Chloroform as hydrogen donor to some organophosphorus compounds and long-chain tertiary alkylamines

Nishimura, Sanji; Ke, Charles H.; Li, Norman C.

doi:10.1021/j100850a039

Cited by 27 publications

(5 citation statements)

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“…The similarity between the proton donating properties of N-methylaniline and chloroform has been commented upon by Lady and Whetsel.7 The heat of formation of the chloroform-TBP complex in cyclohexane has been determined to be -4.3 kcal/mol by a proton magnetic resonance method. 8 The agreement with our value of -4.17 kcal/mol is particularly noteworthy, when we consider the fact the ranges of the TBP and chloroform concentrations used in the present research (infrared method) are 0.07-0.18 and 7.5-10 M, respectively, whereas the corresponding ranges in the proton magnetic resonance method8 are 0.5-1.5 and 0.05 M, respectively.…”

Section: Discussionsupporting

confidence: 85%

Infrared studies of amine complexes with some organophosphorus compounds

Nishimura¹,

Li²

1968

J. Phys. Chem.

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Section: Discussionsupporting

confidence: 85%

Infrared studies of amine complexes with some organophosphorus compounds

Nishimura¹,

Li²

1968

J. Phys. Chem.

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“…On the other hand, TBP molecules do also enter the water layer and drag chloroform with them, two of them forming a dimer via hydrophobic association of their alkyl chains. Such mode of TBP dimerization in water is supported by experimental ,− as well as theoretical studies …”

Section: Resultsmentioning

confidence: 65%

TBP at the Water−Oil Interface: The Effect of TBP Concentration and Water Acidity Investigated by Molecular Dynamics Simulations

2001

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Molecular dynamics simulations provide microscopic pictures of the behavior of TBP (tri-n-butyl phosphate) at the water−“oil” interface, and in water−“oil” mixtures where “oil” is modeled by chloroform. It is shown that, depending on the TBP concentration and water acidity, TBP behaves as a surfactant, an interface modifier, or a solute in oil. At low concentrations, TBP is surface active and forms an unsaturated monolayer at the “planar” interface between the pure water and oil phases, adopting an “amphiphilic orientation”. Increasing the TBP concentration induces water−oil mixing at the interface which becomes very rough while TBP orientations at the phase boundary are more random and TBP molecules solubilize in oil. The effect of water acidity is investigated with three nitric acid models: neutral NO3H, ionic NO3 - H3O+ and TBPH+ NO3 -. The role of these species on the properties of the water−oil boundaries and on the outcome of water−oil demixing experiments is presented. The neutral NO3H form is highly surface active. Hydrogen bonding between TBP and NO3H, TBPH+, or H3O+ disrupts the first TBP layer and leads, at high TBP concentrations, to a mixed third phase or to a microemulsion. These results are important for our understanding of the microscopic solution state of liquid−liquid extraction systems.

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“…Fig.3Association constants (K 1 ) measured for six different complexes using31 P NMR titrations in a linear alkane (n-octane) compared with the corresponding association constants measured in a cyclic alkane (cyclohexane, squares, and cis-decalin, circles). The line represents y = x.…”

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confidence: 99%

Hydrogen bonding properties of non-polar solvents

2010

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A combination of high-throughput NMR titration experiments, UV-Vis absorption titrations and data collected from the literature on 1:1 H-bonded complexes has been used to characterise the H-bond properties of non-polar organic solvents: alkanes, perfluorocarbons, aromatic and halogenated organic solvents. The results are analysed in the context of the electrostatic solvent competition model, which assumes that solvent effects on intermolecular interactions can be interpreted based on the exchange of specific functional group contacts, with minimal involvement of the bulk solvent. For solvents where the H-bond parameters have been measured as solutes in carbon tetrachloride solution, the H-bond parameters measured here for the same compounds as solvents are practically identical, i.e. solute and solvent H-bond parameters are directly interchangable. For the very non-polar solvents, alkanes and perfluorocarbons, the experimental H-bond parameters are significantly larger than expected based on calculated molecular electrostatic potential surfaces. This suggests an increase in the relative importance of van der Waals interactions when electrostatic effects are weak, but there is no detectable difference between the solvation properties of cyclic and linear alkanes, which have different van der Waals interaction properties.

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Chloroform as hydrogen donor to some organophosphorus compounds and long-chain tertiary alkylamines

Cited by 27 publications

References 0 publications

Infrared studies of amine complexes with some organophosphorus compounds

Infrared studies of amine complexes with some organophosphorus compounds

TBP at the Water−Oil Interface: The Effect of TBP Concentration and Water Acidity Investigated by Molecular Dynamics Simulations

Hydrogen bonding properties of non-polar solvents

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