Amphoteric behavior of di-2-pyridyl ketone benzoylhydrazone in ethanol-water mixtures*
Main Article Content
Abstract
The ligand di-2-pyridyl ketone benzoylhydrazone (DPKBH) is widely used for the determination of transition metal ions in environmental samples. Due to its low solubility in water it is used in aqueous-ethanol (1:1) solvent and for higher sensitivity the pH must be properly adjusted. The properties of DPKBH solutions must be known at different ethanol-water percentages in order to achieve higher sensitivity and/or selectivity for metal analysis. The acid-base behavior of this reagent in aqueous-ethanol solvent and the dissociation/ionization constants (pK1 and pK2) of DPKBH have been determined in different aqueous-ethanol solvent mixtures (10, 20, 30 and 50 % V/V of ethanol) from potentiometric titrations at 25.0 ± 0.1° C. As the amount of ethanol increases from 10 to 30% the pK1 and pK2 values increased, but they decreased in 50% of the organic solvent. The results are correlated with the medium composition and its effects.
Metrics
Article Details
This work is licensed under a Creative Commons Attribution 4.0 International License.
The corresponding author transfers the copyright of the submitted manuscript and all its versions to Eclet. Quim., after having the consent of all authors, which ceases if the manuscript is rejected or withdrawn during the review process.
When a published manuscript in EQJ is also published in other journal, it will be immediately withdrawn from EQ and the authors informed of the Editor decision.
Self-archive to institutional, thematic repositories or personal webpage is permitted just after publication. The articles published by Eclet. Quim. are licensed under the Creative Commons Attribution 4.0 International License.
References
AHMED, I.T., EL-ROUDI, O.M., BORAEI, A. A. A., IBRAHIM, S. A. Equilibrium studies of the ternary complex systems Mn+ + dipicolinic acid + N-(2-acetamide)iminodiacetic acid or amino acids J. Chem. Eng. Data (Washington), v.41, p.386-90, 1996. [ Links ]
ALBERT, A., SERJEANT, E.P. Ionization Constants of Acids and Bases. New York: John Willey & Sons Inc., 1962. p. 1-41. [ Links ]
Al-NURI, M.A., ABU-EID, M., ZATAR, N.A., KHALAF, S., HANNOUN, M. Spectrophotometric determination of cobalt in aqueous solution using di-2-pyridyl ketone derivates. Anal. Chim. Acta. (Amsterdam), v.259, p.175-9, 1992. [ Links ]
BATES, R.G. The modern meaning of pH. Crit. Rev. Anal. Chem. (Amsterdam), v.10, p.247-78, 1981. [ Links ]
BATES, R.G. Determination of pH, Theory and Practice, New York: John Wiley, 1964. 435p. [ Links ]
BATES, R.G., PAABO, M., ROBINSON, R.A. Interpretation of pH measurements in acohol-water solvents. J. Phys.Chem. (Washington), v.67, p.1833-8, 1963. [ Links ]
BENET, L.Z., GOYAN, J.E. Potentiometric determination of dissociation constants. J. Pharm. Sci., v.56, p.665-80, 1967. [ Links ]
BERTOTTI, M., TOKORO, R. Potentiometric studies of indium(III) azide complexes in aqueous medium. Talanta (Great Britain), v.36, p.424-6, 1989. [ Links ]
BROUTY-CABANE, F. Dosage du cuivre dans le sulfure de cadmium. Anal. Chim. Acta (Amsterdam), v.47, p.511-6, 1969. [ Links ]
BROWN, G., ROHLE, R.K. Spectrophotometric determination of copper in lead, tin, aluminum, zinc, and their alloys with biscyclohexanone oxalyldihydrazone. Anal. Chem.(Washington), v.38, p.911-3, 1966. [ Links ]
BUDESINSKY, B. Analytical determination of carbonyl group. Chem. Listy (Prague), v.54 p.916-46, 1960. [ Links ]
CAMERON, A.J., GIBSON, N.A. Metal-pyridine-2-aldehyde-2`-pyridylhydrazone complexes as visual acid-base indicators. Anal. Chim. Acta (Amsterdam), v.51, p.249-56,1970. [ Links ]
