Polarographic determination of the rate of dehydration of chloral hydrate

Harder, P; Sørensen, P. E.; Ulstrup, Jens

doi:10.1016/s0022-0728(77)80324-0

Cited by 3 publications

(2 citation statements)

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“…Under common conditions, the aldehydes are converted to the geminal diols: for example, 0.05 mol% CH 2 O, 99.95% H 2 C(OH) 2 ; 43.5% CH 3 CHO, 56.5% CH 3 CH(OH) 2 ; <0.01% CCl 3 CHO, >99.99% CCl 3 CH(OH) 2 ; 58.5% CH 3 CH 2 CHO, 41.5% CH 3 CH 2 CH(OH) 2 (29). In addition to the equilibria, the kinetics and mechanisms of the hydrolytic hydration of methanal (24)(25)(26)(27)(28)(29)(30)(31)(32)(33)(34)(35) and other small aldehydes (36)(37)(38), including trichloroethanal, have been studied extensively.…”

Section: Evidence For Carbinolamines and Geminal Diolsmentioning

confidence: 99%

Carbinolamines and Geminal Diols in Aqueous Environmental Organic Chemistry

Urbansky

2000

J. Chem. Educ.

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Section: Evidence For Carbinolamines and Geminal Diolsmentioning

confidence: 99%

Carbinolamines and Geminal Diols in Aqueous Environmental Organic Chemistry

Urbansky

2000

J. Chem. Educ.

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“…Even though they have mentioned the presence of two reduction waves for chloral, one for the reduction of the unhydrated form and one for the hydrated form, they were not able to show simultaneous replacement of all three chlorines. In the other paper by Harder et al., [ 20 ] rate constants for the hydration and dehydration reactions and using the ratio of these rate constants hydration‐dehydration equilibrium constant, K d , has been calculated. Therein, the rate constants were determined using the measured limiting currents and Ilković equation.…”

Section: Introductionmentioning

confidence: 99%

Role of acid‐base and hydration‐dehydration equilibria on reductions of chloral and chloral hydrate

Baymak

2021

Electrochemical Science Adv

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The electrochemical behavior of chloral hydrate in aqueous solutions at various pH values was investigated by using polarography. Reduction of chloral hydrate takes place in two steps: one appears as a small limiting current value that corresponds to the reduction of the unhydrated form, present in solutions in less than 3%, and another larger limiting current value at more negative potentials corresponding to a reduction of C-Cl bonds in the hydrated form. Reduction schemes for both the hydrated and unhydrated forms and of an oxidation process for chloral hydrate are proposed. The reduction scheme supports the stepwise removal of chloride ions from the hydrated form of chloral that is electroactive in its protonated form, yielding ethanol as the final product. A rate constant for the protonation of chloral hydrate is calculated from its measured pK a value and electrochemical data. The role of hydration-dehydration equilibria involving the reduction intermediates, which are reduced at more negative potentials than that of chloral, was concluded based on a comparison of limiting currents of chloral hydrate with those of 2,2,2-trichloroethanol. The alcohol yields, in medium pH range a diffusion-limited current, corresponding to cleavage of three C-Cl bonds. This allowed the calculation of the equilibrium constant of the hydrationdehydration equilibria.

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