CHAPTER 3.

Dilute Solutions
Takahiro Miki
Associate Professor, Tohoku University, Japan

3.6.1. HENRYS LAW AND SIEVERTS LAW

The activity-composition diagram for a binary solution that exhibits negative
deviation from Raoults law is shown in Figure 3.6.1. The Raoultian standard state
for component i is located at point A where the activity of i is unity. The deviations from
Raoults law by the actual solution is described in terms of the activity coefficient gI,
where gi is given by the ratio: ai/Xi. The activity coefficient is less than 1 when the interaction between solute and solvent is attractive and is greater than 1 for the case of repulsive interaction between solute and solvent. In infinitely dilute solutions, the Raoultian
activity of component i, ai, is directly proportional to its mole fraction, Xi, this is known as
Henrys law:
ai g Xi

3:6:1

Here, g is the activity coefficient of component i in the infinitely dilute solution,

and at any given temperature has a constant value given by the slope of the Henrys
law line, Figure 3.6.1. For this reason it is known as the Henrian coefficient and the value
is independent of composition.
The dissolution of a diatomic gas A2 into a molten metal can be expressed by the
following reaction:
A2 gas 2Ain
K

a2A
pA2

metal

3:6:2
3:6:3

Here, K is the equilibrium constant and pA2 is the partial pressure of A2 gas. For the
condition that the concentration of A in molten metal is sufficiently low to satisfy Henrys
law, the activity coefficient will be constant. Therefore, the solubility of A in the molten
metal is proportional to the square root of the partial pressure of A2:
p
3:6:4
xA pA2
This is known as Sieverts law.
Treatise on Process Metallurgy, Volume 1
http://dx.doi.org/10.1016/B978-0-08-096986-2.00034-5

2014 Elsevier Ltd.

All rights reserved.

557

Takahiro Miki

558

Figure 3.6.1 Illustration of the Raoultian, Henrian and 1 mass% standard states.

3.6.2. HENRIAN ACTIVITIES AND THE CONVERSION

OF STANDARD STATES
During refining processes, solutes or impurities at relatively low concentrations are
usually considered. In these circumstances, it is often convenient to use a scale of activities
defined with respect to Henrys law rather than Raoults law. The Henrian standard state
is located at Xi 1 on the Henrys law line, point B in Figure 3.6.1. This point represents
pure i in the hypothetical nonphysical state in which its activity is defined as unity. The
activity of i in a solution with respect to the Henrian standard state is given by Equation (3.6.5), where superscript H denotes the Henrian standard state. If solute i obeys
Henrys law, the activity coefficient giH which represents the deviation from Henrys
law is unity.
H
aH
i gi xi

3:6:5

As the mole fraction of i is virtually proportional to the mass% of i in a dilute solution,

a third standard state can be defined, which is located at the point on Henrys law line
corresponding to 1 mass% of i, shown as point C in Figure 3.6.1. The activity of i in
a solution with respect to the 1 mass% standard state is given by Equation (3.6.6), where
ai%, fi, and [%i] represent the activity based on the 1 mass% standard state, the

Dilute Solutions

559

corresponding activity coefficient for the deviation from Henrys law on a mass% basis,
and the concentration of i in mass%, respectively,
a%
i fi %i

3:6:6

The standard Gibbs energy change for a reaction will depend on the selected standard
states of the components. The conversion from one standard state to another can be calculated from the difference between the Gibbs energy of the two standard states. For
example, the conversion of the standard state from Raoultian (point A) to Henrian (point
B) can be obtained as follows:
iRaoult; pure liquid iHenry

3:6:7

mi m0i Raoult RT ln ai

3:6:8

mi m0i Henry RT ln aH
i

3:6:9

Here, mi, R, and T are the chemical potential of component i, gas constant, and absolute temperature, respectively. Subtracting Equation (3.6.8) from (3.6.9), the following
equation is obtained:
DGi0 Raoult ! Henry m0i Henry  m0i Raoult RT ln

ai
g
RT ln Hi 3:6:10
aH
g
i
i

0
For infinite dilute solution, gi and gH
i will be gi and 1.

DGi0 Raoult ! Henry m0i Henry  m0i Raoult RT ln g0i

3:6:11

This is the Gibbs energy change accompanying the change in the standard state.
The conversion of the standard state from Henrian (point B) to mass% (point C) is
given as follows:
iHenry iHenry;1 mass%