CAMERON, A.J., GIBSON, N.A. Metal-pyridine-2-aldehyde-2`-pyridylhydrazone complexes as visual acid-base indicators. Anal. Chim. Acta (Amsterdam), v.51, p.257-63, 1970. [ Links ]
CHATTOPADHYAY, A.K., LAHIRI, S. C. Studies on the solvatation of amino acids in ethanol and water mixtures. Eletrochim. Acta (Great Britain), v.27, p.269-72, 1982. [ Links ]
COETZEE, J.F. and RITCHIE, C.D. Solute-Solvent Interactions. New York: Editors Dekker, 1969. 653p. [ Links ]
EL-GYAR, S.A, HAMED, M.M.A., ABDALLA, E.M., MAHMOUD, M.R. Medium effects on the acid dissociation constants of some diimine heterocyclic bases. Monatshefte für Chemie (Austria), v.124, p.127-33, 1993. [ Links ]
EREL, Y., PEHKONEN, S.O., HOFFMANN, M. R. Redox chemistry of iron in fog stratus clouds. J. Geophys.Res. (California), v.98 (D10), p.18423-34, 1993. [ Links ]
GARCIA-VARGAS, M., BELIZÓN, M., HERNÁNDEZ-ARTIGA, M.P., MARTINEZ, C., PÉREZ-BUSTAMANTE, J.A. Ligands with the "ONNN" group as chelanting and preconcentrating substances of heavy metal ions: aroylhydrazone derivates from di-2- pyridyl ketone. Applied Spectroscopy(Washington), v. 40, p.1058-62, 1986. [ Links ]
GOING, J.E., PFLAUM, R.T. Spectrophotometric studies of complexes of 2-benzoylpyridine-2-pyridylhydrazone. Anal. Chem. (Washington), v.42, p.1098-100,1970. [ Links ]
GRASES, F., GARCIA-SANCHEZ, F., VARCARCEL, M. Fluorimetric determination of copper and mercury based on their catalytic effects on the autoxidation of 2,2`- dipyridylketone hydrazone. Anal. Chim. Acta (Amsterdam), v.119, p.359-65, 1980. [ Links ]
HARNED, H.S., OWEN, B.B. The Physical Chemistry of Eletrolytic Solutions New York: Reinhold Pub. Cap. 1943. p.118. [ Links ]
HAYWOOD, L.J.A., SUTCLIFFE, P. Determination of copper in steel. The Analyst (Cambridge), v.81, p.651-5, 1956. [ Links ]
HAZRA, D.K., LAHIRI, S.C. Studies on the dissociation constants of 2,2`-dypyridyl and its iron (II) complex in ethanol-water mixtures. J. Indian Chem. Soc. (India), v. 53, p. 787-92, 1976. [ Links ]
HEDWING, G.R., POWELL, H.K.J. Direct potentiometric measurement of hydrogen ion concentrations in sodium chloride solutions of fixed ionic strength. Anal. Chem.(Washington), v.43, p.1206-12, 1971. [ Links ]
KATYAL, M., DUTT, Y. Analytical aplications of hydrazones. Talanta (Great Britain), v.22, p.151-66, 1975. [ Links ]
KILIÇ, E., KOSEOGLE, F., BASGUT, O. Protonation constants of some pyridine derivates in ethanol-water mixtures. Anal. Chim. Acta (Amsterdam), v. 294, p.215-20, 1994. [ Links ]
KOUIMTZIS, T.H.A., APOSTOLOPOULOS, C., STAPHILAKIS, I. Spectrophotometric determination of cobalt in sea water and brines by solvent extraction with 2,2`- dipyridyl-2'-pyridylhidrazone Anal. Chim. Acta (Amsterdam), v.113, p.185-8, 1980. [ Links ]
LOPES, C.F.F., NEVES, E.A., SUÁREZ-IHA, M.E.V. Potentiometric study of acetate complexes of lanthanum (III). Analytical Letters (New York), v.27, p. 1749-61, 1994. [ Links ]
MIDDLETON, K.R. Colorimetric determination of copper in plants. The Analyst (Cambridge), v.90, p.234-40, 1965. [ Links ]
MOHAN, M, GUPTA, M.P., CHANDRA, L., JHA, N. K. Synthesis, characterization and antitumor properties of some metal (II) complexes of 2-pyridinecaborxaldehyde 2`- pyridylhydrazone and related compounds. Inorg. Chim. Acta (Switzerland), v.151, p.61-8, 1988. [ Links ]
MOLINA, M., ANGST, M., GARCIA, E.K., MELIOS C.V. Influence du solvent sur la stabilité des ions complexes-II; Interaction de l’argent (I) avec la pyridine en solutions d’éthanol-eau. J. Inorg. Nucl. Chem (Great Britain), v.34, p.3215-20, 1972. [ Links ]
MOLODYKH, Zh.V., BUZYKIN, B.I., BYSTRYKN, N.N., KITAEV, Yu.P. Anthelmintic activity of some hydrazones, phthalazones, and phthalazinylhydrazones in rice with nippostrongylus infestation. Khim. Farm. Zh (Moscow), v.11, p.37-40, 1978. [ Links ]
