Vapor−Liquid Equilibrium for Acetonitrile + Propanenitrile and 1-Pentanamine + 1-Methoxy-2-propanol

Antosik, Maria; Gałka, and Maria; Malanowski, Stanisław K.

doi:10.1021/je025660t

Cited by 21 publications

(11 citation statements)

References 14 publications

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“…A semiempirical approach was therefore used to establish the thermodynamic parameters (Δ G rxn , Δ H rxn , and Δ S rxn ) for the conversion of [ 3Me ][OTf] to [ 5Me ][OTf] in neat MeCN. To determine Δ H rxn , the DFT-calculated gas-phase enthalpy for the reaction of [ 5Me ] + and MeCN (Δ H g = −109 kJ mol –1 ) was combined in a thermochemical cycle (Figure S2, Supporting Information) with the lattice enthalpies for the two salts (Δ H lat ), and the experimental enthalpy of vaporization of MeCN (Δ H vap = 33.25 ± 0.21 kJ mol –1 ) . Lattice enthalpies were extracted from crystallographic unit cell volumes using the method of Jenkins, Passmore, and Glasser , and found to be 397 ± 16 kJ mol –1 for [ 3Me ][OTf] and 391 ± 16 kJ mol –1 for [ 5Me ][OTf] (see Experimental).…”

Section: Resultsmentioning

confidence: 99%

Influence of Ring Strain and Bond Polarization on the Ring Expansion of Phosphorus Homocycles

et al. 2017

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Heterolytic cleavage of homoatomic bonds is a challenge, as it requires separation of opposite charges. Even highly strained homoatomic rings (e.g., cyclopropane and cyclobutane) are kinetically stable and do not react with nucleophiles or electrophiles. In contrast, cycloalkanes bearing electron-donating/withdrawing substituents on adjacent carbons have polarized C-C bonds and undergo numerous heterolytic ring-opening and expansion reactions. Here we show that upon electrophile activation phosphorus homocycles exhibit analogous reactivity, which is modulated by the amount of ring strain and extent of bond polarization. Neutral rings (BuP), 1, or (BuP), 2, show no reactivity toward nitriles, but the cyclo-phosphinophosphonium derivative [(BuP)Me], [3Me], undergoes addition to nitriles giving five-membered PCN heterocycles. Because of its lower ring strain, the analogous four-membered ring, [(BuP)Me], [4Me], is thermodynamically stable with respect to cycloaddition with nitriles, despite similar P-P bond polarization. We also report the first example of isonitrile insertion into cyclophosphines, which is facile for polarized derivatives [3Me] and [4Me], but does not proceed for neutral 1 or 2, despite the calculated exothermicity of the process. Finally, we assessed the reactions of [4R] R = H, Cl, F toward 4-dimethylaminopyridine (dmap), which suggest that the site of nucleophilic attack varies with the extent of P-P bond polarization. These results deconvolute the influence of ring strain and bond polarization on the chemistry of inorganic homocycles and unlock new synthetic possibilities.

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Section: Resultsmentioning

confidence: 99%

Influence of Ring Strain and Bond Polarization on the Ring Expansion of Phosphorus Homocycles

et al. 2017

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“…As will be shown in the following sections, the description of the fluid‐phase equilibria of n ‐alkylamines is very sensitive to the values of the interaction parameters for the NH 2 group. The parameters of the NH 2 group and its interactions with the CH 3 and CH 2 groups are estimated using target experimental data for the fluid‐phase equilibria of pure primary n ‐alkylamines, specifically ethylamine, 63 n ‐propylamine, 64 n ‐butylamine, 54 n ‐pentylamine, 61 n ‐hexylamine, n ‐heptylamine, 55 and n ‐octylamine 56 . The adequacy of the theoretical description of the fluid‐phase equilibria for each one of these compounds is apparent from Figure 3a,b and Table 5.…”