3:6:12

mi m0i Henry RT lnaH

i

3:6:13

mi m0i mass% RT lna%i

3:6:14

m0i mass%  m0i Henry RT ln

aH
i
a%i

RT ln

gH
i
fi

RT ln

xi
:
%i

3:6:15

xi
M
For infinite dilute solution, gH
i , fi, and %i will be 1, 1, and 100Mi , respectively, where M
is the molecular weight of the solvent and Mi is that of solute i. The Gibbs energy change
accompanying this change in standard state is given by:
DGi0 Henry ! mass% m0i mass%  m0i Henry RT ln

M
100Mi

3:6:16

Takahiro Miki

560

The conversion of the standard state from Raoultian (point A) to mass% (point C) is
given by Equation (3.6.18):
iRaoult;pure liquid iHenry;1 mass%
DGi0 Raoult ! Henry RT ln

g0i M
100Mi

3:6:17
3:6:18

3.6.3. DESCRIPTION OF ACTIVITIES OF MINOR SOLUTE ELEMENTS

IN METALLIC SOLUTION (WAGNERS EQUATION)
The presence of other solutes may have effects in changing the activity coefficient
of a solute in a dilute solution. If solute 2,3, . . ., c are dissolved in solvent 1, a Taylors
expansion of ln g2 as a function of the mole fractions of the solutes is given by
Equation (3.6.19):
lng2 lng02
@ lng2
@ lng2
@ lng2
@ lng2
X3
X4
  Xc
@X2
@X3
@X4
@Xc
!
c
X
1 @ 2 lng2 2 1 @ 3 lng2 3

X
X 
2 @Xi2 i 6 @Xi3 i
i2
!
c
X
@ 2 lng2
Xi Xj  

@Xi @Xj
X2

3:6:19

i2
j3

The interaction parameter for the effect of j on i, eji, is defined by Equation (3.6.20):


@ lngi
j
lim
ei
3:6:20
x1 !1
@Xj T ,p, Xk6j
Also, the following relation is valid:
j

e i eij

3:6:21

If the activity coefficient of solute 2 is influenced by various solutes, it can be

expressed by Equation (3.6.22) as a first approximation:
lng2 lng02 e22 X2 e32 X3 e42 X4   ec2 Xc

3:6:22

When the solute becomes more concentrated or the interactions between the solutes are
strong, the cross terms defined by Equations (3.6.23) and (3.6.24) should be considered

Dilute Solutions

561

!
1
@ 2 lngi
j
ri
lim
2 X1 !1 @Xj2
T ,p, Xk6j
 2

@ lngi
j ,k
ri
lim
X1 !1 @Xj @Xk
T ,p, Xl6j,k

3:6:23
3:6:24

The activity coefficient of solute 2 is expressed by Equation (3.6.25) by considering

the cross terms:
lng2 lng02 e22 X2 r22 X22 e32 X 3 r32 X32 r22,3 X2 X3  

3:6:25

For practical purposes, it is convenient to define an interaction parameter e ji in terms

of the concentration in mass% and logarithms to the base 10:

lim

%1!100

@ log fi
@ %j


j

T ,p, Xk6j

ei

3:6:26

The activity of solute 2 in a solution with respect to the 1 mass% standard state is
expressed by Equation (3.6.27) as a first approximation:
log f2 e22 %2 e32 %3 e42 %4   ec2 %c 

3:6:27

The relation between e ji and e ji is given by Equation (3.6.28), M is the molecular

weight of the solvent and Mi is that of solute i:
j
ei



Mj j
Mj
230 e i 1 
M
M

Also, the cross terms are defined by Equations (3.6.29) and (3.6.30)
!
1
@ 2 logfi
j
ri
lim
2
X
!1
2 1
@ %j T ,p, X
k6j
 2

