Effect of sodium metasilicate on natural flotability of coal

The effect of the quantity of sodium metasilicate and conditioning time in one set of experiments, and the effect of the solution concentration of sodium metasilicate, added at the same dosage and conditioning time to coal slurry, on flotability of a typical Indian coal in another set of experiments are studied. Two sets of 3² full factorial experiments are carried out to assess the effects of the aforementioned variables. The generated data are analyzed quantitatively and explained qualitatively. At 0.1% (w/v) solution concentration of solution added (0.02 g/kg) and 8 min conditioning time, sodium metasilicate acted as activator for kaolinite, whereas at 1.0% (w/v) solution concentration (0.2 g/kg), it acted as dispersant. The best observed condition of depressant is obtained at an added concentration of 10.0% (w/v, 0.2 g/kg) and 8 min conditioning time. The desired effect of the sodium metasilicate can be achieved by controlling its quantity, solution concentration added, and conditioning time.     

Chemoselective thioacetalisation and transthioacetalisation of carbonyl compounds catalysed by tetrabutylammonium tribromide (TBATB)

Thioacetals and thioketals of various aldehydes and ketones were obtained directly from carbonyl compounds or by a transthioacetalisation process from cyclic O,O-acetals in the presence of dithiols and a catalytic amount of tetrabutylammonium tribromide (TBATB). Chemoselective thioacetalisation of aromatic aldehydes containing an electron-donating group in the presence of an aldehyde containing an electron-withdrawing group, aldehydes in the presence of ketones, aliphatic cyclic ketones in the presence of aromatic ketones and less hindered ketones in the presence of more hindered ketones have been achieved. A cyclic acetal containing an electron-donating group has been chemoselectively transthioacetalised in the presence of an acetal having an electron-withdrawing substituent. These selectivities are due to the intrinsic reactivity of the substrate themselves and are independent of the catalyst and reaction conditions. Shorter reaction times, mild reaction conditions, stability of acid sensitive protecting groups, high efficiencies, facile isolation of the desired products and the catalytic nature of the reagent are the attractive features of the present method.     

Pulse-radiolysis studies on 4-pyridinemethanol and 4-pyridinecarboxaldehyde in aqueous solutions: dimer radical anion formation in the case of 4-pyridinecarboxaldehyde

Reactions of e _aq ^– , H atom and OH radicals with 4-pyridinemethanol (4-PM) and 4-pyridinecarboxaldehyde (4-PCA) have been studied at various pH values using the pulse radiolysis technique. Reaction of e _aq ^– with 4-PM and 4-PCA leads to the formation of pyridinyl and ketyl radicals of 4-PM and 4-PCA, respectively. Ketyl radicals formed from 4-PCA react with the parent molecule to give a dimeric radical species. At pH 7, the equilibrium constant for the dimer formation was determined to be 13 500 M^-1. At pH 13 also dimer radical formation was observed. Reaction of e _aq ^– with 4-PM was found to give highly reducing pyridinyl radicals. Reaction of OH radicals with 4-PM gives a mixture of species,viz., OH adducts and radicals formed by H-atom abstraction from the –CH₂OH moiety. Radicals formed by H-atom abstraction reaction from 4-PM were found to be reducing in nature. O^– radicals were found to react with 4-PM exclusively by H-abstraction pathway.     

Use of organophosphorus extractants impregnated on silica gel for the extraction chromatographic separation of minor actinides from high level waste solutions

