Chelatometric titration of tin in non-ferrous alloys with hedta

A new titrimetric method for determination of tin (4%) in aluminium alloys, tin- and lead-base alloys, solders, white bearing alloys, special bronzes and silver brazing alloys is proposed. HEDTA, Semi-Xylenol Orange and bismuth perchlorate are used as titrant, indicator and back-titrant respectively. Measures are taken to overcome the hydrolysis of Sn(IV). Monochloroacetic acid and ethylene glycol are added as auxiliary agents. The standard deviation of this method was found to be 0.2 mg and its coefficient of variation to vary from 0.25 to 2%, according to amount of tin. A novel method of sample decomposition and a modified method for separating Sn(IV) are also suggested.     

Dehydrochlorination of monodisperse poly(vinylidene chloride) latex

The objective of the work described in this paper was to produce dispersions of small spherical carbon particles, having particle diameters in the region of 0.1 μm. To this end, the dehydrochlorination of poly(vinylidene chloride) (PVDC) latex particles was attempted. The PVDC latex was prepared by a dispersion polymerization route. Both chemical and thermal dehydrochlorination routes were attempted. Chemical dehydrochlorination, using a variety of base/solvent systems, led to nonporous, spherical black particles of the required size, but which contained only 60% carbon; most of the remainder was oxygen, introduced by nucleophilic substitution reactions. Thermal dehydrochlorination, at 700°C under a nitrogen atmosphere, using a fluidized bed arrangement, on the other hand, led to black particles, having 90% carbon and which retained their sphericity, but which were highly porous. Initial chemical dehydrochlorination, prior to thermal treatment, did not seem to reduce the porosity of the final carbons. Dispersions of the carbon particles in a variety of solvents were readily achieved.     

A supported gold catalyst for the elimination of hydrogen from CO2 feed gas in the production of urea

Supported gold catalyst for eliminating hydrogen from CO₂ feed gas in the production of urea is found to be superior to other industrial catalysts (e.g. Pt/Al₂O₃ and PdPt/Al₂O₃) in catalytic activity and resistance to sulfur poisoning.     

Unprecedented intermolecular aldol-type condensation involving CH-acid and the nitro group

The first evidence that α-acylnitrone is an intermediate in the base-promoted reaction of 4-nitro-N,N-diethylaniline with aceptophenome to give an enaminoketone was obtained. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1645–1647, August, 1998.     

Excess enthalpies of (methyl propanoate or methyl pentanoate + 1-alkanol) at 298.15 K

The excess molar enthalpies H_m^E of methyl propanoate or methyl pentanoate + 1-butanol, + 1-hexanol, + 1-octanol, and + 1-decanol have been determined experimentally at 298.15 K using a Calvet microcalorimeter. For all these mixtures H_m^E > 0; the values increase with the chain length of the alkanol but decrease as the ester chain lengthens.     

Electrode kinetics of the metal complexes with aminopolycarboxylic acids: Part II. Cadmium-ethylenediamine-N,N,N′,N′-tetraacetate (EDTA) complexes

The d.c. polarographic current-potential curves of Cd(II)-EDTA complexes were examined in the pH range 0.5–10.0, to elucidate the mechanism of their electrode processes and to determine the relevant electrochemical kinetic parameters. It was shown that the first wave observed below pH 3 at ?0.58 to ?0.65 V vs. SCE is the reversible reduction wave of Cd(II) aquo-ion with kinetically-controlled limiting current, and the second wave observed above pH 1.5 at ?0.75 to ?1.21 V vs. SCE corresponds to the simultaneous irreversible reduction of four complex species, CdH₃L⁺, CdH₂L, CdHL^? and CdL^2?, where CdH_pL^(p?2)+ and L^4? denote the protonated complex species with p protons and the unprotonated EDTA ion, respectively. Analysis of the dependence of limiting current on the hydrogen ion concentration led to the conclusion that the preceding reaction determining the behaviour of limiting current is CdH₃L⁺?Cd²⁺+H₃L^? with k₃^d=6.3×10² s^?1 and k₃^f=3.3×10⁶ s^?1M^?1, where k₃^d and k₃^f are the dissociation and formation rate constants, respectively. On the other hand, from analysis of the dependence of half-wave potentials of the second wave on the hydrogen ion concentration, the kinetic parameters of the four complex species were evaluated, and are given in Table 1. Further, it was shown that the cathodic rate constants of these four charge transfer processes at some reference potential together with those of Cd(II)-HEDTA complexes fulfil the linear free energy relationship.     

Magnesium-butadiene addition compounds: Isolation,structural analysis and chemical reactivity

The magnesium-butadiene 1 : 1 (1), 1 : 2 (II) and 1 : 3 addition compounds obtained by the direct metalation of butadiene with metallic magnesium were isolated. These compounds have a polymeric structure. Structural analysis of these compounds by NMR and IR methods was carried out. The process for the formation of II via I and III via II was investigated. The results of protolysis and alkylation of the above magnesium compounds corresponded well to those of crotylmagnesium compounds.     

The chemistry and the sterechemistry of Poly(N-Alkyliminoalanes: XIII. The crystal and molecular structure of the hexamers (ClAlN-i-Pr)6 and (Me0.83H0.17AlN-i-Pr)6MeAlN-i-Pr)6

The crystall and molecular structures of (ClAlN-i-Pr)₆ (I), and of (Me_0.83H_0.17AlN-i-Pr)₆(MeAlN-i-Pr)₆ have been determined by single crystal three-dimensional X-ray analysis. Block-matrix least-squares refinements led to conventional R factor of 0.039 for I and 0.037 for II. The compounds are isostructural, as the cage molecules consist of a prismatic hexagonal framework, (AlN)₆, similar to that observed for the parent hydrogenated analogue (HAlN-i-Pr)₆.Some differences in bond distances and angles are discussed, in connection with the different Al-bonded substituents. Crystal data: I, trigonal space group R$\text{3}$; a = 17.083(2), c = 9.652(1); Z = 3; D_c 1.46 g cm^?3; II, trigonal space group R$\text{3}$, a = 17.378(3), c = 9.706(3) »; Z = 3; D_c 1.15 g cm^?3.     

meso－四（4－磺酸苯基）卟啉与Co（Ⅱ）的显色反应的研究

本文研究了弱酸性介质中钴（Ⅱ）与ＴＰＰＳ４的显色反应条件。实验发现胺类化合物质子化后，不参与成络反应，而均能使ＴＰＰＳ４试剂的吸光度大大降低，从而提高了测定的灵敏度，Ｃｏ（Ⅱ）－ＴＰＰＳ４络合比为１：１，ε＿（４２６）＝３．５４×１０￣５，钴含量在０～５．０μｇ／２５ｍＬ范围内呈线性，并用于烟草、茶叶中痕量钴的测定，得到了满意的结果。