@ logfi
j,k
lim
r i
X1 !1 @ %j@ %k
T ,p, Xl6j,k

3:6:28

3:6:29
3:6:30

The activity of solute 2 in a solution with respect to the 1 mass% standard state is
expressed by Equation (3.6.31) by considering the cross terms.
log f2 e22 %2 r22 %22 e32 %3 r23 %32 r22,3 %2%3 

3:6:31

Takahiro Miki

562

3.6.4. EXAMPLES FOR THE CALCULATION OF HENRIAN ACTIVITIES

To determine the equilibrium state for a chemical reaction, the equilibrium
constant, K, must be defined:
aA bB cC dD
K

acC adD
aaA abB

3:6:32
3:6:33

Partial pressure, P, will be used instead of activity, a, in Equation (3.6.33) if a gas phase is
involved in the reaction. At equilibrium, the free energy change for the reaction, DG  ,
can be expressed by the following equation:
DG RT ln K

3:6:34

The following example is presented to illustrate the calculation process.

Molten Fe was held in a SiO2 crucible at 1800 K and the equilibrium Si content in Fe
was 0.5 mass%. Calculate the equilibrium oxygen partial pressure. The activity coefficient

of component Si in dilute solution, molar weight of Fe and Si are gSi 0.0008, MFe 56,
and MSi 28, respectively. Also, the free energy change for SiO2 formation at 1800 K is
shown below.
Sil O2 g SiO2 s


DG 557800 J=mol

3:6:35
3:6:36

Interaction between solutes in molten Fe is neglected.

From Equations (3.6.17) and (3.6.18), the free energy of Si dissolution into molten Fe
can be expressed as follows:
Sil Simass%,inFe
DG R ! H,%

3:6:37

g MFe
RT ln Si
100MSi
8:3141800 ln

0:000856
165,300J=mol 3:6:38
10028

From Equations (3.6.35)(3.6.38), the following can be obtained:

Simass%,inFe O2 g SiO2 s

3:6:39

DG 557800  165300 392500J=mol

3:6:40

Dilute Solutions

563

The activity of SiO2 is unity and also activity coefficient fSi is unity because interaction
between solutes can be neglected. Hence, the free energy change can be expressed as
follows:
DG RT ln

aSiO2
1
RT ln
fSi mass%SiPO2
mass%SiPO2

3:6:41

Finally, equilibrium oxygen partial pressure can be determined as follows:

!
1
DG
PO2
exp
RT
mass%Si
!
3:6:42
1
392500
12

exp
8:14  10 atm
0:5
8:3141800

3.6.5. DATA COMPILATIONS FOR DILUTE LIQUID ALLOYS

Considerable data on the thermodynamic behavior of elements in liquid alloys
have been reported. Sigworth and Elliott [14] have summarized the available data on
the thermodynamic behavior of elements in Fe-, Cu-, Ni-, and Co-based alloys. Also,
thermodynamic data for Fe-based alloys have been summarized by The Japan Society for
Promotion of Science [5].

3.6.5.1. The Thermodynamics of Liquid Iron Alloys

Interaction parameters of elements in iron alloys (e ji) at1873 K

j
Ag

Ag 0.04
Al

0.017

Al

As

Au

Be

0.08

0.22

0.043

0.091

As

Ca

Ce

0.047

0.25

Au
B

0.038

0.22

0.244

0.243
(0.14)

Be
C

0.028

0.043

0.043

0.097 0.0026
Continued

Takahiro Miki

564
i

j
Ag

Al

As

Au

0.072

Ca

Be

Ca

0.34

0.002

Ce

0.077

Co

0.02

Cr 0.0024

0.114

Cu

0.066

Ge

0.03

0.013

0.058(0.05)

Ce

0.0039

0.06

Hf
La

0.03

Mg

0.15
0.0236

Mn

0.0538
(0.07)
0.14
(0.097)

Mo
N

0.01
0.018
(0.028)

0.094

0.13

Nb

0.486

Ni

0.032
(0.042)

0.054

0.011

1.17
(3.9)

0.037

Pb

0.021

0.007
(0.005)

0.31
(2.6)
0.015

2.4 0.421
(0.45)

0.066
515

64

110

9.1

0.126
0.1
(0.066)

