Chemical Thermodynamics of Tin - Volume 12 - OECD Nuclear ...

II.1 Symbols, terminology and nomenclature 17
For the addition of a ligand, the notation shown in Eq. (II.7) is used.
HL + L HL
q−1
q
K
q
⎡HL
=
⎣ q
⎤
⎦
⎡HL
⎤⎡⎣
L ⎤⎦
⎣ q−1
⎦
Eq. (II.8) refers to the overall formation constant of the species HL
r q
.
(II.7).
+
r q
r H + q L HrL
q
qr ,
=
+
r q
⎡HL
⎤
β
⎣ ⎦
(II.8).
⎡
⎣H
⎤
⎦
⎡
⎣L
⎤
⎦
In Eqs. (II.5), (II.6) and (II.8), the second subscript r can be omitted if r = 1, as
shown in Eq. (II.7).
Example:
H + PO HPO
+ 3−
2−
4 4
⎡HPO
⎤
⎡
⎣
⎤⎡
⎦⎣
⎤
⎦
2−
4
1,1
=
1
=
⎣ ⎦
+ 3−
H PO4
β β
2 H + PO H PO
+ 3−
−
4
2 4
β
=
−
⎡
⎣HPO⎤
2 4⎦
1,2
+
2
3−
H PO4
⎡
⎣
⎤
⎦
⎡
⎣
⎤
⎦
II.1.7.2 Formation of metal complexes
ML + L ML
q−1
q
K
q
=
⎡
⎣ML
⎤
q ⎦
⎡ML
⎤⎡L
⎤
⎣ q−1
⎦⎣ ⎦
(II.9)
M + q L ML
q
⎡ML
⎤
q
β
q
=
⎣ ⎦
(II.10)
q
⎡
⎣M
⎤⎡
⎦⎣L
⎤
⎦
For the addition of a metal ion, i.e., the formation of polynuclear complexes, the following
notation is used, analogous to Eq. (II.5):
M + M L M L
m−1
m
1, m
K
=
⎡
⎣M L ⎤
m ⎦
⎡M ⎤⎡M L ⎤
⎣ ⎦⎣ m−1
⎦
(II.11)
Eq. (II.12) refers to the overall formation constant of a complex M L
m q .
⎡M L ⎤
m q
m M + q L MmL
q
β
qm ,
=
⎣ ⎦
(II.12)
m q
⎡
⎣M
⎤
⎦
⎡
⎣L
⎤
⎦
The second index can be omitted if it is equal to 1, i.e., βqm
,
becomes β
q
if
m = 1. The formation constants of mixed ligand complexes are not indexed. In this case,
CHEMICAL THERMODYNAMICS OF TIN, ISBN 978-92-64-99206-1, © OECD 2012