Heat capacity and corresponding states in alkan-1-ol–n-alkane systems

Andreoli-Ball, Lina; Patterson, Donald; Costas, Miguel; Cáceres-Alonso, Mercedes

doi:10.1039/f19888403991

J. Chem. Soc., Faraday Trans. 1

1988

DOI: 10.1039/f19888403991

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Heat capacity and corresponding states in alkan-1-ol–n-alkane systems

Lina Andreoli-Ball¹,

Donald Patterson²,

Miguel Costas³

et al.

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Cited by 79 publications

(58 citation statements)

References 7 publications

(29 reference statements)

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“…9 together with those for the corresponding linear alcohol (1-heptanol) from ref. 3. As expected, the methylcyclohexanols show a self-association behaviour which corresponds to that of 1-heptanol at T > 25OC.…”

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confidence: 59%

“…It has been found that, with the exceptions of methanol and ethanol, the associational part of the apparent molar heat capacity +c(assoc) of all linear alcohols is independent of both alcohol and alkane chain length. As a consequence, values of +c(assoc) for different systems follow a single corresponding states curve when plotted against a new concentration variable, essentially the hydroxyl concentration in solution (3). This remarkable result is predicted by the Treszczanowicz-Kehiaian (TK) theory (4) for self-associated liquids + inert solvents with a unique equilibrium constant for H-bond formation.…”

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confidence: 61%

“…A@ and Kiq, can be fitted in the least square sense to experimental +c(assoc) = +, -lim + C (~O H + 0) where the infinite dilution apparent molar heat capacity represents the contribution to the heat capacity of the alcohol in the absence of any association, each alcohol molecule being isolated in an inert solvent. For linear alcohols (1,3) tetramers turned out to be the predominant species; the K4q were found to change rapidly with the 1-alcohol studied reflecting the inter-alcohol rather than inter-hydroxyl character of these volumetric equilibrium constants. However, these K4Q can be translated into a single equilibrium constant for H-bond formation in tetramers, K4.…”

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confidence: 99%

“…[I] to [3]; note that although the TK model parameters were fitted to dilute alcohol concentration data, good predictions throughout the concentration range are obtained. In Fig.…”

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confidence: 99%

“…According to eq . [3] CpE corresponds to the difference between two Schottky curves, one for the alcohol in solution and the other in the pure state. At very low alcohol concentration (curve 111 in Fig.…”

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confidence: 99%

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Steric effects on the self-association of branched and cyclic alcohols in inert solvents. Apparent heat capacities of secondary and tertiary alcohols in hydrocarbons

Cáceres-Alonso¹,

Costas²,

Andreoli-Ball³

et al. 1988

Can. J. Chem.

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Chem. 66,989 (1988).Apparent heat capacities have been measured for fifteen branched and cyclic alcohols in dilute n-decane solution at 25OC. The alcohols were 2-methyl-2-propanol, cyclohexanol, 3-methyl-3-pentanol, trans-, cis-, and mixed isomer 2-methylcyclohexanol, I-methylcyclohexanol, 3-ethyl-3-pentanol, cyclooctanol, 3,7-dimethyl-I-octanol, 5-decanol, 4-propyl-4-heptanol, cyclododecanol, 5-butyl-5-nonanol, and 8-hexadecanol (in n-hexane). Excess heat capacities cPE throughout the concentration range were measured at 25OC for: 1-hexanol + n-hexadecane (11-CI6) and + 2,2,4,4,6,8,8-heptamethylnonane (br-C16), 4-propyl-4-heptanol, and 1-decanol + n-decane, 3-methyl-3-pentanol + 11-c~~ and + br-C16 and at 27OC for cyclohexanol + 1 1 -c~~ and + br-CI6 Also, for 3-methyl-3-pentanol + n-decane CpE was measured at 10, 25, 40, and 50°C. For a series of isomeric alcohols, the apparent molar heat capacities show a maximum against concentration which decreases and moves to higher alcohol concentration as the hydroxyl group on the alcohol becomes increasingly hindered, effectively reducing the alcohol self-association capabilities. This situation is also reflected by the heat capacities of the pure alcohols which increase strongly in magnitude in going from a linear I-alcohol to an isomeric alcohol which has its hydroxyl group on a quaternary carbon atom. cPE of the mixtures are negative at low alcohol concentrations turning positive at increasingly higher alcohol concentrations as the steric hindrance on the hydroxyl group increases. Throughout most of the concentration range cPE for the branched or cyclic alcohols is considerably more positive than for the corresponding isomeric 1-alcohol. For the highly hindered 3-methyl-3-pentanol c P E (~) passes through a maximum. All of the above behaviour is explained by the Treszczanowicz -Kehiaian model for self-associated liquids + inert solvents which has been applied to the present data. Equilibrium constants have been obtained for alcohol association and are sensitive to alcohol structure. At low alcohol concentrations, while for the linear I -alcohols tetramers are the predominant species and dimer are almost absent, for the corresponding isomeric alcohols the concentration of tetramers is severely reduced and the lower species, i.e. trimers and dimers, are more important. For the highly hindered alcohols, monomers are the predominant species in dilute solution reflecting the decrease in self-association ability that steric hindrance of the hydroxyl group imposes on them.MERCEDES CACERES-ALONSO, MIGUEL COSTAS, LINA ANDREOLI-BALL et DONALD PATTERSON. Can. J. Chem. 66, 989 (1988).OpCrant i 25"C, on a mesure les capacitis calorifiques apparentes de quinze alcools ramifiCs et cycliques en solutions diluCes dans le n-dCcane. I1 s'agit des alcools suivants : methyl-2 propanol-2, cyclohexanol, methyl-3 pentanol-3, les isomtres cis-et trans-du mCthyl-2 cyclohexanol, methyl-l cyclohexanol, Cthyl-3 pentanol-3, cyclooctanol, dimethyl-3,7 octanol-1, dCcanol-5, propyl-4 heptanol-4,...