Pd
Pt
Rh
S

0.041
(0.035)

0.0041 0.0028
(0.0042)

0.134

Sb

0.111
0.11

Sc
Se
Si

0.058

0.2

0.18

0.066

j
Ag

Al

As

Au

Be

Ca

Sn

0.18
(0.37)

Ta

3.5
(0.37)

Ce

Te
Ti
U

0.059

0.14
(0.34)

0.15

Y
Zr
Values in ( ) are from Sigworth and Elliott. Others are from The Japan Society for Promotion of Science.

j
Co

Cr

Cu

Ge

Hf

La

Mg

0.0066

0.07

0.0097

Ag
Al

0.24

As
Au
B

0.58(0.49)

Be
C

0.0075
(0.0009)
{0.0002}

0.023

0.016

0.008 0.67

Ca
0.6

Ce
Co 0.00509
(0.0022)
0.000024

0.022

0.14

Cr 0.019

0.0003

0.016

0.34
(0.33)

Cu

0.018

0.02
(0.023)
0.00013

0.19
(0.24)
Continued

Takahiro Miki

566
i

j
Co

Cr

Cu

Ge
H

Ge

Hf

La

Mg

0.007 0.41
0.0018

0.0024
(0.0022)

0.0013
(0.0005)

0.01

0.027

Hf

0.007

La

4.3

0.0078
0.11

Mg
Mn 0.0036

0.0039

0.34
(0.31)

Mo

0.0003

0.13
(0.20)

0.012

0.046
(1.56/
T  0.00053)

0.009

0.7
(0.61)

Nb
0.0003

Ni

0.36
(0.25)

0.008

0.055
(0.04)
[Cr < 3]
380/
T 0.151
(10.2/
T  0.00487)
[3 < Cr < 30]

0.013

0.73(3.1) 0.28

0.004

0.018
(0.03)

0.035
(0.024)

0.33(0.21)

0.02

0.028

Pb 0

5

0.021
(0.20)

Pd
Pt
Rh
S
Sb
Sc

0.13(0.37)
0.0026

0.0105

0.0084

0.014 0.41(0.12) 0.045 18.3

1.98

Dilute Solutions

567

j
Co

Cr

Cu

Ge

Si

0.0003

0.0144

0.64

Sn

0.015

0.024

0.16(0.12)

Hf

La

Mg

Se

0.47
(4.4)

Ta
Te

1.1

Ti
U
V

0.59

0.0119

0.088

Y
1.2

Zr

j
Mn

Mo

Nb

Nd

Ni

Ag
Al

0.015
(0.058)

As

0.077

Au
B

0.00086

0.73(0.074)

Be
C

0.0084
(0.012)

0.0137
(0.0083)

0.11

0.059

0.01
0.044

Ca
Ce 0.13
Co 0.0042
Cr 0.0039

0.037(0.032)
0.0018

Cu

0.182

0.0002

0.025

Ge
H

0.002
(0.0014)

0.0029(0.0022)

0.0033
(0.0023)

0.038 0.0019(0)
Continued

Takahiro Miki

568
i

j
Mn

Mo

Nb

Nd

Ni

Mn 0

0.0046

0.091

0.0073

0.0072

Mo 0.0048

0.0121

0.1

0.02

0.011

0.068

0.007(0.01)

Nb 0.0093

0.0475
(0.42)

Ni 0.008

0.015(0.028)

0.0007
(0.0009)
0.006

Hf
La

0.28

Mg

0.021

0.005(0.0035)

0.14(0.057) 0.12(0.14)

0.032(0)

0.001

0.13(0.094)

Pb 0.023

0.012

0.003
(0.0002)
0.019

Pd
Pt
Rh
S

0.026

0.0027

Sb

0.01

0.013

0.005

0.043

Sc
Se
Si

0.014
0.0146
(0.002)

2.36

0.092

Sn

0.027

Ta 0.0016

0.685
(0.47)

Te

0.6

Ti

0.043

2.06(1.8)

0.0056

0.455
(0.35)

U
V

Dilute Solutions

569

j
Mn

Mo

Nb

Nd

Ni

0.079
(0.072)