Silica-gel has been used as an inert support for the extraction chromatographic separation of actinides and lanthanides from HNO₃ and synthetic high level waste (HLW) solutions. Silica-gel was impregnated with tri-butyl phosphate (TBP), to yield STBP; 2-ethylhexyl phosphonic acid, mono 2-ethylhexyl ester (KSM-17, equivalent to PC-88A), SKSM; octyl(phenyl)-N,N-diisobutyl carbamoylmethylphosphine oxide (CMPO), SCMPO; and trialkylphosphine oxide (Cyanex-923), SCYN and sorption of Pu(IV), Am(III) and Eu(III) from HNO₃ solutions was studied batchwise. Several parameters, like time of equilibration, HNO₃ and Pu(IV) concentrations were varied. The uptake of Pu(IV) from 3.0M HNO₃ followed the order SCMPO>SCYN>SKSM>STBP. With increasing HNO₃ concentration, D _Pu increased up to 3.0M of HNO₃ for STBP, SKSM and SCMPO and then decreased. In the case of Am and Eu with SCMPO, the D values initially increased between 0.5 to 1.0M of HNO₃, remained constant up to 5.0M and then slightly decreased at 7.5M. Also, the effects of NaNO₃, Nd(III) and U(VI) concentrations on the uptake of Am(III) from HNO₃ solutions were evaluated. With increasing NaNO₃ concentration up to 3.0M, D _Am remained almost constant while it was observed that it decreases drastically by adding Nd(III) or U(VI). The uptake of Pu and Am from synthetic pressurized heavy water reactor high level waste (PHWR-HLW) in presence of high concentrations of uranium and after depleting the uranium content, and finally extraction chromatographic column separation of Pu and Am from U-depleted synthetic PHWR-HLW have been carried out. Using SCMPO, high sorption of Pu, Am and U was obtained from the U-depleted HLW solution. These metal ions were subsequently eluted using various reagents. The sorption results of the metal ions on silica-gel impregnated with several phosphorus based extractants have been compared. The uptake of Am, Pu and rare earths by SCMPO has been compared with those where CMPO was sorbed on Chromosorb-102, Amberchrom CG-71 and styrene divinylbenzene copolymer immobilized in porous silica particles.     

The kinetics and mechanism of reaction between ethylenediaminetetraacetomanganate(III) and cyanide ion

Summary The title reaction has been followed spectrophotometrically at 325 nm (_max of [Mn(CN)₆]^3–) under pseudo-first order conditions with cyanide in a large excess at pH=10.0, I=0.1M (NaClO₄) and 25°C. The reaction follows first-order kinetics in [MnEDTA(OH)]^2– and exhibits variable-order dependence in [CN^–] one at high cyanide concentration, and two at low cyanide concentration. The product of above reaction has been identified as [Mn(CN)₆]^3–.The kinetics of the reverse reaction,i.e., the reaction of [Mn(CN)₆]^3- with EDTA^4– have also been followed spectrophotometrically. This reactions is first-order with respect to both [Mn(CN) ₆ ^3– ] and [EDTA^4–] and exhibits an inverse first-order dependence on [CN^–]. A six-step mechanism has been proposed in which the penultimate step is rate-determining. The activation parameters have been obtained and support the postulated mechanism.     

Polarographic determination of Pb, Tl, Bi and Sb in ethylenediamine in presence of mannitol

Summary Pb, Tl, Bi and Sb yield well defined polarograms in 1 M ethylenediamine in presence of 3% mannitol, with half-wave potentials at – 0.71 V, – 0.51 V, – 0.60 V and – 1.10 V, respectively. Only Pb and Tl develop maxima which can be suppressed by 0.02% gelatin. Presence of mannitol prevents the precipitation of Pb, Bi, and Sb in the alkaline solution. Simultaneous determinations of Pb/Tl, Bi/Sb, and Pb/Sb can be carried out.

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Polarographische Bestimmung von Pb, Tl, Bi und Sb in Äthylendiamin in Gegenwart von Mannit

Zusammenfassung Gut ausgebildete Polarogramme kann man von diesen Elementen in 1 M Äthylendiamin in Gegenwart von 3% Mannit erhalten. Die Halbstufenpotentiale liegen bei – 0,71 V (Pb), – 0,51 V (Tl), – 0,60 V (Bi) und – 1,10 V (Sb). Maxima, die im Falle von Pb und Tl gebildet werden, können durch 0,02% Gelatine unterdrückt werden. Durch Mannit wird die Fällung von Pb, Bi, und Sb in der alkalischen Lösung verhindert. Simultanbestimmungen von Pb/Tl, Bi/Sb und Pb/Sb sind möglich.

