Polarographic and Acid Properties of Thorium Perchlorate in Acetonitrile

Kolthoff, I. M.; Ikeda, Shizuyo

doi:10.1021/j100824a033

Cited by 28 publications

(13 citation statements)

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“…The presence of base decreased the standard potential and increased the reversibility of NHPI oxidation. The reported p K a values of NHPI (23.5) and the 2,6-lutidinium ion (14.1) in MeCN suggest that proton exchange is highly unfavorable. Nevertheless, the plausibility of a hydrogen bond formation between NHPI and pyridine derivative was assessed through IR spectroscopy.…”

Section: Resultsmentioning

confidence: 99%

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Mechanism of Electrochemical Generation and Decomposition of Phthalimide-N-oxyl

et al. 2021

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Phthalimide N-oxyl (PINO) is a potent hydrogen atom transfer (HAT) catalyst that can be generated electrochemically from N-hydroxyphthalimide (NHPI). However, catalyst decomposition has limited its application. This paper details mechanistic studies of the generation and decomposition of PINO under electrochemical conditions. Voltammetric data, observations from bulk electrolysis, and computational studies suggest two primary aspects. First, base-promoted formation of PINO from NHPI occurs via multiple-site concerted proton–electron transfer (MS-CPET). Second, PINO decomposition occurs by at least two second-order paths, one of which is greatly enhanced by base. Optimal catalytic efficiency in PINO-catalyzed oxidations occurs in the presence of bases whose corresponding conjugate acids have pK a’s in the range of ∼11–15, which strikes a balance between promoting PINO formation and minimizing its decay.

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Section: Resultsmentioning

confidence: 99%

“…Similarly, the formation of a NHPI–DMAP H-bonded complex is more thermodynamically favored (Δ G = −4.1 kcal/mol) than its NHPI–pyridine counterpart. The smaller Δ G between full deprotonation and NHPI–DMAP formation (+6.0 kcal/mol) is consistent with the higher p K a of DMAP’s conjugate acid (17.7) …”

Section: Resultsmentioning

confidence: 99%

Mechanism of Electrochemical Generation and Decomposition of Phthalimide-N-oxyl

et al. 2021

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“…Finally, the small water traces can strongly influence the experimental results in protophobic media, such as AN or AC, because the lyonium ions can exist as H 3 O + , H 5 O

_{2}^{+}

, etc., owing to the extremely low basicity of the solvent. In contrast, in protophilic solvents, such as DMSO, the small amounts of water cannot compete with the more basic solvent for the proton 14, 15. For example, the protonation constants for water and DMSO in AN as solvent are 3 × 10 2 and 6 × 10 5 , respectively, as reported by Kolthoff and Ikeda 14.…”

Section: Introductionmentioning

confidence: 74%

“…In contrast, in protophilic solvents, such as DMSO, the small amounts of water cannot compete with the more basic solvent for the proton 14, 15. For example, the protonation constants for water and DMSO in AN as solvent are 3 × 10 2 and 6 × 10 5 , respectively, as reported by Kolthoff and Ikeda 14. Only when studying acids weaker than H 2 O, even small water traces in DMSO can hinder the determination of true p K a values 16…”

Section: Introductionmentioning

confidence: 99%

A generic framework for constructing cross‐realm C2C‐PAKA protocols based on the smart card

Xu¹,

Zhu²,

Jin³

2011

Concurrency and Computation

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SUMMARYA cross-realm client-to-client password-authenticated key agreement (C2C-PAKA) protocol allows network clients from different realms managed by different servers to agree on a session key in an authentic manner based on easily memorizable passwords. In this paper, we present a generic framework for constructing a cross-realm C2C-PAKA protocol from any secure smart card-based password authentication (PA-SC) protocol. The security proof of our construction can be derived from the underlying PA-SC protocol employing the same assumptions. Our generic framework appears to be the first one with provable security. In addition, compared with similar protocols, the instantiation of our construction achieves improved efficiency.

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“…6 The energy factor E * is in principle related to8 (though not equal to) isosteric heats of adsorption at zero coverage but in fact the measurement is sufficiently difficult that one must turn to the capacity factor, Aso, for really sensitive tests of the model. That is, a number of diff ereiit (polynomial) functions have been employed in calculating the dimensionless function B~s l A s~.~ Little practical effect mas noted on the values of the parameters obtained or on the goodness of fit.…”

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confidence: 99%

High Temperature Physical Adsorption of Homologous Series of Gases on Heterogeneous Surfaces

Freeman¹,

Kolb²

1963

J. Phys. Chem.

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The theory of high tcmpcraturc gns-surfacc interaction has been simply cxtctndcd to include a two-energy hetcrogcneous surface. Equilibrium adsorption or giis chroirii~togrt~~~hic (lata from :It h s t t w o members of a homologous scrics of gascs interacting at sevcral temperaturcs are rcquircd to charactcrixc the degree of heterogeneity. Available suitable data from the literature involving up to five rneinbcrs of a homologous series have been tried. Thc agreement between predicted and measurcd values is quite generally excellent. An unambiguous surface area is obtained for the solid.(3) J. 1: . lIanlari and 11. 1'. I'rcenian, Can. J . Chem., 97, 1575 (IlGY).

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Polarographic and Acid Properties of Thorium Perchlorate in Acetonitrile

Cited by 28 publications

References 1 publication

Mechanism of Electrochemical Generation and Decomposition of Phthalimide-N-oxyl

Mechanism of Electrochemical Generation and Decomposition of Phthalimide-N-oxyl

A generic framework for constructing cross‐realm C2C‐PAKA protocols based on the smart card

High Temperature Physical Adsorption of Homologous Series of Gases on Heterogeneous Surfaces

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