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Guide to
the Realization of the ITS-90
APPENDIX 1
alA
lA 0 RT ln ,
0 (A1.2)
lA
a
lA
asA
sA 0 RT ln .
0
(A1.3)
sA
a
sA
In these expressions, a is the symbol for the chemical activity, and the zero marks the
reference values. If the pure host material A is used as the reference, one has
0
asA alA
0
1 , and (A1.4)
with GMA being the free enthalpy of fusion of material A. For ideal solutions, the
chemical activity a is equal to the concentration c. In a binary system, the
concentrations of the components A and B are directly linked: csA = 1-csB and
clA = 1-clB. From Equations (A.1) to (A.5) it follows in this case:
1 csB
GMA RT ln . (A1.6)
1 clB
For small concentrations of component B, the following approximation can be used:
1 csB (A1.7)
ln (clB csB ) .
1 clB
The application of the Gibbs-Helmholtz equation (G = H – TS) to the melting
yields
GMA H MA T SMA , (A1.8)
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Guide to the Realization of the ITS-90
Fixed Points: Influence of Impurities – Appendix 1
where HMA is the enthalpy of fusion and SMA = HMA/TMA is the entropy of fusion
(TMA melting temperature of the pure material A). Since the equilibrium distribution
coefficient is defined by k0B csB / clB , Equations (A.6) to (A.8) yield
H MA (TMA T )
k0B 1 . (A1.9)
RTclBTMA
H MA (TMA T ) (T T ) (A1.10)
k0B 1 2
1 A MA .
RTMA clB clB
In Equation (10), A is the first cryoscopic constant. Since the ratio (T-TMA)/clB is
practically equal to the slope of the liquidus line mlB l / clB , one obtains finally
the following approximate relation
In summary, the following assumptions were made for deriving Equation (A.11) at
low concentrations of component B: (i) ideal solution, (ii) Relation (7), (iii) T TMA,
and (iv) HMA is independent of concentration and temperature.
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