250
C. De Stefano· C. Foti . A. Gianguzza . D. Piazzese . S. Sammartano
but can be considerable for the metallic and organometallic cations. A recent investigation (Foti et al. 2000) showed that the addition of carbonate ([CO~-] + [HCO;]
= 2.7 mmol rl, for sea water 35 S) to the basic inorganic speciation model of organotins
in synthetic sea water leads to the formation (at pH = 8) of a very stable mixed species (CH3)Sn(C03)(OHh in the monomethyltin system, whilst it is absolutely negligible for the other dimethyl and trimethyltin systems at the same pH value
(see Table A9.8, Sect. A9.2 of appendix). Interactions of organotin cations and hydroxo
species with floride ions ([F-] = 0.07 mmol rI, for sea water 35 S) are very weak, and
no complex species are formed.
As concerns the possibility of having predictive relationships, we showed that
polycarboxylic anions form complexes whose stability follows very regular trends.
Moreover, apparent protonation constants can be expressed as a function of salinity
by simple polynomial equations, whose empirical parameters mainly depend on the
protonation step.
References
Armstrong FAJ (1965) Phosphorus. In: Riley JP, Skirrow G (eds) Chemical oceanography, 1st edn, vol I.
Academic Press, New York, pp 323-364
Atlas E, Culberson C, Pytkowicz RM (1976) Phosphate association witii Na +, Ca2+ and Mg2+ in seawater.
Mar Chern 4:243-254
Bates RG, Calais JG (1981) Thermodynamics of the dissociation of BisH+ in seawater from 5 to 40°C.
J Sol Chern 10(4):269-279
Bates RG, Erickson WP (1986) Thermodynamics of the dissociation of 2-aminopyridinium ion in synthetic seawater and a standard for pH in marine systems. J Sol Chern 15(11):891-901
Bremmer JM (1967) In: Mc Laren AD, Peterson GH (eds) Soil Biochemistry, vol I. Marcel Dekker,
New York
Buffle J (1988) Complexation reactions in aquatic systems - an Analytical approach. Ellis Horwood Series in Analytical Chemistry, Chichester, England
Campbell JW, Goldstein L (eds) (1972) Nitrogen metabolism and the environment. Academic Press,
London
Casale A, De Robertis A, De Stefano C, Gianguzza A (1989) Thermodynamic parameters for tlIe formation of calcium a-alalinate complexes in aqueous solution. Thermochim Acta 140:59-66
Casale A, Foti C, Sammartano S, Signorino G (1998) Thermodynamic parameters for the protonation
of some polyamines C(2n_2jNnH(Sn_2j in NaCI aqueous solution at different ionic strengtiis. Ann Chim
(Rome) 88:55-70
Craig PJ, Miller D (1997) Analysis and speciation of organometallic compounds in tlIe marine environment. In: Gianguzza A, Pelizzetti E, Sammartano S (eds) Marine chemistry - an environmental analytical chemistry approach. Kluwer Academic, Dordrecht (Water Science and Technology Library,
vol XXv, pp 161-172)
Culberson C, Pytkowicz RM, Hawley JE (1970) Seawater alkalinity determination by tlIe pH method.
J Mar Res 28:15-21
Czerminski JB, Dickson AG, Bates RG (1982) Thermodynamics of tlIe dissociation of morpholinium ion
in seawater: J Sol Chern 11(2):79-89
Daniele PG, De Robertis A, De Stefano C, Sammartano S, Rigano C (1985) On tlIe possibility of determining the thermodynamic parameters for the formation of weak complexes using a simple model
for tlIe dependence on ionic strengtii of activity coefficients. Na +, K+ and Ca 2 + complexes of low
molecular weight ligands in aqueous solution. J Chern Soc Dalton Trans 2353-2361.
