Liquid Heat Capacity of tert-Butyl Alcohol, Isobutyl Alcohol, and Isopropyl Alcohol at High Temperature

1977 ◽  
Vol 22 (4) ◽  
pp. 385-388 ◽  
Author(s):  
Steven Hoffman ◽  
Juan San Jose ◽  
Robert Reid
Keyword(s):  
Heat Capacity ◽  
High Temperature ◽  
Isopropyl Alcohol ◽  
Butyl Alcohol ◽  
Isobutyl Alcohol ◽  
Tert Butyl ◽  
Tert Butyl Alcohol ◽  
Liquid Heat

A new method for the determination of the relative acidities of alcohols in alcoholic solutions. The nucleophilicities and competitive reactivities of alkoxides and phenoxides

1979 ◽  
Vol 57 (20) ◽  
pp. 2747-2754 ◽  
Author(s):  
Wilkins Reeve ◽  
Charles M. Erikson ◽  
Patrick F. Aluotto
Keyword(s):  
Isopropyl Alcohol ◽  
Butyl Alcohol ◽  
New Method ◽  
Butyl Bromide ◽  
Tert Butyl ◽  
Ether Mixture ◽  
Tert Butyl Alcohol ◽  
Relative Nucleophilicity ◽  
Semiquantitative Method

A new semiquantitative method has been developed for measuring the relative acidities of methanol, ethanol, isopropyl alcohol, and tert-butyl alcohol in mixed hydroxylic solvents. A solution of the alkoxides of two alcohols in an excess of the two alcohols is allowed to react with n-butyl bromide to form a mixture of two ethers. The composition of the ether mixture is a measure of the "competitive reactivity" of thetwo alkoxides. This can be measured directly, and in theory can be factored into two components: the relative nucleophilicity and the relative basicity of the two alkoxides. Relative nucleophilicities are determined by using solutions in which phenol is one component. Knowing the competitive reactivities and nucleophilicities, the relative acidities of methanol, ethanol, isopropyl alcohol, and tert-butyl alcohol in alcoholic media are shown to be 4.4, 1.0, 0.24, and 0.21, respectively. The relative nucleophilicities of hydroxide, methoxide, ethoxide, isopropoxide, tert-butoxide, phenoxide, and m-cresoxide are 0.08, 0.82, 1.0, 0.4, 0.04, 0.46, and 0.57 respectively.

A Kinetic Study of High Pressure Aqueous Oxidations of Organic Compounds Using Elemental Oxygen

1974 ◽  
Vol 52 (10) ◽  
pp. 1925-1933 ◽  
Author(s):  
Jay E. Taylor ◽  
John C. Weygandt
Keyword(s):  
Carbon Dioxide ◽  
High Pressure ◽  
Butyl Alcohol ◽  
Primary Alcohols ◽  
Isobutyl Alcohol ◽  
First Order ◽  
Tert Butyl ◽  
Tert Butyl Alcohol ◽  
First Time ◽  
Bimolecular Mechanism

The high pressure (< 136 atm) and high temperature (< 250°) reactions of elemental oxygen with aqueous solutions of selected soluble alcohols, ketones, and acids have been examined in detail for the first time. Saturated acids and methyl alcohol are not oxidized under the imposed conditions. The end product for the oxidation of ketones and primary alcohols is mainly carbon dioxide at 200 °C; however, appreciable yields of acids are obtained at 250 °C. tert-Butyl alcohol and secondary alcohols form the corresponding ketones which are then further oxidized. Those alcohols and ketones which were studied quantitatively all exhibited second-order kinetics, first order in organic compound and first order in oxygen. The compounds are listed below in the order of decreasing rate at 200°, ΔH≠ in kcal/mol and ΔS≠ in entropy units are noted in parentheses: 2-butanone (16.0, −25) > tert-butyl alcohol (24.2, −9) > cyclopentanone (12.4, −36) > isobutyl alcohol (21.5, −17) > sec-butyl alcohol (23.9, −15) > n-butyl alcohol > (21.3, −22) > acetone (15.1, −37). The alcohols have both higher entropies and enthalpies of activation than the ketones. Two non-chain mechanisms are proposed. (I) A ketone equilibrates with its enol which oxidizes to a metastable oxygenated intermediate. At 250° the intermediate decomposes to an acid or at 200° it is further oxidized to carbon dioxide. (II) Alcohols oxidize by an initial bimolecular mechanism to the corresponding ketone or aldehyde which may then be oxidized further.

Influence of solvent on kinetics of reactions of Cr(II) ions

1981 ◽  
Vol 46 (7) ◽  
pp. 1554-1559 ◽  
Author(s):  
Peter Ševčík ◽  
Ján Tkáč
Keyword(s):  
Mole Fraction ◽  
Methyl Alcohol ◽  
Maleic Acid ◽  
Redox Reaction ◽  
Isopropyl Alcohol ◽  
Butyl Alcohol ◽  
Dichloroacetic Acid ◽  
Tert Butyl ◽  
Tert Butyl Alcohol ◽  
Kinetics Of

This paper deals with the study of redox reactions of Cr(II) ions with hydroxylamine, hydrazoic acid, maleic acid, di- and trichloroacetic acids in so-called typically aqueous mixtures of water with methyl alcohol, isopropyl alcohol, or tert-butyl alcohol. The kinetics of the redox reaction with dichloroacetic acid was studied also in the medium of aqueous acetone and in a typically nonaqueous medium water-acetonitrile. The dependences of activation Gibbs energies on the mole fraction of the nonaqueous component have no minima and maxima characteristic for the thermodynamic behaviour of the mentioned binary systems. However, the change of the activation Gibbs energy with the mole fraction of tert-butyl alcohol is not monotonous with all the studied reactions of Cr(II) ions. At a constant mole fraction of the nonaqueous component, the usual trend of the influence on the rate constants decreases in the sequence tert-butyl alcohol > isopropyl alcohol > methyl alcohol. Tert-butyl alcohol hinders most strongly the redox reaction with trichloroacetic acid, whereas it accelerates the reaction of Cr(II) ions with maleic acid and hydroxylamine.

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