Titrations in Nonaqueous Solvents

Harlow, G. A.; Morman, Donald H.

doi:10.1021/ac60261a602

Cited by 9 publications

(5 citation statements)

References 247 publications

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“…These experiments suggest that a physical mixture of an iodide source and a proton source (aside from the solvent) is not equivalent to HI. This could be due to the degree of dissociation of mineral acids, which is dependent on the nature of the solvent (Leveling effect). , Computations, discussed next, shed light on the acid dissociation trend in an organic acid solvent.…”

Section: Resultsmentioning

confidence: 99%

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Adipic Acid Production via Metal-Free Selective Hydrogenolysis of Biomass-Derived Tetrahydrofuran-2,5-Dicarboxylic Acid

et al. 2017

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Biomass-derived furans offer sustainable routes to adipic acid (AA), a key chemical in Nylon-6,6 synthesis. In this work, we show that tetrahydrofuran-2,5-dicarboxylic acid (THFDCA) is a viable precursor for AA production, achieving up to 89% yield in a metal-free system containing HI and molecular H2 in a propionic acid solvent at 160 °C. Reactivity studies demonstrate that the interplay between HI, H2, and the solvent is essential for effective THFDCA ring opening. By measuring the reaction orders of HI and molecular H2 and calculating an acid–base equilibrium constant in a nonaqueous solvent, we show that HI plays a multifaceted role in the reaction by acting both as a proton source and an iodide source to selectively cleave C–O bonds without overhydrogenation of carboxylic acid groups. Using reactivity studies, kinetic measurements, and first-principles computational insights, we demonstrate that metal-free activation of molecular H2 plays a key role in the reaction, following HI-mediated cleavage of the etheric C–O bond in THFDCA.

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Section: Resultsmentioning

confidence: 99%

“…This could be due to the degree of dissociation of mineral acids, which is dependent on the nature of the solvent (Leveling effect). 54,55 Computations, discussed next, shed light on the acid dissociation trend in an organic acid solvent.…”

Section: Resultsmentioning

confidence: 99%

Adipic Acid Production via Metal-Free Selective Hydrogenolysis of Biomass-Derived Tetrahydrofuran-2,5-Dicarboxylic Acid

et al. 2017

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“…period since the last review (93) there has been a high level of research activity that relates, directly or indirectly, to titrations in nonaqueous solvents. In organizing this review, an attempt has been made to cover the pertinent literature which appeared in the period October 1967 through October 1969.…”

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confidence: 99%

Titrations in nonaqueous solvents

Lagowski¹

1970

Anal. Chem.

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“…In the past, a series of basic papers have been produced aiming to demonstrate that the spectrophotometric determination of amines after derivatization into colored compounds was a reliable, sensitive, and reproducible analytical technique. Such papers mostly referred to amines transformed in Meisenheimer intermediates, in charge transfer complexes, − in colored ammonium ion pairs, , in nitrogen donor ligands able to give rise to colored metal complexes, ,− and so on. − …”

Section: Results and Discussionmentioning

confidence: 99%

Metal Complexes as Self-Indicating Titrants for Acid–Base Reactions in Chloroform

et al. 2018

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The paper reports an unprecedented spectrophotometric determination of amines in chloroform, in which amines are not transformed into colored derivatives. This result has been achieved by exploiting the acid-base properties of the tight-ion-paired metal complexes [(HRDTO)Pt(HRDTO)][Cl], which are able to donate a HCl molecule to an amine, giving rise to an ammonium salt and to the neutral complexes [(HRDTO)Pt]. The circumstance that [(HRDTO)Pt(HRDTO)][Cl] and [(HRDTO)Pt] species show different absorptions in the visible region of the electromagnetic spectrum enables the aforementioned platinum complexes to behave as self-indicating titrants in the spectrophotometric determination of aliphatic amines, which are known to be UV-vis transparent. The new method has been tested by determining a series of fatty amines in the bulk and gave excellent results. The limits of applicability of this method (pK > 4) were found by testing a series of benzodiazepines.

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Titrations in Nonaqueous Solvents

Cited by 9 publications

References 247 publications

Adipic Acid Production via Metal-Free Selective Hydrogenolysis of Biomass-Derived Tetrahydrofuran-2,5-Dicarboxylic Acid

Adipic Acid Production via Metal-Free Selective Hydrogenolysis of Biomass-Derived Tetrahydrofuran-2,5-Dicarboxylic Acid

Titrations in nonaqueous solvents

Metal Complexes as Self-Indicating Titrants for Acid–Base Reactions in Chloroform

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