RuCl 3 can further catalyze the reaction between hexacyanoferrate(III) and iodide ions, which is already catalyzed by the hydrogen ions obtained from perchloric acid. Rate, when the reaction is catalyzed only by the hydrogen ions, was separated graphically from the rate when ruthenium(III) and H + ions both catalyze the reaction. Reactions studied separately in the presence as well as in the absence of RuCl 3 under similar conditions were found to follow second order kinetics w.r.t. [I ) ]. While the rate showed direct proportionality w.r.t. [Fe(CN) 6 ] 3) and [RuCl 3 ]. At low concentrations the reaction shows direct proportionality with respect to [H + ] which tends to become proportional to the square of hydrogen ion concentrations. External addition of [Fe(CN) 6 ] 4) ions retards the reaction velocity while change in ionic strength of the medium has no effect on the rate. With the help of the intercept of the catalyst graph, extent of the reaction, which takes place without adding ruthenium(III) was calculated and it was in accordance with the values obtained from the separately studied reaction in which only H + ions catalyze the reaction. It is proposed that ruthenium forms a complex, which slowly disproportionates into the rate-determining step. Arrhenius parameters at four different temperatures were also calculated.
RuCl 3 further catalyzes the oxidation of iodide ion by K 3 Fe(CN) 6 , already catalyzed by hydrogen ions. The rate of reaction, when catalyzed only by hydrogen ions, was separated graphically from the rate when both Ru(III) and H + ions catalyzed the reaction. Reactions studied separately in the presence as well as absence of RuCl 3 under similar conditions were found to follow second-order kinetics with respect to [I − ], while the rate showed direct proportionality with respect to [Fe(CN) 6 ] 4− ions retards the reaction velocity, while changing the ionic strength of the medium has no effect on the rate. With the help of the intercept of the catalyst graph, the extent of the reaction that takes place without adding Ru(III) was calculated and it was in accordance with the values obtained from the reaction in which only H + ions catalyzed the reaction. It is proposed that ruthenium forms a complex, which slowly disproportionates into the rate-determining step. Arrhenius parameters at four different temperatures were also calculated. C
Volatile double ethoxides and isopropoxides, MHf,(OR)9 and M,Hf3(OR)14. of hafnium with alkali metals ( M = Li, Na, or K) and KHf(OBut), have been synthesised. Alcoholysis reactions of the double isopropoxides have been studied. Volatile double isopropoxides, HfM(OPr'), and HfM,(OPr*)lo, have also been prepared ( M = Al or Ga).The i.r. and n.m.r. spectra of the compounds have been recorded.
Oxidation of iodide ions by K 3 Fe(CN) 6 , catalyzed by hydrogen ions obtained from hydrochloric acid was found to be further catalyzed by iridium(III) chloride. Rate, when the reaction is catalyzed only by the hydrogen ions, was separated from the rate when iridium(III) and H + ions both, catalyze the reaction. Reactions studied separately in the presence as well as in the absence of IrCl 3 under similar conditions were found to follow second order kinetics with respect to [I ) ]. While the rate showed direct proportionality with respect to [K 3 Fe(CN) 6 ] and [IrCl 3 ]. At low concentrations the reaction shows direct proportionality with respect to [H + ] which tends to become proportional to the square of hydrogen ions at higher concentrations. Strong retarding affect of externally added hexacyanoferrate(II) ions was observed in the beginning but further addition affects the rate to a little extent. Changes in [Cl ) ] and also ionic strength of the medium have no effect on the rate. With the help of the intercept of catalyst graph, the extent of the reaction, which takes place without adding iridium(III), was calculated and was found to be in accordance with the values obtained from the separately studied reactions in which only H + ions catalyze the reaction. It is proposed that iridium forms a complex, which slowly disproportionates into the rate-determining step. Thermodynamic parameters at four different temperatures were calculated.
Auf dem angegebenen Weg wird aus der gut zugänglichen Carbonsäure (I) zunächst der Halbester (III) hergestellt, aus dem photochemisch mit Iod die w‐Iodcarbonsäune (IV) erhalten werden kann.
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