Association of the Butyl Alcohols and n-Decanol

Abstract

The dielectric constants at 0.1 MHz of n-, iso-, sec-, and t-butanol and n-decanol each at nine concentrations in the range 0.2-1.0 mole fraction in cyclohexane, p-dioxane, mesitylene, andp-xylene have been measured at 25 "C. Apparent dipole moments and Kirkwood correlation factors have been evaluated. Cyclohexane is regarded as an inert solvent in which alcohol self association alone is considered responsible for the anomalous electric polarization. The other three solvents have a disassociating effect which increases p-xylene < mesitylene < p-dioxane. At the lowest concentrations the alcohols have larger apparent dipole moments in these solvents than in cyclohexane. The opposite tends to be the case for the more concentrated alcohol solutions. The results suggest that alcohol association is initially dominated by the formation of small, weakly polar multimers, and eventually larger highly polar multimers predominate.Les constantes diClectriques a 0.1 MHz du n-, iso-, sec-, et t-butanol et du n-dCcanol, chacun avec neuf concentrations dans le domaine de 0.2-1.0 mole dans le cyclohexane, p-dioxane, mCsitylbne et le p-xylkne, ont 6tC mesurees 25 "C. Les moments dipolaires apparents et les facteurs de corrClation de Kirkwood ont Ct C 6valuCs. On considere le cyclohexane comme un solvant inerte dans lequel seule une association intermolkulaire de I'alcool est considBrCe comme responsable de la polarisation Cletrique anormale.Les trois autres solvants ont un effet de dissociation qui croft p-xylene d misitylene < p-dioxane. Aux concentrations les plus basses, les alcools ont des moments dipolaires apparents plus grands dans ces solvants que dans le cyclohexane. L'inverse a tendance a se produire pour des solutions alcooliques plus concentrBes. Les rksultats suggkrent que I'association de l'alcool est d'abord le fait de la formation de petites multimeres 1Cgerement polaires et Bventuellement une plus grande quantitC de multimeres hautement polaires prkdomine.

Application of a new theoretical procedure for calculating Kirkwood correlation factors in alkanol + hexane and alkanol + pentane mixtures

“…To evaluate eqn (20) f 1 has to be substituted from eqn (17) in case of mixtures or eqn (18) in case of a pure alcohol considering that…”

“…For K 1 = K and K c4 = 0 eqn (26) reduces to eqn (20) and the solution of eqn (25) for f 1 reduces to eqn (17).…”

“…3 There is a considerable number of authors and research groups who have dealt with the experimental determination of Kirkwood factors g K of alcohol + hydrocarbon and also alcohol + CCl 4 mixtures including pure alcohols. [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27] Early attempts to develop a statistical theory of g K based on Wertheim's model of rigid dipoles have been made by Winkelmann and Quitzsch. 28 However, no consistent and successfully working molecular theory exists up to now for describing g K simultaneously with other physical properties of alcohol + inert solvent mixtures such as thermodynamic excess functions and spectroscopic data taking into account the chain-like association of alcohol molecules.…”

Poly(hydroxybutyrate-co-hydroxyvalerate) Porous Matrices from Thermally Induced Phase Separation

“…Note that there are hydroxyl and carboxyl functional groups on both ends of a PHBV chain and two exposed oxygen atoms in the molecular structure of 1,4 dioxane. Interactions between these functional groups and the oxygen lone pair electrons of dioxane are not negligible [36]. In fact, it should be expected that hydrogen bonds were established between 1,4-dioxane and the molecular chains [37].…”

Estudio experimental y teórico de mezclas líquidas binarias formadas por 1-alcoholes y ciclohexilamina

“…Los sistemas con valores negativos de revelan que en el proceso de mezcla ha disminuido la polarización dipolar a causa, fundamentalmente, de la geometría y tamaño de los multímeros formados, como es el caso del sistema 1-propanol + propanal citado anteriormente ( 3.79 a T = 298.15 K y 0.5 [75]), y que los dipolos formados de la interacción de las moléculas distintas (alcohol-solvente) no compensan el efecto negativo de la ruptura de las interacciones entre moléculas iguales. : símbolos: (•) 1-butanol [89], (▼) 1-pentanol [84], (■) 1-hexanol [84], (♦) 1-heptanol [84], (▲) 1-decanol [89] a temperatura T = 298.15 K. Líneas sólidas: ajuste a la ecuación Redlich-Kister de los datos experimentales originales.…”