0.0136

Y
4.13

Zr

j
O

Pb

0.033

0.0065

Pd

Pt

Rh

Ag 0.099
Al

1.98
(6.6)

0.035(0.030)

As

0.0037

Au 0.14
(0.11)

0.0051
(0.0037)

0.21
(1.8)

0.008

0.048

Be 1.3
C

0.32
(0.34)

0.051

0.0099
(0.0079)

0.044(0.046)

Ca 580

140

Ce 560

40

Co 0.018

0.0037

0.0031

0.0011

Cr 0.16
(0.14)

0.033
(0.053)

0.0083

0.17
(0.020)

Cu 0.065

0.076
(0.044)

0.0056

0.021

Ge
H

0.026(0.027)
0.05(0.19) 0.015(0.011)

0.0041
(0.0062)

Hf 3.2
La

0.0056
(0.0063)

0.017(0.008)
0.27

43

79

Mg 3
Mn 0.083

0.06
(0.0035)

0.0029

0.048
Continued

Takahiro Miki

570
i

j
O

Mo 0.0083
(0.0007)
N

Pb

0.006

0.0023

Pd

Pt

Rh

0.0006
(0.0005)

0.12(0.05) 0.059(0.045)

Nb 0.72
(0.83)

0.045

Ni 0.01

0.0018
(0.0035)

0.007
0.046
(0.047)
0.0023

0.0036
(0.0037)

0.17
(0.20)

0.07

0.13

0.054(0.062) 0.011

0.034()

0.048

0.32

Pb

0.009

Pd 0.084
Pt

0.0045 0.0136

0.133

0.002

0.0063

0.032

Rh 0.064(0.11)
S

0.27

Sb

0.2

Sc

3.7

0.035(0.29)

0.046

0.0089

0.046
(0.028)
0.0019

Se
Si

0.119
(0.23)

0.09(0.11)

0.01
(0.01)

0.066(0.056)

Sn

0.11

0.036

0.035

0.028

Ta 1.2

0.13
(0.021)

Te
Ti

3.4(1.8)

6.6

0.46
(0.97)

0.042

0.052
(0.052)

0.16

2.6

0.77

Zr

23

0.61(0.16)

0.06

0.27(0.11)
0.53
0.033
(0.028)
0.0005

0.043(0.035)

Dilute Solutions

571

j
Sb

Sc

Se

Si

Sn

Ta

0.022

0.23(0.021)

Te

Ag
Al

0.056

As
Au
B

0.078

Be
C

0.015

0.08
0.096

Ca
Ce
Co
Cr

0.004

0.009

Cu

0.027

0.011

0.027

0.0057

Ge
H

0.0017(0.02)

Hf
La
Mg
Mn

0.0327(0)

Mo

8.05

0.0035

0.007

0.049(0.032)

0.066(0.131)

0.0111

0.1

0.099(0.12)

0.013

Pb

0.048

0.057

0.075(0.063)

0.0044

0.0088

0.006

0.048

Nb

0.01

Ni

0.006

0.023

1.3

0.07

Pd
Pt
Rh
S

0.0037

0.019(0.0002)

Sb
Continued

Takahiro Miki

572
i

j
Sb

Sc

Se

Si

Sn

Ta

Si

0.103

0.017

0.04

Sn

0.057

0.0017

Ta

0.23

Te

Sc
Se

0.11

Te
Ti

2.1

U
V

0.042

W
Y
Zr

j
Ti

0.03(0.077)

0.0056

Zr

Ag
Al

0.011

As
Au
B
Be
C
Ca
Ce
Co
Cr

0.059

0.012

0.019

0.0074

Cu
Ge
H

0.0048

0.0088

Dilute Solutions

573

j
Ti

0.0057

0.0071

Zr

Hf
La
Mg
Mn 0.05
Mo
N

0.6(0.53)

0.123(0.093) 0.002(0.0015)

0.63

Nb
Ni
O

1.12(0.6)

0.04

0.44

0.14(0.3)

0.0085(0.0085)

0.024

0.023

Pb

0.46

4

Pd
Pt
Rh
S

0.18(0.072) 0.067 0.019(0.016) 0.011(0.0097)

