Alcohol-water mixtures revisited

Franks, Felix; Desnoyers, Jacques E.

doi:10.1017/cbo9780511565380.004

Cited by 100 publications

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“…While all these views presented here are not entirely new (3,4), the present work provides some additional data to support such views within a limited power of the thermodynamic Can. J. Chem.…”

Section: [2]mentioning

confidence: 55%

“…Figure 5 shows the excess partial molar entropies, SmE(i), calculated by eq. [4]. The partial molar enthalpies, HmE(i), are also replotted.…”

Section: [2]mentioning

confidence: 99%

“…While this system had been investigated previously long range. If TBA molecules are distributed randomly among (3,4), it was the first time that the partial molar enthalpies were H 2 0 molecules without any preferential association, a TBA measured directly for the TBA-water mixtures. Generally, molecule is surrounded by (1 -xTBA)/xTBA molecules of H20, evaluation of these quantities is possible by differentiating the existing values of excess (integral) molar enthalpies, HmE.…”

Section: Introductionmentioning

confidence: 99%

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Excess partial molar enthalpies of water in water–tert-butanol mixtures

Koga¹

1988

Can. J. Chem.

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The excess partial molar enthalpies of H20, H,,,~(H~O), in water-tert-butanol mixtures were measured at 30.00, 36.75, and 40.45". Using the values of H,~(TBA) of the previous work (Y. Koga, Can. J. Chem. 66, 1187(1988), the excess (integral) molar enthalpies of the solution, H,,~, were calculated at 30.00°C, and compared with the literature values. The comparison was satisfactory. From the literature values of the excess free energy, the chemical potentials of each component were evaluated for the range, XTBA > 0.1. With the measured values of the excess partial molar enthalpies, the excess partial molar entropies were also calculated. These partial molar thermodynamic quantities and their dependence on temperature and composition clearly support the following views: (1 ) in the intermediate region, 0.1 < XTBA < 0.5, the system is very close to a critical demixing, and (2) in the TBA-rich region, XTBA > 0.6, TBA molecules in the solution are in almost the same environment as in the pure liquid, while H20 molecules lose the hydrogen bond network completely and are dispersed in the TBA liquid structure.YOSHIKATA KOGA. Can. J . Chem. 66, 317 1 (1988).On a mesurC les enthalpies molaires partielles en excks du H20, HmE(~,O), dans des melanges eau-tert-butanol 2 30,00, 36,75 et 40,45"C. Utilisant les valeurs du H,:(TBA)de travaux antirieurs (Y. Koga, J . Can. Chem. 66, 1187(1988), on a calculC les enthalpies molaires (integral) en excks 2 30,0OoC, du HmE en solution et on les a comparCes aux valeurs existantes. La comparaison s'est rkvklke satisfaisante. A partir des valeurs d'knergie libre rCpertoriCes dans la littkrature, on a kvaluk les potentiels chimiques de chaque composante dans l'intervalle de xT,, > 0 , l . On a Cgalement calculk les entropies molaires en excks 2 partir des valeurs mesurCes des enthalpies molaires partielles en excks. Ces quantitks thermodynamiques partielles en excks, leurs relations avec la tempkrature i t la composit~on confirment nettement les faits suivants : (1 ) dans la rkgion intermkdiaire, 0,1 < XTBA < 0,5, le systemeest trks prks de ladkmixion critique, et (2) dans larCgion richeenTBA, XTBA > 0,6, les molCcules de TBA en solution sont 2 peu prks dans le mCme environnement que dans le liquide pur; par ailleurs, les molkcules de H 2 0 perdent complktement le reseau de liaisons hydrogknes et se dispersent dans la structure du TBA.[Traduit par la revue] Introduction solute-solute interaction is apparently repulsive. This suggests In the previous papers (called paper I (1) and I1 (2) that already at this concentration TBA molecules have more hereinafter), results were reported on the excess partial molar enthalpic difficulty in settling into the solution, i.e. the structure enthalpies of tert-butanol (TBA) in TBA-H20 mixtures, enhancement by a previously settled TBA molecule spans a H,~(TBA). While this system had been investigated previously long range. If TBA molecules are distributed randomly among (3,4), it was the first time that the partial molar enthalpies were H 2 0 molecules wit...