NAKANISHI, T., OTOMO, M. Extraction-spectrophotometric determination of paladium (II) with di-2-pyridyl ketone benzoylhydrazone. Anal. Sci. (Japan), v.1, p.161-3, 1985. [ Links ]
NAKANISHI, T., OTOMO, M. Solvent extraction and spectrophotometric determination of iron (II) with di-2-pyridyl ketone benzoylhydrazone. Microchemical J.(Florida), v.33, p.172-8, 1986. [ Links ]
NEVES, E.F.A., SILVA, T.V.: Accurate determination of the hydrogen ion in the presence of hydrolisable metal cations. In: IV SIMPÓSIO BRASILEIRO DE ELETROQUÍMICA E ELETROANALÍTICA, 1984, São Carlos. Anais... p.63-8. [ Links ]
NIAZI, M.S.K., MOLIN, J. Dissociation constants of some amino acid and pyridinecarboxylic acids in ethanol-H2O mixtures. Bull. Chem. Soc. Japan (Japan), v.60, p.2605-10, 1987. [ Links ]
PEHKONEN, S.O., EREL, Y., HOFFMANN, M.R. Simultaneous spectrophotometric measurement of Fe (II) and Fe (III) in atmospheric water. Environ. Sci.Technol (Washington),v.26, p.1731-6, 1992. [ Links ]
PETERSON, R.E., BOLLIER, M.E. Spectrophotometric determination of serum copper with biscyclohexanoneoxalyldihydrazone. Anal. Chem (Washington), v.27, p.1195-7, 1955. [ Links ]
ROSSI, M.V., SUÁREZ-IHA, M.E.V., HOFFMANN, M.R. Spectrophotometric determination of the stability constants of Co(II) and DPKBH (di-2-pyridyl ketone benzoylhydrazone). Spectroscopy Letters (New York), v. 28, p.1153-66, 1995. [ Links ]
SHEDLOVSKY, T. in "Eletrolytes" New York. Editors.: Pergamon Press, 1962 p. 146-51. [ Links ]
SHOHRE, R., RAMIN, R., HASHEM, S., MOJTABA, S., GHOLOMHOSSEIN, R. Spectrophotometric determination of acidity constants of some anthraquinone derivates in binary methanol-water mixtures. Microchemical J. (Florida), v.52, p.22-5, 1995. [ Links ]
SINH, R.B., JAIN, P. Hydrazones as analytical reagents: a review. Talanta (Great Britain), v.29, p. 77-84, 1982. [ Links ]
SOMERS, E., GARRAWAY, J.J. Modifications in the method of determining copper with bis-cyclo-hexanone oxalyldihydrazone. Chem. Ind. (London), v.30, p.395, 1957. [ Links ]
SUÁREZ-IHA, M.E.V., PEHKONEN, S.O., HOFFMANN, M.R. Stability, stoichiometry, and structure of Fe(II) and Fe(III) complexes with di-2-pyridyl ketone benzoylhydrazone. Environ. Sci.Technol (Washington ), v.28, p.2080-6, 1994. [ Links ]
TERENT’EV, V.A.; ANDREEVA, R.K. A spectrophotometric method for determining total carbonyl compounds by means of 2,4-dinitroohenylhydrazine. Zh. Anal. Khim. (Moscow), v.33, p.959-61, 1968. [ Links ]
TERRA, L.H.S.A., SUÁREZ-IHA, M.E.V. A new spectrophotometric method with di-2- pyridyl ketone benzoylhydrazone for determination of nickel (II). Spectroscopy Letters (New York), v.30, p.625-39, 1997. [ Links ]
TERRA, L.H.S.A., AREIAS, M.C.C., GAUBEUR, I., SUÁREZ-IHA, M.E.V. Solvent extraction-spectrophotometric determination of nickel(II) in natural waters using di-2-pyridyl ketone benzoylhydrazone. Spectroscopy Letters (New York), v.32, p.257-71, 1999. [ Links ]
YASUDA, M. Dissociation constants of some carboxylic acids in mixed aqueous solvents. Bull. Chem. Soc. Japan (Japan), v.32, p. 429-32, 1959. [ Links ]
ZATAR, N.A., MOHMMED, F.M., AL-NURI, A., ABU-EID, M., HANNOUN, M., ABU-ZUHRI, A. Z, KHALAF, S., KRAMIS, M. Spectrophotometric determination of cobalt with di-2-pyridyl ketone benzoylhydrazone. Spectroscopy Letters (New York), v.24, p.1145-52, 1991. [ Links ]
ZATAR, N.A., ABU-ZUHRI, A. Z., AL-NURI, M.A., MAHMOUD, F.M., ABU-OBAID, A.A. Simultaneous spectrophotometric determination of iron (II) and iron (III) in mixture using di-2-pyridyl ketone benzoylhydrazone. Spectroscopy Letters (New York), v.22, p.1203-14, 1989. [ Links ]