0.275 0.21(0.052)

Sb
Sc
Se
Si

1.23

0.025

Sn
Ta
Te
Ti
U
V

0.042(0.013)
0.013
0.0309(0.015)

W
Y
Zr

0.03
0.032

Takahiro Miki

574

Behavior of elements at infinite dilution in liquid iron

Element

Sigworth and Elliott



JSPS

g (1873 K)

DG
M(pure) M(mass%,inFe)
(J/mol)

g
(1873 K)

DG
M(pure) M(mass%,inFe)
(J/mol)

Ag(l)

200

82400  43.8T

200

82400  43.76T

Al(l)

0.029

63200  27.9T

0.049

71100  19.4T

B(s)

0.022

65300  21.5T

0.022

65300  21.55T

C(gr)

0.57

22600  42.3T

0.538

17230  39.87T

Ca(v)

2240

39500 49.4T
0.322

16700  46.44T

Ce(l)
Co(l)

1.07

1000  38.7T

0.55

Cr(l)

1.0

37.7T

1.0

37.70T

Cr(s)

1.14

19200  46.9T

1.14

19200  46.86T

Cu(l)

8.6

33500  39.4T

8.58

33500  39.37T

36500 30.5T

1/2H2(g)
La(l)

36500 30.46T
9.3

Mn(l)

1.3

4080  38.2T

1.44

Mo(l)

42.8T

1.0

Mo(s)

1.86

27600  52.4T

2.2

3600 23.9T

1/2N2(g)

125900  94.6T

9916 20.17T

Nb(l)

1.0

42.7T

0.2

Nb(s)

1.4

23000  52.3T

1.4

23000  52.3T

Ni(l)

0.66

20900  31.0T

0.66

20900  31.1T

1/2O2(g)

117000  2.89T

117110  3.39T

1/2P2(g)

122000  19.2T

157700 5.4T

Pb(l)

1400

213000  106T

837

135000 23.4T

1/2S2(g)

125100 18.5T

Si(l)

0.0013

132000  17.2T

0.0013

Sn(l)

2.8

16000  44.4T

2.58

Ta(l)

0.04

131500  17.24T

Dilute Solutions

575

Ti(l)

0.037

46000  37.0T

0.004

Ti(s)

0.038

31100  45.0T

0.009

U(l)

0.027

56100  50.2T

0.027

56100  50.3T

V(l)

0.08

42300  36.0T

0.08

42300  36.0T

V(s)

0.1

20700  45.6T

0.1

20700  45.6T

W(l)

48.1T

48.1T

W(s)

1.2

31400  63.6T

7.6

Zr(l)

0.037

51000  42.4T

0.037

51000  42.38T

Zr(s)

0.043

34700  50.0T

0.043

34700  50.00T

3.6.5.2. The Thermodynamics of Liquid Copper Alloys

Interaction parameters of elements in copper alloys (e ji) at 1373  1823 K

576

j
Ag

Al

Au

Bi

Ca

Co

Cr

Fe

Ga

Ge

H Mg Mn

Ag 0.005
Al

0.14

Au

0.008
9.0/
T 0.0052

Bi
Ca

0.14
0.029

Fe
Ga

0.028

Ge
H

0.051
0.0006 0.0058 0.0003

0.015

0.0092 0.015

Mg

0.1

Mn
O

0.006

0.03
0

0.015

0.32

20000/
T 10.8

0.012

0.023

125/
T 0.042

414/
T 0.122

Pb
S
Sb
Sn
Tl
Takahiro Miki

Zn

j
Ni

Pb

Pt

0.026

0.088

0.031

0.0084 0.073

Sb

Si

Sn

Te

Tl

Zn

Dilute Solutions

Ag
Al
Au
Bi
Ca
Fe
Ga
Ge
H

0.031 0.042 0.016

0.012

0.029

Mg
Mn
O

169/T 0.079 6230/T 3.43 0.007

Sb
Sn
Tl
Zn

0.164

62

0.019

179/T  0.004

0.062

0.009

0.0006

Pb
S

0.057

159/T 0.069

0.04
0.025
0.008
0.017

577

Takahiro Miki

578

Behavior of elements at infinite dilution in liquid copper

Element

g  (1473 K)

