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An unexpected 1,2-hydride shift in phosphoric acid-promoted cyclodimerization of styrene oxides under solvent-free conditions. A synthetic route towards 2,4-disubstituted 1,3-dioxolanes

Mazimba, O.; Majinda, R.R.; Masesane, I.B. (Elsevier Science Ltd, http://www.elsevier.com/locate/tetlet, NaN, 2009)

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Abstract:

A 1,2-hydride shift in the phosphoric acid-promoted cyclodimerization of styrene oxide and its chloro derivatives under solvent-free conditions leading to 2,4-disubstituted 1,3-dioxolanes is described. Methoxy substituents on the aromatic ring of the styrene oxide prevent the 1,2-hydride shift reaction leading to substituted 1,4-dioxanes. A possible mechanism for the formation of the 1,3-dioxolanes is proposed.

URI:

http://hdl.handle.net/10311/1026

Files in this item: 1

Masesane_TL_2009.pdf (246.5Kb)

Viscosity behaviour of particles with non-adsorbing polymers Part III—experimental study

Goodwin, J.W.; Hughes, R.W.; Reynolds, P.A.; Kwaambwa, H.M. (Elsevier B.V. www.elsevier.com/locate/colsurfa, NaN, 2004)

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Abstract:

A series of well characterised cis-poly(isoprene) (PIP) polymers (Mw = 1180, 8000, 28 300, 31 500, 86 000, 115 000 and 130 000) have been added to dispersions of poly(12-hydroxystearic acid) (PHS) coated poly(methylmethacrylate) (PMMA) particles in dodecane. The ratio of particle size to adsorbed layer was also varied. For a given added polymer molecular weight, the polymer concentration in the continuous phase covered the dilute, semi-dilute and concentrated regimes as defined by the critical concentrations c and c . The viscosity behaviour of latex dispersions with added polymer were similar for all latex/polymer combinations except when polymer Mw = 1180 was added. In the latter case, the effect of adding polymer reduced both the viscosity and shear thinning behaviour. This supports the contention that the lower molecular weight polymer acts more like a diluent than a depletent. The behaviour of the viscosity ratio (the viscosity of the dispersion relative to that of the medium) as a function of polymer concentration increased with an increase in the polymer concentration until some critical concentration (cmax) for all polymers except for a polymer molecular weight 1180 Daltons. The addition of the polymer Mw = 8000 gave the highest viscosity ratio values in the polymer concentration range studied. It was found that the viscosity of all latex/polymer combinations decreased with an increase in temperature. The results suggest that the viscosity behaviour cannot be explained on the basis of a simple steric–elastic model and require a modified theoretical treatment.

URI:

http://hdl.handle.net/10311/324

Files in this item: 1

Viscosity behaviiour of particles.pdf (4.522Mb)

Viscosity, molecular weight and concentration relationships at 298K of low molecular weight cis-polyisoprene in a good solvent

Kwaambwa, H.M.; Goodwin, J.W.; Hughes, R.W.; Reynolds, P.A. (Elsevier B.V. www.elsevier.com/locate/colsurfa, NaN, 2007)

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Abstract:

Aseries of six well characterised homopolymers of cis-polyisoprene (PIP) ranging from 1180 to 115,000 molecular weight were utilised to explore viscosity and the scaling relationship between viscosity and concentration in dodecane (good solvent). For each polymer molecular weight, the relative viscosity of PIP in dodecane at 298K was measured at several polymer concentrations using capillary viscometry. The linear extrapolation of experimental data based on Huggins, Kramer, Martin and Schulz-Blaschke equations was used to find the intrinsic viscosity at infinite dilution for each polymer molecular weight. The single-point method of evaluation of the intrinsic viscosity was also used for comparison. The Mark-Houwink fit of the data gave power index of 0.72 indicating that dodecane is good solvent for PIP and the latter exists in solution as open flexible coil. Both the radius of gyration and critical chain overlap concentration, c*, were derived from measured intrinsic viscosities. Plot of the relative viscosities versus the scaled concentration c/c*, resulted in single curve with slope value 4.44×10−2 and correlation coefficient r2 = 0.996, indicating good linear fit.

URI:

http://hdl.handle.net/10311/328

Files in this item: 1

Viscosity molecular weight.pdf (3.079Mb)

Volumetric Properties of (Difurylmethane + Alkan-1-ol) Binary Mixtures at 298.15 K

Ddamba, W.A.A.; Mokate, O. (Journal of Solution Chemistry., NaN, 2006)

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Abstract:

Densities (ρ) of the binary systems of {difurylmethane+(ethanol or propan-1- ol or butan-1-ol or pentan-1-ol or hexan-1-ol)} have been measured with an Anton Paar DMA 4500 vibrating-tube densimeter over the entire composition range at 298.15K and atmospheric pressure. Excess molar volumes (V E m ) of each binary system were determined and correlated by the Redlich-Kister equation. Limiting (Vi E,∞) and excess partial molar volumes (V E i ) of components of each binary system have been calculated to provide insight into the intermolecular interactions present and the packing efficiencies. The results have been discussed in terms of specific intermolecular interactions, dispersive forces and structural effects.

URI:

http://hdl.handle.net/10311/318

Files in this item: 1

Volumetric prop.pdf (3.737Mb)

Work in Thermodynamics

Ahmad, J.; Ddamba, W.A.A. (Chemic Publishing Co., http://www.asianjournalofchemistry.com/, NaN, 2006)

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Abstract:	The expression for mechanical work obtained in the expansion of a gas commonly used in physical chemistry textbooks is critically examined. The mathematical form of the first law of thermodynamics is arrived at by a procedure that is consistent with the common definition of mechanical work. The treatment is extended to explain the concept of reversible and irreversible work.
URI:	http://hdl.handle.net/10311/225

Files in this item: 2

license.txt (1.998Kb)

Work in thermodynamics.pdf (1.197Mb)

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