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First Ionization Constant of Phosphoric Acid and of Acetic Acid in H2O and D2O from T = 373 K to 573 K at p = 11.5 and 20 MPa by AC Conductivity Methods

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Abstract

The first ionization constants of phosphoric acid and acetic acid have been measured in H2O and D2O from T = 373 K to T = 573 K and p = 11.5 and 20 MPa to yield accurate values of the deuterium isotope effect. Sequential conductivity measurements using a unique high-precision flow-through AC conductance instrument were made on dilute (m ≤ 10–2 mol·kg−1) aqueous solutions of phosphoric acid, acetic acid, potassium dihydrogenphosphate, sodium acetate, potassium hydroxide, sodium hydroxide, hydrochloric acid, potassium chloride and sodium chloride in light and heavy water under the same experimental conditions (temperature, pressure, flow-rate), so that systematic experimental errors between the two solvents would cancel. The experimental molar conductivities of potassium dihydrogenphosphate, sodium acetate, hydrochloric acid, and the corresponding chloride salts were used to calculate the molar conductivities for the fully dissociated acids [λ(D+), λ(D2PO −4 ) and λ(CH3COO−)]. Together with the molar conductivities measured for partially ionized acids, Λ(D3PO4) and Λ(CH3COOD), these yielded values for the degree of dissociation, α, and the ionization constants, pKa1. The iterative process was repeated at each temperature in both H2O and D2O where the Fuoss-Hsia-Fernández-Prini (“FHFP”) and the Quint-Viallard (“QV”) equations were used to correct for ionic strength. The resulting values of pKa1 for phosphoric acid in H2O agree with those reported from conductivity studies by previous works over the entire temperature range and with low temperature potentiometric studies to within the combined experimental uncertainties. The results for pKa1 above 298.15 K in D2O are the first to be reported in the literature. The new values for pKa(CH3COOD) yield more accurate values for the deuterium isotope effect on the ionization constant of acetic acid than those reported in our previous work (Erickson et al. in J. Phys. Chem. B. 123:9503–9506, 2019). The single-ion limiting conductivities for dihydrogenphosphate and acetate in D2O, λ(D2PO −4 ) and λ(CH3COO−), were found to be the same as those in H2O once corrected for viscosity effects, confirming previous observations for other ions.

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Acknowledgements

The authors are grateful to Prof. R.H. Wood (University of Delaware), Prof. G.H. Zimmerman (Bloomsburg University) for many suggestions and technical discussions related to the experimental work. Technical advice and encouragement were provided by Dr. Jenny Cox. Mr. Ian Renaud and Mr. Case Gielen provided capable electronic and machine-shop support, particularly in reconstructing the conductivity flow cell. The D2O purity analysis was completed using the NMR Center at the University of Guelph. Scientific advice and encouragement were also provided by Dr. Dave Guzonas, Atomic Energy of Canada Ltd.; Dr. Dave Evans, Ontario Power Generation Ltd. (OPG); and Dr. Mike Upton, Bruce Power Ltd. Ontario Power Generation Inc. supplied the heavy water used in this work. This work was originally funded by the Natural Sciences and Engineering Council of Canada (NSERC) and the University Network of Excellence in Nuclear Engineering (UNENE) as NSERC Collaborative Research Grants CRDPJ 381418 – 09 and CRDPJ 447964 – 13. This research was carried out under the NSERC/UNENE Senior Industrial Research Chair Program at the University of Guelph, which is supported by the Natural Science and Engineering Research Council of Canada (NSERC Grant IRCPJ 499567-15), and the University Network of Excellence in Nuclear Engineering (UNENE), the CANDU Owners Group (COG), the Nuclear Waste Management Organization (NWMO), and the Electric Power Research Institute (EPRI).

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  1. Department of Chemistry, University of Guelph, Guelph, ON, N1G 2W1, Canada

    Hugues Arcis, Jacy K. Conrad, Jane P. Ferguson, Kristy M. Erickson & Peter R. Tremaine

  2. Culham Science Centre, National Nuclear Laboratory, D5, Abingdon, OX14 3DB, UK

    Hugues Arcis

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Contributions

The 20 MPa phosphoric and acetic acid studies were carried out as part of the graduate program of KME (Ph.D. Thesis, University of Guelph, 2013). HA carried out a significant reanalysis of the data reported in the PhD thesis. JPF contributed to the development of the methodology used in more recent measurements at 11.5 MPa, carried out the experiments, and contributed to the data analysis. JKC assisted with the 11.5 MPa data collection, performed most of the data analysis with the FHFP and QV conductivity models, density model fits, and preparation of Figures and Tables. The work carried out under the direction of PRT and HA. The manuscript was written by HA and PRT with contributions from JPF and JKC.

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Correspondence to Hugues Arcis or Peter R. Tremaine.

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Arcis, H., Conrad, J.K., Ferguson, J.P. et al. First Ionization Constant of Phosphoric Acid and of Acetic Acid in H2O and D2O from T = 373 K to 573 K at p = 11.5 and 20 MPa by AC Conductivity Methods. J Solution Chem 53, 91–125 (2024). https://doi.org/10.1007/s10953-023-01281-4

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