Abstract
2-Keto-D-gluconate (kG) is naturally produced in soils, sediments and rock faces through the microbial oxidation of glucose. Studies have qualitatively shown kG to enhance the dissolution of soil minerals. However, quantitative information, such as the log K values for the formation of metal–kG complexes, are not available. This paper presents the results of potentiometric titration studies that employ H+ and Ca2+ ion selective electrodes (ISEs) to determine the conditional ion association constants (log Q values) for the protonation and deprotonation of kG and the formation of Ca–kG complexes. The experimentally-determined log Q values were then converted to the corresponding ion association constants (the zero ionic strength condition; log K values) by employing a modified Davies equation for charged species and the Setchenów equation for neutral species. The log K values were determined by potentiometric titrations at constant kG concentration, varied ionic strengths, 25 or 22 ∘C, and in the absence of CO2. The computer model GEOCHEM-PC was used to determine the aqueous speciation of ions other than kG and the computer model FITEQL was used to estimate conditional log Q values for reactions in the various chemical models. Based on our evaluations, equilibrium constants for the following reactions were determined: H++ kG– ⇌ HkG0, log Ka1 = (3.00 ± 0.06), kG–⇌ H–1kG2–+ H+, log Ka–1 = –(11.97 ± 0.41), and Ca2++ kG–⇌ CakG+, log K101 = (1.74 ± 0.04).
Similar content being viewed by others
References
P. M. Huang and A. Violante, in Interactions of Soil Minerals With Natural Organics and Microbes, P. M. Huang and M. Schnitzer, eds. (SSSA Special Publication No. 17, SSSA, Madison, WI, 1986), pp. 159–221.
J. S. Geelhoed, T. Hiemstra, and W. H. Van Riemsdijk, Environ. Sci. Technol. 32, 2119 (1998).
M. Grafe, M. J. Eick, P. R. Grossl, and A. M. Sanders, J. Environ. Qual. 31, 1115 (2002).
U. Kafkafi, B. Bar-Yosef, R. Rosenberg, and G. Sposito, Soil Sci. Soc. Am. J. 52, 1585 (1988).
H. Wijnja and C. P. Schulthess, Soil Sci. Soc. Am. J. 64, 898 (2000).
H. L. Yao and H. H. Yeh, Langmuir 12, 2981 (1996).
T. R. Fox, N. B. Comerford, and W. W. McFee, Soil Sci. Soc. Am. J. 54, 1763 (1990).
W. P. Inskeep and J. C. Silvertooth, Soil Sci. Soc. Am. J. 52, 941 (1988).
K. Inoue and P. M. Huang, Soil Sci. Soc. Am. J. 50, 1623 (1986).
D. L. Jones, Plant Soil 205, 25 (1998).
R. B. Duff, D. M. Webley, and R. O. Scott, Soil Sci. 95, 105 (1963).
A. Moghimi, M. E. Tate, and J. M. Oades, Soil Biol. Biochem. 10, 283 (1978).
G. F. Vance, F. J. Stevenson, and F. J. Sikora, in The Environmental Chemistry of Aluminum, G. Sposito, ed. (Lewis, Boca Raton, FL, 1995), pp. 169–220.
S. Banik and B. K. Dey, Zbl. Mikrobiol. 138, 437 (1983).
T. Chiyonobu, O. Adachi, and M. Ameyama, Agric. Biol. Chem. 37, 2871 (1973).
H. L. Erlich, in Geomicrobiology, H. L. Ehrlich, ed. (Marcel Dekker, New York, 1981), pp. 131–135.
A. K. Halder and P. K. Chakrabartty, Folia Microbiol. 38, 325 (1993).
R. Klasen, S. Bringer-Meyer, and H. Sahm, Biotechnol. Bioeng. 40, 183 (1992).
R. M. N. Kucey, H. H. Janzen, and M. E. Leggett, Adv. Agron. 42, 199 (1989).
O. M. Neijssel and D. W. Tempest, Arch. Microbiol. 105, 183 (1975).
J. R. Sokatch, Bacterial Physiology and Metabolism (Academic, London, 1969), pp.117–119.
D. M. Webley and R. B. Duff, Plant Soil 22, 307 (1965).
A. Moghimi, M. E. Tate, and J. M. Oades, Soil Biol. Biochem. 10, 283 (1978).
M. E. Essington, J. B. Nelson, and W. L. Holden, Soil Sci. Soc. Am. J. 69 (2005).
A. Moghimi and M. E. Tate, Soil Biol. Biochem. 10, 289 (1978).
P. A. W. van Hees, U. S. Lundström, and R. Giesler, Geoderma 94, 173 (2000).
B. W. Strobel, Geoderma 99, 169 (2001).
A. E. Martell and R. E. Smith, Critical Stability Constants, Vol. 3 (Plenum, New York, 1977).
R. J. Motekaitis and A. E. Martell, Inorg. Chem. 23, 18 (1984).
W. L. Holden, The Solubilization of Phosphates in the Presence of Organic Acids, MS. Thesis (The University of Tennessee, Knoxville, 1996).
R. B. Duff and D. M. Webley, Chem. Ind. Lond. 1959, 1376 (1959).
J. D. Wolt, Soil Solution Chemistry: Applications to Environmental Science and Agriculture (Wiley, New York, 1994).
M. E. Essington, Soil and Water Chemistry: An Integrative Approach (CRC, Boca Raton, FL, 2003)
M. E. Essington, Soil Sci. Soc. Am. J. 56, 1124 (1992).
A. L. Herbelin and J. C. Westall, FITEQL; A Computer Program for Determination of Chemical Equilibrium Constants from Experimental Data, Version 4.0 (Oregon State University, Corvallis, Report 99-01, 1999).
D. R. Parker, W. A. Norvell, and R. L. Chaney, in Chemical Equilibrium and Reaction Models, R. H. Loeppert et al., eds. (SSSA Special Publication No. 42, SSSA, Madison, WI, 1995), pp. 253–269.
W. Stumm and J. J. Morgan, Aquatic Chemistry: Chemical Equilibria and Rates in Natural Waters, 3rd ed. (Wiley, New York, 1996).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Nelson, J.B., Essington, M.E. The Association Constants of H+ and Ca2 + with 2-Keto-D-Gluconate in Aqueous Solutions. J Solution Chem 34, 789–800 (2005). https://doi.org/10.1007/s10953-005-5116-7
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/s10953-005-5116-7