Our sincere thanks are due to Dr. G. B. Singh, Professor and Head, Department of Chemistry, B.H.U. for providing the necessary facilities.     

A constitutional diagram of the system TiC−HfC−WC

The system TiC?HfC?WC was investigated by means of melting point, differential thermoanalytical, X-ray diffraction and metallographic techniques on hot pressed and heat treated as well as melted alloy specimens and a complete constitutional diagram from 1500°C through the melting range established. According to the peritectic melting of hexagonal WC both isopleths, TiC?WC as well as HfC?WC show a class II reaction at 2760°C in Ti?W?C and at 2730°C in Hf?W?C. The phase behaviour within the TiC?HfC?WC system is characterized by the presence of a (binary) miscibility gap within TiC?HfC [T _c=1780°C, (TiC)_0.55(HfC)_0.45] which extends into the ternary forming a closed ternary miscibility gap at higher temperatures with an isolated ternary critical point:T _c=1800°C, (TiC)_0.55(HfC)_0.45(WC)_0.05. Interaction of the solvus (boundary of the cubic-B 1 monocarbide solid solution) and the ternary miscibility gap was established at 1540°C and (TiC)_0.27(HfC)_0.41(WC)_0.32: Alloys of this composition enter a decomposition reaction on cooling into two isotypic cubic B 1 phases and hexagonal WC. Isothermal sections were calculated assuming regular solutions.     

Thermoanalytical properties of monobasic nitrilotriacetate salts of alkaline earth metals and zinc

Monobasic metal nitrilotriacetate hydrated salts, MH[N(CH₂COO)₃].xH₂O, have been prepared by the reaction of nitrilotriacetic acid with metal carbonate. DTA studies of these salts both in N₂ and air reveal that these salts initially undergo dehydration and then, through acetate intermediates, decompose to oxycarbonates or oxides.     

Reactions of oxidizing radicals with 2- and 3-aminopyridines: a pulse radiolysis study

Reactions of OH radicals and some one-electron oxidants with 2-aminopyridine (2-AmPy) and 3-aminopyridine (3-AmPy) were studied in aqueous solutions using pulse radiolysis technique. The OH adduct of 2-AmPy at pH 9 has an absorption maximum at 360 nm along with a weak absorption band in the visible region and was found to be reactive with oxygen. The rate constant for its reaction with O₂ was determined to be 1.0×10⁸ dm³ mol⁻¹ s⁻¹. At pH 4 also, the OH adduct of 2-AmPy has an absorption band at 360 nm. However, there are differences in the absorption at other wavelengths. From the plot of ΔOD vs. pH at 340 nm, the pK_a of the OH adduct was determined to be 6.5. Among the specific oxidants, only SO₄^−√ radicals were able to oxidize 2-AmPy. In the case of 3-aminopyridine (3-AmPy), the transient species formed by OH radical reaction at pH 9 has an absorption maximum at 410 nm with shoulder bands on both the sides. Its absorption spectrum at pH 4 was different indicating the existence of a pK value for the OH adduct. pK_a of 3-AmPy-OH radical adduct species was evaluated to be 5.7. This adduct species was also found to be reactive with oxygen (k=7.6×10⁶ dm³ mol⁻¹ s⁻¹). Specific one-electron oxidants like N₃^√, Br₂^−√ C₂^−√ and SO₄^−√ were able to oxidize 3-AmPy indicating that it is easier to oxidize 3-AmPy as compared to 2-AmPy.     

Detection of OH on photolysis of styrene oxide at 193 nm in gas phase

Photodissociation of styrene oxide at 193 nm in gas phase generates OH, as detected by laser-induced fluorescence technique. Under similar conditions, OH was not observed from ethylene and propylene oxides, primarily because of their low absorption cross-sections at 193 nm. Mechanism of OH formation involves first opening of the three-membered ring from the ground electronic state via cleavage of either of two CO bonds, followed by isomerization to enolic forms of phenylacetaldehyde and acetophenone, and finally scission of the COH bond of enols. Ab initio molecular orbital calculations support the proposed mechanism.