The Brönsted Equation—Its First Half-Century

Bell, R. P.

doi:10.1007/978-1-4615-8831-3_2

Cited by 11 publications

(6 citation statements)

References 102 publications

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“…The rate constants for H 2 CO 3 and HCO 3 – acid catalysis of the disproportionation reaction are well above the Brønsted relationship (Figure S10 and Table S10) for the other acids and, in fact, fall close to a parallel Brønsted relationship (same α value) with an intercept (interpreted as log C A,CO 3 , which is a proportionality constant specific for carbonate species) of 6.49 compared to log C A of 4.25 (±0.16) for other inorganic acids. When the value of α is the same for two series of acids but the C A differ, the acids are still participating in the same reaction mechanism (differences of several orders of magnitude have been observed) …”

Section: Resultsmentioning

confidence: 99%

“…When the value of α is the same for two series of acids but the C A differ, the acids are still participating in the same reaction mechanism (differences of several orders of magnitude have been observed). 34 The modified model and associated parameters that were estimated for all experiments are outlined in Table 1 for PE4 (Figure S3, step #6). Proportionality constants for the carbonate species (log C A,CO 3 and log C B,CO 3 ) were added as additional estimated parameters to account for the enhanced catalytic activity of the carbonate species in Cl 2 hydrolysis and formation reactions, while the slopes (α and β) were constrained to those from the Brønsted plots (Figures S4 and S5).…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

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Role of Carbonate Species on General Acid Catalysis of Bromide Oxidation by Hypochlorous Acid (HOCl) and Oxidation by Molecular Chlorine (Cl₂)

Brodfuehrer

Wahman

Alsulaili

et al. 2020

Environ. Sci. Technol.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Materials and Methodsmentioning

confidence: 99%

Role of Carbonate Species on General Acid Catalysis of Bromide Oxidation by Hypochlorous Acid (HOCl) and Oxidation by Molecular Chlorine (Cl₂)

Brodfuehrer

Wahman

Alsulaili

et al. 2020

Environ. Sci. Technol.

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“…Yet another consequence of incorrectly assigning the p K a of H 2 O and H 3 O + is found in Brønsted plots that include H 2 O(l), OH – (aq), and/or H 3 O + (aq). It has been known since the 1940s that the 15.7, −1.7 p K a values are obvious statistical outliers in linear Brønsted plots. ,− We are in the process of analyzing dozens of published Brønsted plots, and have found that using the 14.0, 0.0 p K a values dramatically improves the linearity of the plots (manuscript in preparation)…”

Section: Discussionmentioning

confidence: 99%

H₂O(aq) Does Not Exist: Critique of a Proof-of-Concept Derivation

2023

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Although the pK a of water has been shown to be 14.0 at 25 °C both experimentally and theoretically, a subset of organic chemists has listed the pK a of water as 15.7 and the pK a of the aqueous proton (H + or H 3 O + ) as −1.7 since at least the early 1930s. These values were found primarily in research literature until the early 1960s, at which time they began appearing in organic chemistry textbooks. The validity of the 15.7/−1.7 values has been fiercely debated in the literature. At the heart of one argument supporting these values is the proposal that a small concentration of "solute" water molecules, H 2 O(aq), can exist in solution along with the solvent water molecules, H 2 O(l). No experimental evidence of H 2 O(aq) molecules has been reported, but at least one theoretical proof-of-concept for the existence of such molecules has been published in this Journal. Here we show that this theoretical proof is based on flawed assumptions and is therefore incorrect.

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“…When The influence of the dissociation constant K d of the different organic acids on the overall kinetics of the corrosion process can be represented in a similar way as the Brønsted catalysis equation. The Brønsted catalysis equation constitutes the first linear free-energy relationship, i.e., Gibbs energy relation [80]. It gives a relationship between acid strength (dissociation constant K d ) and catalytic activity (reaction rate constant k) in general acid catalysis, cf.…”

Section: Organicmentioning

confidence: 99%

Stress Corrosion Cracking of Steam Turbine Steel: The Influence of Organic Acid Characteristics

Seranno

Lambrechts

Verliefde

et al. 2022

Metals

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This work evaluates the impact of different organic acids on the corrosion sensitivity and stress-corrosion cracking (SCC) of NiCrMoV steam turbine steel. For all organic acids, potentiodynamic measurements shows linear relationships between corrosion rate and hydrogen proton concentration between pH 2.4 and 3.9. For solutions with the same pH, i.e., similar conductivity, the corrosion rate differs depending on the type of organic acid. The anodic dissolution in formic acid is the highest, followed by acetic, propanoic and nonanoic acid. The acid dissociation reaction is identified as the rate determining step in the corrosion process. Nonanoic acid, alternatively, clearly acts as a corrosion inhibitor. In situ four-point constant-extension tests in formic acid, acetic acid and nonanoic acid, at a pH value of 3.4 were performed to evaluate their impact on the SSC sensitivity. The general degradation followed the trend of the corrosion rate, although the synergetic effect of corrosion and stress resulted in a higher degradation depth. Though nonanoic acid induced little visible corrosion, still stress-corrosion cracks were still detected. It was shown that solutions of different organic acids with the same pH do not have the same influence on stress-induced degradation.

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The Brönsted Equation—Its First Half-Century

Cited by 11 publications

References 102 publications

Role of Carbonate Species on General Acid Catalysis of Bromide Oxidation by Hypochlorous Acid (HOCl) and Oxidation by Molecular Chlorine (Cl₂)

Role of Carbonate Species on General Acid Catalysis of Bromide Oxidation by Hypochlorous Acid (HOCl) and Oxidation by Molecular Chlorine (Cl₂)

H₂O(aq) Does Not Exist: Critique of a Proof-of-Concept Derivation

Stress Corrosion Cracking of Steam Turbine Steel: The Influence of Organic Acid Characteristics

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The Brönsted Equation—Its First Half-Century

Cited by 11 publications

References 102 publications

Role of Carbonate Species on General Acid Catalysis of Bromide Oxidation by Hypochlorous Acid (HOCl) and Oxidation by Molecular Chlorine (Cl2)

Role of Carbonate Species on General Acid Catalysis of Bromide Oxidation by Hypochlorous Acid (HOCl) and Oxidation by Molecular Chlorine (Cl2)

H2O(aq) Does Not Exist: Critique of a Proof-of-Concept Derivation

Stress Corrosion Cracking of Steam Turbine Steel: The Influence of Organic Acid Characteristics

Contact Info

Product

Resources

About

Role of Carbonate Species on General Acid Catalysis of Bromide Oxidation by Hypochlorous Acid (HOCl) and Oxidation by Molecular Chlorine (Cl₂)

Role of Carbonate Species on General Acid Catalysis of Bromide Oxidation by Hypochlorous Acid (HOCl) and Oxidation by Molecular Chlorine (Cl₂)

H₂O(aq) Does Not Exist: Critique of a Proof-of-Concept Derivation