS
Example:
system Na
2
O-SiO
2
with compounds
Na
2
Si
2
O
5
, Na
2
SiO
3
, Na
4
SiO
4
( )
( )

.
1
) 1 (
;
1
;
1
) 1 (
;
1
2
2
2
2
2
2
2
2
2
2
2
2
2
2
S NS S NS
S S S N
S NS
S NS S NS
N NS N S N
N N NS
N NS
N NS N S N
x K x K
x x K
s
x K
x K x K
r
x K x K
x x K
q
x K
x K x K
p
+ +

=

+ +
=
+ +

=

+ +
=
This is a simple second degree equation system which can be readily solved:
Either x
N
od x
S
is used as independent input variable:
( ) ( )
.
3 2 3
2
) ( 1 ) (
; ; ;
; 1 4 1
2
1 4 1
2
2 2
2 2
2 2 2 2
2 2
2 2
N S N NS NS S
S N NS NS S
S N NS NS S N NS NS S N S N S N
N S S N
x x x x x
x x x x
O Na x SiO x
x x K x x x K x x x K x
s
r
x x or q
p
x x
+ + + +
+ + +
= =
= = =
= = = =
0.0 0.2 0.4 0.6 0.8 1.0
0.0
0.2
0.4
0.6
0.8
1.0
T = 1400 C
Na
2
O Na
4
SiO
4
Na
2
SiO
3
NaSi
2
O
5
SiO
2
m
o
l
a
r

f
r
a
c
t
i
o
n

o
f

s
p
e
c
i
e
s
molar fraction of SiO
2
constitutional model &
associated species model
0.4 0.6 0.8 1.0
T in C =
400
800
1450
molar fraction of SiO
2
0.4 0.6 0.8 1.0
0.0
0.2
0.4
0.6
0.8
1.0
T in C =
1450
800
450
silica species disilicate species
m
o
l
a
r

f
r
a
c
t
i
o
n

o
f

s
p
e
c
i
e
s