Acid-base strengths in 1,2-dichloroethane

The pKa value of hydriodic acid in 1,2-dichloroethane was determined from conductivity measurements. A glass electrode was calibrated for dichloroethane in the potentiometric titration of hydriodic acid with tetramethylguanidine. From potentiometric titrations, the pKa values in dichloroethane of hydrobromic acid, hydrochloric acid, picric acid and some sulfonphthaleins as well as some protonated nitrogen bases were determined. In the curves of the titrations of the carboxylic acids and the hydrogen halides with TMG, evidence was found for the formation of the complex B(HX)2

Acid-base titrations in solvents of relatively low dielectric constant

From a comparison of the pKa values of various compounds in the solvent 1,2-dichloroethane, m-cresol, acetic acid and pyridine, the differences in basicity of these solvents could be determined. If the basicity of 1,2-dichloroethane is taken as 0 pK units, the basicities of m-cresol, acetic acid and pyridine were found to be 3, 7 and 11 pK units, respectively. It is shown how these differences in basicity can serve to predict pKa values in solvents belonging to the Brønsted classes 5–8

The coulometric titration of acids and bases in m-cresol medium

A method is described for the coulometric titration of acids and bases in the solvent m-cresol. The method is suitable for bases with pKa values greater than 11 in m-cresol, or for acids with pKa values below 13 in m-cresol. Amounts of 5–50 μeq of acid or base can be determined with a relative accuracy of ±1%

The anodic oxidation of bases in the solvent m-cresol

The oxidation of bases in the solvent m-cresol was investigated by polarography, voltammetry at the rotating platinum disc electrode and by chronopotentiometry. It was shown that the m-cresolate ion is the electroactive species in this reaction. The oxidation is a one-electron process giving a phenoxy radical. This phenoxy radical is converted in a chemical reaction of higher than first order, most likely to the dimer

Acid-base strengths in m-cresol

For various acids and bases dissociation constants were determined conductimetrically in m-cresol. A glass electrode was calibrated by means of some compounds with dissociation constants known from conductivity measurements. Potentiometric titrations with this calibrated glass electrode gave dissociation constants of some other acids and bases in m-cresol. The value 2·10−19 was found for the self-dissociation constant of m-cresol. From the difference pKa (cresol) - pKa (pyridine) for those compounds having acid or base strengths which are not levelled either in pyridine or m-cresol, it was found that the solvent m-cresol has a basicity about 8 pK units less than that of pyridine

The coulometric titration of acids and bases in dimethylsulfoxide media

The coulometric titration of 20–200 μeq of acids and bases in DMSO media is described. In the titration of bases, the electro-oxidation of hydrogen at a platinized platinum electrode is used as the source of protons. The conditions for 100 % current efficiency at this electrode are low current density to avoid passivity and regular treatment of the electrode with potassium dichromate—sulfuric acid to remove a poisoning sulfide layer. The accuracy of the titrations is better than ±1 %. Very weak acids like phenols (pKa (DMSO) ≈16) can be titrated successfully. Tris(hydroxymethyl)aminomethane is the weakest base titrated

Transforming mesoscale granular plasticity through particle shape

When an amorphous material is strained beyond the point of yielding it enters a state of continual reconfiguration via dissipative, avalanche-like slip events that relieve built-up local stress. However, how the statistics of such events depend on local interactions among the constituent units remains debated. To address this we perform experiments on granular material in which we use particle shape to vary the interactions systematically. Granular material, confined under constant pressure boundary conditions, is uniaxially compressed while stress is measured and internal rearrangements are imaged with x-rays. We introduce volatility, a quantity from economic theory, as a powerful new tool to quantify the magnitude of stress fluctuations, finding systematic, shape-dependent trends. For all 22 investigated shapes the magnitude $s$ of relaxation events is well-fit by a truncated power law distribution $P(s)\sim {s}^{-\tau} exp(-s/s^*)$, as has been proposed within the context of plasticity models. The power law exponent $\tau$ for all shapes tested clusters around $\tau=$ 1.5, within experimental uncertainty covering the range 1.3 - 1.7. The shape independence of $\tau$ and its compatibility with mean field models indicate that the granularity of the system, but not particle shape, modifies the stress redistribution after a slip event away from that of continuum elasticity. Meanwhile, the characteristic maximum event size $s^*$ changes by two orders of magnitude and tracks the shape dependence of volatility. Particle shape in granular materials is therefore a powerful new factor influencing the distance at which an amorphous system operates from scale-free criticality. These experimental results are not captured by current models and suggest a need to reexamine the mechanisms driving mesoscale plastic deformation in amorphous systems.Comment: 11 pages, 8 figures. v3 adds a new appendix and figure about event rates and changes several parts the tex