Daniele PG, De Stefano C, Prenesti E, Sammartano S (1994) Weak complex formation in aqueous solution. Curr Top Sol Chern 1:95-106
Daniele PG, Prenesti E, De Stefano C, Sammartano S (1995) Formation and stability of proton-amineinorganic anion complexes in aqueous solution. J Solution Chern 24:325-341
Daniele PG, Prenesti E, De Robertis A, De Stefano C, Foti C, Giuffre 0, Sammartano S (1997) Binding of
inorganic and organic polyanions by protonated open chain polyamines in aqueous solution. Ann
Chim (Rome) 87:415-447 (Errata corrige (1998) 88:447-448)
C. De Stefano· C. Foti . A. Gianguzza . D. Piazzese . S. Sammartano
but can be considerable for the metallic and organometallic cations. A recent investigation (Foti et al. 2000) showed that the addition of carbonate ([CO~-] + [HCO;]
= 2.7 mmol rl, for sea water 35 S) to the basic inorganic speciation model of organotins
in synthetic sea water leads to the formation (at pH = 8) of a very stable mixed species (CH3)Sn(C03)(OHh in the monomethyltin system, whilst it is absolutely negligible for the other dimethyl and trimethyltin systems at the same pH value
(see Table A9.8, Sect. A9.2 of appendix). Interactions of organotin cations and hydroxo
species with floride ions ([F-] = 0.07 mmol rI, for sea water 35 S) are very weak, and
no complex species are formed.
As concerns the possibility of having predictive relationships, we showed that
polycarboxylic anions form complexes whose stability follows very regular trends.
Moreover, apparent protonation constants can be expressed as a function of salinity
by simple polynomial equations, whose empirical parameters mainly depend on the
protonation step.
References
Armstrong FAJ (1965) Phosphorus. In: Riley JP, Skirrow G (eds) Chemical oceanography, 1st edn, vol I.
Academic Press, New York, pp 323-364
Atlas E, Culberson C, Pytkowicz RM (1976) Phosphate association witii Na +, Ca2+ and Mg2+ in seawater.
Mar Chern 4:243-254
Bates RG, Calais JG (1981) Thermodynamics of the dissociation of BisH+ in seawater from 5 to 40°C.
J Sol Chern 10(4):269-279
Bates RG, Erickson WP (1986) Thermodynamics of the dissociation of 2-aminopyridinium ion in synthetic seawater and a standard for pH in marine systems. J Sol Chern 15(11):891-901
Bremmer JM (1967) In: Mc Laren AD, Peterson GH (eds) Soil Biochemistry, vol I. Marcel Dekker,
New York
Buffle J (1988) Complexation reactions in aquatic systems - an Analytical approach. Ellis Horwood Series in Analytical Chemistry, Chichester, England
Campbell JW, Goldstein L (eds) (1972) Nitrogen metabolism and the environment. Academic Press,
London
Casale A, De Robertis A, De Stefano C, Gianguzza A (1989) Thermodynamic parameters for tlIe formation of calcium a-alalinate complexes in aqueous solution. Thermochim Acta 140:59-66
Casale A, Foti C, Sammartano S, Signorino G (1998) Thermodynamic parameters for the protonation
of some polyamines C(2n_2jNnH(Sn_2j in NaCI aqueous solution at different ionic strengtiis. Ann Chim
(Rome) 88:55-70
Craig PJ, Miller D (1997) Analysis and speciation of organometallic compounds in tlIe marine environment. In: Gianguzza A, Pelizzetti E, Sammartano S (eds) Marine chemistry - an environmental analytical chemistry approach. Kluwer Academic, Dordrecht (Water Science and Technology Library,
vol XXv, pp 161-172)
Culberson C, Pytkowicz RM, Hawley JE (1970) Seawater alkalinity determination by tlIe pH method.
J Mar Res 28:15-21
Czerminski JB, Dickson AG, Bates RG (1982) Thermodynamics of tlIe dissociation of morpholinium ion
in seawater: J Sol Chern 11(2):79-89
Daniele PG, De Robertis A, De Stefano C, Sammartano S, Rigano C (1985) On tlIe possibility of determining the thermodynamic parameters for the formation of weak complexes using a simple model
for tlIe dependence on ionic strengtii of activity coefficients. Na +, K+ and Ca 2 + complexes of low
molecular weight ligands in aqueous solution. J Chern Soc Dalton Trans 2353-2361.
Daniele PG, De Stefano C, Prenesti E, Sammartano S (1994) Weak complex formation in aqueous solution. Curr Top Sol Chern 1:95-106
Daniele PG, Prenesti E, De Stefano C, Sammartano S (1995) Formation and stability of proton-amineinorganic anion complexes in aqueous solution. J Solution Chern 24:325-341
Daniele PG, Prenesti E, De Robertis A, De Stefano C, Foti C, Giuffre 0, Sammartano S (1997) Binding of
inorganic and organic polyanions by protonated open chain polyamines in aqueous solution. Ann
Chim (Rome) 87:415-447 (Errata corrige (1998) 88:447-448)