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confidence: 59%

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confidence: 61%

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confidence: 99%

“…[I] to [3]; note that although the TK model parameters were fitted to dilute alcohol concentration data, good predictions throughout the concentration range are obtained. In Fig.…”

mentioning

confidence: 99%

mentioning

confidence: 99%

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Steric effects on the self-association of branched and cyclic alcohols in inert solvents. Apparent heat capacities of secondary and tertiary alcohols in hydrocarbons

Cáceres-Alonso¹,

Costas²,

Andreoli-Ball³

et al. 1988

Can. J. Chem.

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Proton NMR and IR study of self‐association in pyridylalkanols: open or cyclic dimers? higher polymers?

Lomas

Adenier

Cordier

2006

J of Physical Organic Chem

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1 H NMR measurements indicate that (X-pyridyl)alkanols of the general formula (C 5 H 4 N)(CH 2 ) n OH, where n ¼ 1, 2 or 3, self-associate as open dimers, cyclic dimers, trimers and tetramers, with considerable variations depending on the position of the alkyl chain and its length. 2-(X-Pyridyl)propan-2-ols behave like the corresponding pyridylmethanols with, however, somewhat lower association constants. The IR spectra of 3-(X-pyridyl)-2,2,4,4tetramethylpentan-3-ols (X ¼ 3 or 4) in carbon tetrachloride suggest weak association, while the 2-pyridyl derivative occurs mainly as the intramolecularly hydrogen-bonded rotamer. The OH NMR shifts for the 3-and 4-pyridyl derivatives in benzene are concentration-dependent, but neither the equilibrium constants nor the degree of association can be evaluated. Benzyl alcohol in benzene associates as an open dimer and a cyclic tetramer, as does 2phenylpropan-2-ol, only more weakly. Rotation barriers for 3-(X-pyridyl)-2,2,4,4-tetramethylpentan-3-ols (X ¼ 2, 3 or 4) in DMSO or nitrobenzene are 20-21 kcal mol À1 .

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Excess molar heat capacities and excess molar volumes of (propan-2-ol, or butan-2-ol, or pentan-2-ol, or pentan-3-ol, or 2-methylbutan-2-ol +n-heptane) at the temperature 298.15 K

Tanaka

Toyama

1996

The Journal of Chemical Thermodynamics

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Heat capacity and corresponding states in alkan-1-ol–n-alkane systems

Cited by 79 publications

References 7 publications

Steric effects on the self-association of branched and cyclic alcohols in inert solvents. Apparent heat capacities of secondary and tertiary alcohols in hydrocarbons

Steric effects on the self-association of branched and cyclic alcohols in inert solvents. Apparent heat capacities of secondary and tertiary alcohols in hydrocarbons

Proton NMR and IR study of self‐association in pyridylalkanols: open or cyclic dimers? higher polymers?

Excess molar heat capacities and excess molar volumes of (propan-2-ol, or butan-2-ol, or pentan-2-ol, or pentan-3-ol, or 2-methylbutan-2-ol +n-heptane) at the temperature 298.15 K

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