Phase transport of HCl, HFeCl4, water, and crude oil components in acid-crude oil systems

A model describing the transport of HCl and HFeCl(4) from a water phase to a crude oil phase and subsequent sludge formation is proposed. Crude oil phase transfer compounds (PTCs) that are basic in nature facilitate transport of acid to the crude oil phase. These crude oil PTCs are able to migrate to the acid-oil interface and form acid-base complexes that can return to the oil phase. Once in the crude phase, these protonated compounds have a propensity to form aggregates. Growth of small aggregates into larger aggregates eventually generates a precipitate known as acid-sludge. Under certain conditions the model predicts the amount of acid-sludge formed to be proportional to the acid activity, or acidity function H(0), in the water phase. This relation was confirmed experimentally. Furthermore, the total amount of phase-transported acid is proportional to the base content of the crude oil. In strong HCl formulations containing Fe(3+), the acid HFeCl(4) is formed in small amounts that can be transported to the crude oil phase. In principle, the behavior of HFeCl(4) is similar to that of HCl. It was shown that HCl and HFeCl(4) compete for basic, or receptor, sites and that exchange between these two acids is reversible. The antisludging agent dodecylbenzenesulfonic acid, DBSA, intervenes through the same mechanism; that is, it competes for receptor sites with HCl and HFeCl(4). Exchange between HCl/HFeCl(4) and DBSA was also shown to be reversible.     

A new oxidative alkoxylation reaction The preparation of 5-alkoxy-4,4-dialkyl-1-aryl-3-pyrazolidinones

A new oxidative alkoxylation method is described. According to this method alkoxy groups are introduced in the 5-position of 4,4-dialkyl-1-aryl-3-pyrazolidinones by oxidation with HgO or SeO₂ in alcohols. The mechanism, the scope and limitations of the reaction are discussed. The 5-alkoxy-4,4-dialkyl-1-aryl-3-pyrazolidinones may be converted to 1-aryl-4,4-dialkyl-5-(1-aryl-3-oxo-4,4-dialkyl-5-alkoxy-5-pyrazolidinyl)-3-pyrazolidinones. The structure of the reaction products was studied by IR and NMR analyses.     

Determination of the reactivity ratios of methyl acrylate with the vinyl acetate,vinyl 2,2-dimethyl-propanoate,and vinyl 2-ethylhexanoate

The course of composition drift in copolymerization reactions is determined by reactivity ratios of the contributing monomers. Since polymer properties are directly correlated with the resulting chemical composition distribution, reactivity ratios are of paramount importance. Furthermore, obtaining correct reactivity ratios is a prerequisite for good model predictions. For vinyl acetate (VAc), vinyl 2,2-dimethyl-propanoate also known as vinyl pivalate (VPV), and vinyl 2-ethylhexanoate (V2EH), the reactivity ratios with methyl acrylate (MA) have been determined by means of low conversion bulk polymerization. The mol fraction of MA in the resulting copolymer was determined by ¹H-NMR. Nonlinear optimization on the thus-obtained monomer feed–copolymer composition data resulted in the following sets of reactivity ratios: r_MA = 6.9 ± 1.4 and r_VAc = 0.013 ± 0.02; r_MA = 5.5 ± 1.2 and r_VPV = 0.017 ± 0.035; r_MA = 6.9 ± 2.7 and r_V2EH = 0.093 ± 0.23. As a result of the similar and overlapping reactivity data of the three methyl acrylate–vinyl ester monomer systems, for practical puposes these data can be described with one set of reactivity data. Nonlinear optimization of all monomer feed–copolymer composition data together resulted in r_MA = 6.1 ± 0.6 and r_VEst = 0.0087 ± 0.023. © 1994 John Wiley & Sons, Inc.     

Dichloro{N‐[3‐(η5‐cyclopentadienyl)propyl]‐4‐toluenesulfonamido‐κ2N,O}titanium(IV)

The title compound, [Ti(C₁₅H₁₇NO₂S)Cl₂], has a Ti atom bound to the N and O atoms of a p‐toluene­sulfon­amide ligand, which is tethered by a three‐carbon chain to a η⁵‐cyclo­penta­dienyl group. The distorted square‐pyramidal geometry is completed by two Cl atoms. The Ti—N bond length of 2.0375 (13) Å is longer than that in related compounds, the N atom having asymmetric trigonal–planar geometry. Conformational strain relief is noted when compared with ethyl‐tethered compounds.     

Growth and optical characterisation of multilayers of InGaN quantum dots

We report on the growth (using metal-organic vapour phase epitaxy) and optical characterisation of single and multiple layers of InGaN quantum dots (QDs), which were formed by annealing InGaN epilayers at the growth temperature in nitrogen. The size and density of the nanostructures have been found to be fairly similar for uncapped single and three layer QD samples if the GaN barriers between the dot layers are grown at the same temperature as the InGaN epilayer. The distribution of nanostructure heights of the final QD layer of three is wider and is centred around a larger size if the GaN barriers are grown at two temperatures (first a thin layer at the dot growth temperature, then a thicker layer at a higher temperature). Micro-photoluminescence studies at 4.2 K of capped samples have confirmed the QD nature of the capped nanostructures by the observation of sharp emission peaks with full width at half maximum limited by the resolution of the spectrometer. We have also observed much more QD emission per unit area in a sample with three QD layers, than in a sample with a single QD layer, as expected.