Section: Resultsmentioning

confidence: 99%

“…(a) The vapor pressure P (Clausius–Clapeyron representation), and (b) coexisting vapor–liquid densities ρ as a function of temperature T for ethylamine (red circles 63 ), n ‐propylamine (blue squares 64 ), n ‐butylamine (green diamonds 54 ), n ‐pentylamine (grey triangles 61 ), n ‐hexylamine (cyan triangles 55 ), n ‐heptylamine (magenta triangles 55 ), and n ‐octylamine (black crosses 56 ). (c) The vapor pressure P (Clausius–Clapeyron representation), and (d) coexisting vapor–liquid densities ρ as a function of temperature T for N‐methylcyclohexylamine (MCA, red circles 65 ), N‐ethylcyclohexylamine (ECA, blue squares 65 ), and N,N ‐dimethylcyclohexylamine (DMCA, green diamonds 65 ).…”

Section: Resultsmentioning

confidence: 99%

Description of the thermodynamic properties and fluid‐phase behavior of aqueous solutions of linear, branched, and cyclic amines

et al. 2021

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The SAFT-γ Mie group-contribution equation of state is used to represent the fluid-phase behavior of aqueous solutions of a variety of linear, branched, and cyclic amines. New group interactions are developed in order to model the mixtures of interest, including the like and unlike interactions between alkyl primary, secondary, and tertiary amine groups (NH 2 , NH, N), cyclic secondary and tertiary amine groups (cNH, cN), and cyclic methine-amine groups (cCHNH, cCHN) with water (H 2 O). The group-interaction parameters are estimated from appropriate experimental thermodynamic data for pure amines and selected mixtures. By taking advantage of the group-contribution nature of the method, one can describe the fluid-phase behavior of mixtures of molecules comprising those groups over broad ranges of temperature, pressure, and composition. A number of aqueous solutions of amines are studied including linear, branched aliphatic, and cyclic amines. Liquid-liquid equilibria (LLE) bounded by lower critical solution temperatures (LCSTs) have been reported experimentally and are reproduced here with the SAFT-γ Mie approach. The main feature of the approach is the ability not only to represent accurately the experimental data employed in the parameter estimation, but also to predict the vapor-liquid, liquid-liquid, and vapor-liquid-liquid equilibria, and LCSTs with the same set of parameters. Pure compound and binary phase diagrams of diverse types of amines and their aqueous solutions are assessed in order to demonstrate the main features of the thermodynamic and fluid-phase behavior.

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“…For allyl alcohol and 1-propanol, data from Table were used, and for benzene and 2-methylpentane, previously published parameters were used. The detailed procedure was given by Antosik et al…”

Section: Methodsmentioning

confidence: 99%

Vapor−Liquid Equilibrium for Benzene + 2-Methylpentane and Allyl Alcohol + 1-Propanol

and¹,

Malanowski²

2004

J. Chem. Eng. Data

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The saturation pressures of 1-propanol at (311 to 353) K were measured by the ebulliometric method. The vapor−liquid equilibrium (VLE), simultaneous measurements of pressure, temperature, and composition of liquid and vapor phases (x, y, p, T), was measured by an ebulliometric method for the system benzene + 2-methylpentane at (313.14, 323.14, and 333.13) K and for the system allyl alcohol + 1-propanol at (313.15, 333.15, and 353.15) K. The experimental vapor pressures were correlated with the Antoine and association + equation of state (AEOS) equations, and VLE was correlated with equations representing the activity coefficient and with the AEOS equation of state.

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Vapor−Liquid Equilibrium for Acetonitrile + Propanenitrile and 1-Pentanamine + 1-Methoxy-2-propanol

Cited by 21 publications

References 14 publications

Influence of Ring Strain and Bond Polarization on the Ring Expansion of Phosphorus Homocycles

Influence of Ring Strain and Bond Polarization on the Ring Expansion of Phosphorus Homocycles

Description of the thermodynamic properties and fluid‐phase behavior of aqueous solutions of linear, branched, and cyclic amines

Vapor−Liquid Equilibrium for Benzene + 2-Methylpentane and Allyl Alcohol + 1-Propanol

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