A potentiometric study of (acid + base) equilibria in substituted 4-nitropyridine N-oxide systems in methanol and dimethyl sulfoxide

Gurzyński, Łukasz; Puszko, Aniela; Makowski, Mariusz; Chmurzyński, Lech

doi:10.1016/j.jct.2006.06.013

Cited by 4 publications

(3 citation statements)

References 39 publications

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“…Standard state of 1 atm in the gas phase and 1 mol L –1 in solution. b Values taken from NIST. c Values calculated with the SMD model. For CH 3 OH, the experimental value was used. d Taken from refs , , . e Determined through X3LYP/DZVP+diff calculations. …”

Section: Resultsmentioning

confidence: 99%

Absolute Single-Ion Solvation Free Energy Scale in Methanol Determined by the Lithium Cluster-Continuum Approach

Pliego

Miguel

2013

J. Phys. Chem. B

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Absolute solvation free energy of the lithium cation in methanol was calculated by the cluster-continuum quasichemical theory of solvation. Clusters with up to five methanol molecules were investigated using X3LYP, MP2, and MP4 methods with DZVP, 6-311+G(2df,2p), TZVPP+diff, and QZVPP+diff basis sets and including the cluster solvation through the PCM and SMD continuum models. Our calculations have determined a value of -118.1 kcal mol(-1) for the solvation free energy of the lithium, in close agreement with a value of -116.6 kcal mol(-1) consistent with the TATB assumption. Using data of solvation and transfer free energy of a pair of ions, electrode potentials and pKa, we have obtained the solvation free energy of 25 ions in methanol. Our analysis leads to a value of -253.6 kcal mol(-1) for the solvation free energy of the proton, which can be compared with the value of -263.5 kcal mol(-1) obtained by Kelly et al. using the cluster pair approximation. Considering that this difference is due to the methanol surface potential, we have estimated that it corresponds to -0.429 V.

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Section: Resultsmentioning

confidence: 99%

Absolute Single-Ion Solvation Free Energy Scale in Methanol Determined by the Lithium Cluster-Continuum Approach

Pliego

Miguel

2013

J. Phys. Chem. B

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“…Electronically, PyO is a weaker donor than OPPh 3 by the 4-fluorophenol hydrogen-bond basicity scale, 15 while buried volume calculations (% V bur ) support a significantly reduced steric profile for PyO relative to OPPh 3 (% V bur (PyO): 12.4%, % V bur (OPPh 3 ): 16.3%; Tables S30 and S31, ESI†). Alternatively, 4-substituted 2,6-dimethylpyridine (lutidine) N -oxide derivatives, R LO (R = NO 2 , Cl, H, OMe, NMe 2 ), display steric profiles comparable to OPPh 3 (ESI,† Table S32; % V bur : 15.9%), while experimental aqueous p K a values (p K a W ( NO 2 LO): 1.01, p K a W ( NMe 2 LO): 4.75) 16 and calculated natural charges of the N -oxide oxygen ( q O ( NO 2 LO): −0.541, q O ( NMe 2 LO): −0.658; Fig. S15 and Table S6, ESI†) support electronically tunable donor profiles (Scheme 1).…”

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N-Oxides amplify catalyst reactivity and isoselectivity in the ring-opening polymerization of rac-β-butyrolactone

et al. 2022

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“…Poulias and colleagues (Ritzoulis et al, 1984) studied the conductance behavior of halogen-salicylic acid (X-C 6 H 4 OHCOOH, X = 5-nitro, 5-chloro, 5-bromo, 5-fluoro and 3,5-dinitro) in MeOH + H 2 O at 25 • C (Poulias et al, 1985(Poulias et al, , 1986. Srivastava and Samant (1995) measured the dissociation constants of 2,5-dichlorobenzesulfonic acid in 20% (%w PC) PC + EC at 25 • C. Niazi et al (1993b) determined the pK of chloroacetic acid (Niazi, 1993a) and salicylic acid in binary mixtures of water and MeOH, EtOH, 1-PrOH, DMF, Ac, and AN in addition to benzoic and nitrobenzoic acids in binary Ac + H 2 O and THF + H 2 O (Niazi et al, 1992) and morin in MeOH + H 2 O (Niazi et al, 2006) at 25 • C. Recently, research work in this field seems directed toward generating more experimental data for heterocyclic organic acids and bases including 4-nitropyridine in nonaqueous solvents such as AN, MeOH, PC, and DMSO (Gurzyński et al, 2007a(Gurzyński et al, , 2007b and polycarboxilic acids in MeOH + H 2 O (Garrido et al, 2006) and AN + H 2 O (Espinosa et al, 2002). Others have measured the pK of perfluorooctanoic acid in MeOH + H 2 O at 25 • C (Burns et al, 2008) and of n-butylamine + acetic acid in AN + dioxane (Czaja et al, 2006).…”

Section: -Prohmentioning

confidence: 99%

Solution Properties of Inorganic Contamination in Mixed Solvents: Theory, Progress, and Limitations

Srour¹,

McDonald

2011

Critical Reviews in Environmental Science and Technology

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Most of what is known about the environmental fate and transport of contaminants comes from studies of dilute, aqueous solutions. Theoretical and practical aspects of hydrophobic organic contaminants in aqueous mixtures of organic solvents are well developed, but relatively little attention has been paid to those situations where inorganic contaminants such as metals, water, and organic solvents occur simultaneously. The authors discuss changes in solution properties accompanying the addition of organic solvents. They review more than 500 references to available data on ion solvation, solubility, activity, acidity, pairing, and pH in electrolyte and electrolyte-free solvent mixtures and tabulate selected experimental values. Whenever available, equations developed to estimate these properties are given and their applications and limitations described. The implications of the progress in mixed-solvents solution chemistry on contaminant behavior and transport are described. Major limitations to the study of inorganic contamination in mixed solvents include the absence of complete and comprehensive data (e.g., type of ionic species, activity coefficients, solubility constants) that characterize solute and solvent properties in these mixtures and the indefinite number of possible solute and solvent combinations. The generation of models predicting such data from easily measured benchmark solute and solvent properties is a major challenge. The availability of such database and models may open the field for environmental engineers and soil scientists to study the basic chemical processes and mechanisms of metal contamination in complex multicomponent systems.

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A potentiometric study of (acid + base) equilibria in substituted 4-nitropyridine N-oxide systems in methanol and dimethyl sulfoxide

Cited by 4 publications

References 39 publications

Absolute Single-Ion Solvation Free Energy Scale in Methanol Determined by the Lithium Cluster-Continuum Approach

Absolute Single-Ion Solvation Free Energy Scale in Methanol Determined by the Lithium Cluster-Continuum Approach

N-Oxides amplify catalyst reactivity and isoselectivity in the ring-opening polymerization of rac-β-butyrolactone

Solution Properties of Inorganic Contamination in Mixed Solvents: Theory, Progress, and Limitations

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