DG
M(pure) M(mass%,inCu)(J/mol)

Ag(l)

3.23

16300  44.0T

Al(l)

0.0028


As(v)

4.8  10

Au(l)

0.14

Bi(l)

1.25

36100  57.9T
4

93500  39.5T
19400  50.6T
24900  63.2T

1.4  10

35800 50.2T

Ca(l)

5.1   10

4

92900  34.3T

Cd(v)

15.6

108000 53.1T

Cd(l)

0.53

7780  42.7T

Co(s)

15.4

33500  37.7T

Cr(s)

43

46000  36.5T

Fe(s)

24.1

54300  47.4T

Fe(l)

19.5

38900  38.8T

Ga(l)

0.034

45200  36.3T

Ge(l)

0.009

66900  32.9T

C(gr)

43500 31.4T

1/2H2(g)
In(l)

0.41

40000  23.3T

Mg(v)

0.08

168000 63.2T

Mg(l)

0.044

36300  31.5T

Mn(l)

0.51

8160  36.9T

Mn(s)

0.53

6490  46.6T

Ni(l)

2.22

9790  37.7T

Ni(s)

2.66

27400  48.1T
85400 18.5T

1/2O2(g)
Pb(l)

5.27

36100  58.6T

Pd(s)

1.3

3350  42.3T

Pt(s)

0.05

42700  43.8T

1/2S2(g)

120000 25.2T

Dilute Solutions

579

Sb(l)

0.014

52300  43.5T

Se(v)

0.002

76200  40.1T

Si(l)

0.006

62800  31.4T

Si(s)

0.01

12100  61.4T

Sn(l)

0.048

37200  43.5T

Te(v)

0.0328

41800  44.1T

Tl(l)

8.5

28200  49.1T

V(s)

130

118000  75.7T

Zn(l)

0.146

23600  38.4T

3.6.5.3. The Thermodynamics of Liquid Cobalt Alloys

Interaction parameters of elements in cobalt alloys (e ji) at 1873 K

580

j
Al

As

Au

Ce

Cr

Cu

Fe

Ge

H Mn

Mo

N Nb

Ni

0.0009

0.54

Al 0.076
C

0.017 0.017 0.006

0.068 0.008 0.015 0.007

0.0013 0.0083

0.0035 0.0053

0.0062

Fe
Ge

0.033

0.014

0.04

0.09

0.003 0.0014

0 0.0035 0.0041

0.043 0.009 0.01

0.008

0
0.07

0.0026

0.009 0.019

0.002

0 0.042 0.024

0.2

0.0011 0

Pd
0.016 0.0034

S
Si

0.05

Ti

0.035

0.007

Pb

Pd

Rh

Ru

Si

Sn

Ta

Te

Ti

Al
C

0.029 0.0018 0.0044 0.0019 0.0008 0.034

0.024 0.01

0.0023 0.014

0.0019 0.021 0.0006

Fe
Ge
H

0.021 0.006 0.0054

0.12

Pd
S
Si
Ti

0.45

0.1
0.28

0.002
0.0036
0.05

0.007
Takahiro Miki

0.133

0.029

0.0064

Dilute Solutions

581

Behavior of elements at infinite dilution in liquid cobalt

Element

g  (1873 K)

DG
M(pure) M(mass%,inCo)
(J/mol)

Al(l)

0.005

91200  27.2T

Au(l)

3.3

18400  48.1T

C(gr)

6.7

20900  20.4T

Cr(s)

0.6

6990  45.6T

Cr(l)

0.53

9960  37.2T

Fe(l)

1.6

12100  27.5T

Ge(l)

0.12

33100  40.0T
35600 31.5T

1/2H2(g)
Mn(l)

1.0

37.7T
41800 21.9T

1/2N2(g)
Ni(l)

0.53

1260  44.1T

Ni(s)

0.47

18800  54.4T
61600  9.71T

1/2O2(g)
Pb(l)

370

92100  48.7T

Pd(l)

1.9

29300  53.6T

Pt(s)

0.03

54400  48.1T
135000 30.3T

1/2S2(g)
Si(l)