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Section: [2]mentioning

confidence: 55%

“…Figure 5 shows the excess partial molar entropies, SmE(i), calculated by eq. [4]. The partial molar enthalpies, HmE(i), are also replotted.…”

Section: [2]mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Excess partial molar enthalpies of water in water–tert-butanol mixtures

Koga¹

1988

Can. J. Chem.

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“…[3] and [5]) and volume fraction weighted averaging (eqs. [4] and [5]) for comparison. These data and the thermodynamic constants used in eq.…”

Section: °Cmentioning

confidence: 99%

“…Water and alcohol mixtures themselves show unique minima and maxima in their thermodynamic properties at low alcohol concentrations (4)(5)(6)(7)(8)(9)(10). The formation of "clathrate-like" structures is believed to be the cause of these unusual properties in the case of alcohols having alkyl groups with 3-or 4-carbon atoms.…”

Section: Introductionmentioning

confidence: 99%

Ultrasonic velocity, excess adiabatic compressibility, apparent molar volume, and apparent molar compressibility properties of binary liquid mixtures containing 2-butoxyethanol

Rao¹,

Verrall²

1987

Can. J. Chem.

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. Can. J. Chem. 65, 810 (1987). Ultrasonic velocity and density data of binary systems of water-2-butoxyethanol (BE), 2-butoxyethanol-benzene, and 2-butoxyethanol-decane are reported for temperatures of 25, 40, and 55°C. Adiabatic compressibility coefficients, apparent molar volumes, and apparent molar compressibilities were calculated from these data. Excess adiabatic compressibility properties were evaluated using volume fraction weighting of the individual component properties to estimate ideal mixture behavior. These results are compared with the data obtained based on the use of mole fraction weighting of the individual component properties for the ideal behavior value. A sharp ultrasonic velocity maximum and compressibility minimum is observed at low BE concentration in mixtures of water-BE at all temperatures. These maxima in ultrasonic velocity and minima in adiabatic compressibility are attributed to the formation of "clathrate-like" structures of water and alcohol. A shift of the velocity maximum towards lower concentrations of BE was observed with increase of temperature. A minimum in the ultrasonic velocity and a maximum in adiabatic compressibility coefficient values are observed in systems of BE-benzene and BE-decane. These results are discussed in terms of the breakdown of associated alcohol structures and the interstitial location of hydrocarbon molecules in alcohol aggregates. N. P. RAO et RONALD E. VERRALL. Can. J. Chem. 65, 810 (1987). OpCrant des tempkratures de 25, 40 et 55"C, on a mesurC les vitesses ultrasoniques et les densitCs des systemes binaires eau/butoxy-2 tthanol (BE), butoxy-2 Cthanollbenzkne et butoxy-2 CthanolldCcane. A partir de ces donnCes, on a calculC les coefficients de compressibilitC adiabatique, les volumes molaires apparents et les compressibilitCs molaires apparentes. Utilisant les poids relatifs des fractions du volume des propriCtCs des composantes individuelles pour Cvaluer le comportement du mClange idCal, on a CvaluC les propriCtCs de compressibilitC adiabatique en exces. On compare ces rCsultats avec les donnCes obtenues en se basant sur I'usage des poids relatifs des fractions molaires des propriCtCs des composantes individuelles pour Cvaluer le comportement du mClange ideal. A toutes les temperatures, on observe un maximum important de la vitesse ultrasonique et une compressibilitC minimale a des faibles concentrations de BE dans les mClanges eau/BE. On attribue ces maxima dans la vitesse ultrasonique et ces minima dans la compressibilitC adiabatique a la fom~ation de structures de l'eau et de llCthanol "ressernblant a des chlathrates". Lorsqu'on augmente la tempCrature, on observe un dCplacement du maximum de la vitesse vers les concentrations plus basses de BE. Dans les systemes BEIbenzkne et BEldCcane, on observe un minimum dans la vitesse ultrasonique et un maximum dans les valeurs des coefficients de compressibilitC adiabatique. On discute de ces rCsultats en fonction d'un bris des structures associCes de l'alcool et de la position des molCcules interstiti...

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