Viscosity and density of isomeric butanol/water mixtures as functions of composition and temperature

Senanayake, P. Chandani; Gee, Norman; Freeman, Gordon R.

doi:10.1139/v87-407

Cited by 39 publications

(21 citation statements)

References 11 publications

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“…The physical properties of tert-butanollwater mixed solvents vary markedly with composition (9,10). The present paper reports a continuation of the study of e; reaction rates in this solvent system (1 1).…”

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confidence: 82%

Solvent effects on the reactivity of solvated electrons with ions in tert-butanol/water mixtures

Zhao¹,

Freeman²

1995

Can. J. Chem.

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Reactions of e; with the ions N H i V s , and H: showed different variations of rate with solvent composition in rerr-butanollwater mixtures from 0 to 100 mol% water. In pure rerr-butanol solvent at 298 K the respective values of k2 (lo6 m3 mol-I s-I) are 3.2, 13, and 42. The estimated value of reaction radius R, depends on the minimum number of solvent molecules needed between e; and the reactant ion to attain the static values of E of the bulk solvent used in the calculation of the Debye factor f ; R, is assumed to be larger in the alcohol-rich region than in the water-rich region, because the solvent molecules are larger. The Smoluchowski-Debye-Nernst-Einstein model is used to evaluate the effective reaction radius KR,, where K is the probability of reaction per encounter; KR, decreases from pure ferr-butanol to pure water. In the water-rich region the activation energies E2 of the efficient reactions, 11-24 kJ mol-I, are similar to EAo of the reactant electrolyes, 12-23 kJ mol-l. For the inefficient reactant NH: CIO;, E2 = 30 kJ mol-I. The high values of E2 = 43-53 kJ mol-I in pure rerr-butanol solvent are attributed to a high activation energy for diffusion of e; in this solvent.Ke.y words: rert-butanollwater solvents, solvated electron, ions, reactivity, solvent effects. RCsumC : Les vitesses de rtaction des e; avec les ions N H i T S et H l prtsentent des variationsdifferentes avec la composition des mtlanges de solvant rerr-butanolleau en allant de 0 B 100% en eau. Dans le tert-butanol pur, B 298 K, les valeurs relatives de k? (lo6 m h o l -I s-I) sont 3,2, 13 et 42.La valeur estimte du rayons de reaction R, dtpend du nombre minimal de moltcules de solvant requis entre le e; et I'ion rtactif pour atteindre les valeurs statiques de E de I'ensemble du solvant utiliste par le facteur f de Debye; comme les moltcules de solvant sont plus volumineuses que celles de I'eau, on considere que R, est plus Clevt dans la rtgion riche en alcool que dans la rtgion riche en eau. On a utilist le rnodttle de Smoluchowski-Debye-Nernst-Einstein pour tvaluer le rayon rtactionnelle efficace, KRI., dans lequel K est la probabilitt de rtaction par rencontre; KRr diminue en allant du rerr-butanol pur B l'eau pure.Dans la rtgion riche en eau, les energies d'activation E? des reactions efficaces, 11-24 kJ mol-l, sont semblables aux valeurs de EA0 des Clectrolytes qui rtagissent, 12-23 kJ mol-I. Pour le reactif inefficace N H ; CIO;, E? = 30 kJ mol-I. On attribue les valeurs tlevtes de E2 = 43-53 kJ rnol-' observtes dans le rerr-butanol B une Cnergie tlevte d'activation de la diffusion des e; dans ce solvant.

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confidence: 82%

Solvent effects on the reactivity of solvated electrons with ions in tert-butanol/water mixtures

Zhao¹,

Freeman²

1995

Can. J. Chem.

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“…Alcohol/water mixtures are good systems to study the effects of solvent structure on solvated electron reactivity because varying the composition of the mixture results in strong variations in the solvent structure, as reflected in physical properties such as viscosity (5) and dielectric relaxation time (6).…”

Section: Introductionmentioning

confidence: 99%

Solvent structure effects on solvated electron reactions with ions in 2-butanol/water mixed solvents

Peiris¹,

Freeman²

1991

Can. J. Chem.

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The Smoluchowski-Debye-Stokes-Einstein equation for the rate constant kz of a bimolecular reaction between charged or polar species was used to evaluate effects of bulk solvent properties on reaction rates of solvated electrons with NOT,,, H: , TI:, Cu:' , and AI:' in 2-butanol/water mixed solvents. To explain detailed effects it was necessary to consider more specific behavior of the solvent. Rate constants k 2 , activation energies E2, and pre-exponential factors Az of these reactions vary with the composition of 2-butanol/water mixtures. The values of E2 were in general similar to activation energies of ionic conductance EAo of the solutions, except for much higher values of E2 of (e; + NOT,,) in alcohol-rich solvents and of (e; + ~1:') in pure water solvent.The solvent apparently participates chemically in the NOT, reaction, and the ~1:' reaction is multistep. Rate constant and conductance measurements of thallium acetate solutions in 2-butanol containing zero and 10 mol% water were complicated by the formation of ion clusters larger than pairs.

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“…This observation is in agreement with that made by Tanaka et al 31 . In the study of the viscosity of aqueous solutions of isomeric butanols, Scnanayake et al 32 noticed similar minima. A work by Kipkemboi et al 33 on the viscosity aqueous mixtures of t-Butanol in the temperature range 288-318K also confirmed this phenomenon.…”

Section: Resultsmentioning

confidence: 83%

Effect Of Sodium Dodecyl Sulfate On Viscometric Properties Of Methanol, Ethanol, n-Propanol And iso-Propanol At Different Temperatures

Motin

Mia

Islam

et al. 2013

J. Bangla. Chem. Soc.

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Viscosity and density of isomeric butanol/water mixtures as functions of composition and temperature

Cited by 39 publications

References 11 publications

Solvent effects on the reactivity of solvated electrons with ions in tert-butanol/water mixtures

Solvent effects on the reactivity of solvated electrons with ions in tert-butanol/water mixtures

Solvent structure effects on solvated electron reactions with ions in 2-butanol/water mixed solvents

Effect Of Sodium Dodecyl Sulfate On Viscometric Properties Of Methanol, Ethanol, n-Propanol And iso-Propanol At Different Temperatures

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