0.0017

146000  7.03T

Sn(l)

0.34

16700  43.9T

Ti(l)

0.0009

109000  36.6T

Ti(s)

0.00091

94100  44.4T

V(l)

0.048

47200  37.0T

V(s)

0.06

25700  46.6T

W(l)

1.4

5400  47.6T

W(s)

4.3

40800  57.2T

3.6.5.4. The Thermodynamics of Liquid Nickel Alloys

Interaction parameters of elements in nickel alloys (e ji) at 1873 K

582

j
Al

Al

Au

Ca

Ce

Co

Cr

Cu

Fe

Ga

0.013 0.004

0.012 0.021

0.059

0.035

0.0083

0.01

0.027 0.017 0.004

0.006 0.001

0.064
0.004

Co

Cu

0.009 0.0017
0.04

0.0076

Fe

0.013
0.014

0.0076

0.0031

0.0036

0.0017

Mg

0.0024

0.0096

0.03
0.55

O
S

Mn

Cr

H In

0.003

Ca

Ge

0.08

Au
C

As

0
0.133

0.57

0.0054 0.11

0.02

0.006

0.2

0.008 0.029

0.007

0.03

0.0003

0.45

0.005

Si

Takahiro Miki

Dilute Solutions

j
Mo

Pd

Pt

0.04

0.002

0.003

Sb

Se

Si

Sn

Te

Ti

Zn

0.012

0.011

0.031

0.01

0.008

0.022

0.015

0.001

0.008

0.013

0.011

Al
Au
C

0.005

Ca

0.086

Co
Cr

0.09

0.06

Cu
Fe
H

0.011

0.033

Mg
N

0.04

O
S
Si

0.2

0
0

0.053

0.089
0.028

0.137

0.46
0.048

0.26

0.24

0.4

0.16

0.11

583

Takahiro Miki

584

Behavior of elements at infinite dilution in liquid nickel

Element

g  (1873K)

DG
M(pure) M(mass%,inNi)(J/mol)

Al(l)

0.0002

155000  19.3T

Au(l)

1.62

7530  48.3T

B(s)

0.0016

59400  46.0T

B(l)

0.009

110000  24.2T

C(gr)

0.31

20800  46.0T

Ca(l)

0.6

8030  35.0T

Ca(v)

1.27

186000 66.4T

Co(l)

0.45

1260  45.5T

Cr(s)

0.46

10500  49.6T

Cr(l)

0.39

9210  40.1T

Cu(l)

2.18

12100  38.9T

Fe(l)

0.36

41800  24.1T

Ge(l)

0.13

31300  40.0T
20100 35.0T

1/2H2(g)
Mg(l)

0.32

17600  30.9T

Mg(v)

2.2

163000 62.6T

Mn(l)

37.7T

Mo(s)

2.1

32600  53.5T

Mo(l)

42.3T

1/2N2(g)

27900 39.7T

1/2O2(g)

71000 1.41T

Pb(l)

1.4

5020  48.7T

Pd(s)

1.35

4690  43.1T
119000 15.1T

1/2S2(g)
Si(l)

0.000015

176000  30.3T

Sn(l)

0.14

105000  4.48T

Ti(s)

0.00019

118000  44.6T

V(s)

0.011

52100  46.7T

Dilute Solutions

585

V(l)

0.009

73600  37.0T

W(s)

13.5

69000  62.9T

W(l)

11.3

37700  47.7T

Zr(s)

0.00007

289000 32.9T

REFERENCES
[1]
[2]
[3]
[4]
[5]

G.K. Sigworth, J.F. Elliott, Metal Sci. 8 (1974) 298.

G.K. Sigworth, J.F. Elliott, Can. Met. Q. 13 (1974) 455.
G.K. Sigworth, J.F. Elliott, Can. Met. Q. 15 (1976) 123.
G.K. Sigworth, J.F. Elliott, G. Vaughn, G.H. Geiger, Can. Met. Q. 1617 (19771978) 104.
The Japan Society for Promotion of Science, The 19th Committee in Steelmaking: Steelmaking Data
Sourcebook, Gordon and Breach Science Publishers, New York, 1988.