Studies on Metal Hydroxy Compounds. XIII. Thermal Analyses and Decomposition Kinetics of Hydroxystannates of Bivalent Metals

1971 ◽  
Vol 49 (17) ◽  
pp. 2813-2816 ◽  
Author(s):  
P. Ramamurthy ◽  
E. A. Secco

The thermal analyses of hexahydroxystannates of bivalent metals of the type Me[Sn(OH)6], where Me = Zn, Co, Cu, Ni, Mn, Ca, Mg, Cd, Sr, reveal that the primary mode of decomposition occurs by dehydroxylation and subsequent decomposition of the metastannate residue occurs in the Zn, Cu, Mn, Ca, and Mg compounds. Calorimetric measurements along with related enthalpic values for the decomposition reaction are given. The kinetics of thermal decomposition of all compounds studied, except the Cd and Mg analogues, follow first order reaction kinetics up to α ~ 0.9.

1970 ◽  
Vol 48 (17) ◽  
pp. 2656-2661 ◽  
Author(s):  
P. Ramamurthy ◽  
E. A. Secco

The thermal analyses of Cd2(OH)3X type of basic halides reveal that the decomposition occurs via a two-step dehydroxylation pattern, yielding CdOHX as an intermediate product after the initial mode. These results suggest that Cd2(OH)3X is an addition compound of the hydroxide and the 1:1 hydroxy-halide, i.e. Cd(OH)2•CdOHX. Calorimetric measurements along with related enthalpy values for the decomposition reaction are given.The kinetics of thermal decomposition of the compounds are classified into two main groups: (i) two-dimensional contracting plate model equation and (ii) first-order rate law.The infrared spectral data of thirteen Cd and Zn basic halides in the frequency region 4000–250 cm−1 are presented with their assignments.


1970 ◽  
Vol 48 (22) ◽  
pp. 3510-3519 ◽  
Author(s):  
P. Ramamurthy ◽  
E. A. Secco

The thermal analyses of copper basic oxysalts of the type Cu2(OH)2XOy, where X = S, C, Cl, Br, I, N, HC and y = 4, 3, or 2 reveal that decomposition occurs, in most cases, by dehydroxylation with concomitant disproportionation of the oxysalt. An outstanding exception to this pattern of decomposition is the basic sulfate. Calorimetric measurements along with related enthalpic values for the decomposition reaction are given.The kinetics of thermal decomposition of the compounds are classified into three main categories: (i) three-dimensional contracting sphere model, (ii) first-order rate, and (iii) nucleation controlled rate processes.The infrared spectral data of nine copper basic oxycompounds in the frequency region 4000–250 cm−1 are presented with their assignments. The fundamental infrared inactive modes of the anionic species SO42−, NO3−, etc. become active by the presence of the copper hydroxide ligand indicating a lowering of symmetry in the anion.


1970 ◽  
Vol 48 (16) ◽  
pp. 2617-2622 ◽  
Author(s):  
P. Ramamurthy ◽  
E. A. Secco ◽  
M. Badri

The thermal analyses, thermogravimetry (TG), and differential thermal analysis (DTA) of PbOHCl, PbOHBr, and PbOHI reveal that the initial mode of decomposition is via dehydroxylation. Calorimetric measurements along with related enthalpy values for the decomposition reaction are given.The infrared spectra of these compounds are interpreted in terms of folded bands of (PbOH+)n tied together by halide ions consistent with their crystal structures.The kinetics of thermal decomposition of lead hydroxyhalides follow a diffusion-type rate equation which is in contrast to the simple first-order rate equation observed for most Cd, Zn, and Cu compounds. These two distinct rates are interpreted in terms of mobile OH or H species in the dehydroxylation step.


2014 ◽  
Vol 44 (3) ◽  
pp. 195-201
Author(s):  
L. KUNIGK ◽  
S. P. GALIZIA ◽  
R.T. K. SHIKISHIMA ◽  
R. GEDRAITE ◽  
C. H. JURKIEWICZ

Peracetic acid (PAA) is a strong oxidant used by the food industry as a sanitizer, in medical area as a disinfectant and by the textiles and paper industries as a bleacher. Its decomposition rate is an important parameter in these applications. The main purpose of this paper is to study the decomposition kinetics of PAA between 25 and 45 °C in solutions with pH 3.11, 5.0 and 7.0. The decomposition of PAA is a first-order reaction for all solutions and temperatures studied. The rate constants were between 2.08·10-3 and 9.44·10-3 h-1 (pH 3.11), between 2.61·10-3 and 16.69·10-3 h-1 (pH 5.0) and between 7.50·10-3 and 47.63·10-3 h-1 (pH 7.0). The activation energy of PAA decomposition in aqueous solutions are 58.36 and 72.89 kJ·mol-1 when pH was 3.11 and 5.0, respectively.


1993 ◽  
Vol 28 (2) ◽  
pp. 135-144 ◽  
Author(s):  
S. Matsui ◽  
R. Ikemoto Yamamoto ◽  
Y. Tsuchiya ◽  
B. Inanc

Using a fluidized bed reactor, experiments on glucose decomposition with and without sulfate reduction were conducted. Glucose in the reactor was mainly decomposed into lactate and ethanol. Lactate was mainly decomposed into propionate and acetate, while ethanol was decomposed into propionate, acetate, and hydrogen. Sulfate reduction was not involved in the decomposition of glucose, lactate, and ethanol, but was related to propionate and acetate decomposition. The stepwise reactions were modeled using either a Monod expression or first order reaction kinetics in respect to the reactions. The coefficients of the kinetic equations were determined experimentally. The modified Monod and first order reaction equations were effective at predicting concentrations of glucose, lactate, ethanol, propionate, acetate, and sulfate along the beight of the reactor. With sulfate reduction, propionate was decomposed into acetate, while without sulfate reduction, accumulation of propionate was observed in the reactor. Sulfate reduction accelerated propionate conversion into acetate by decreasing the hydrogen concentration.


1992 ◽  
Vol 57 (7) ◽  
pp. 1451-1458 ◽  
Author(s):  
Refat M. Hassan

The kinetics of oxidation of arsenic(III) by hexachloroiridate(IV) at lower acid concentrations and at constant ionic strength of 1.0 mol dm-3 have been investigated spectrophotometrically. A first-order reaction in [IrCl62-] and fractional order with respect to arsenic(III) have been observed. A kinetic evidence for the formation of an intermediate complex between the hydrolyzed arsenic(III) species and the oxidant was presented. The results showed that decreasing the [H+] is accompanied by an appreciable acceleration of the rate of oxidation. The activation parameters have been evaluated and a mechanism consistent with the kinetic results was suggested.


1970 ◽  
Vol 48 (21) ◽  
pp. 3291-3299 ◽  
Author(s):  
K. G. McCurdy ◽  
B. P. Erno

An investigation has been made of the kinetics of hydration of tricalcium silicate at several temperatures in a large excess of water in the presence of various added ions. The rate data have been interpreted by a reaction mechanism which involves: (a) the first order hydration of tricalcium silicate to form an intermediate product, 1.5CaO•SiO2, which can react by two pathways, (b) the direct first order decomposition of intermediate, 1.5CaO•SiO2, to form lime and silica or (b′) complexing of intermediate with silica and subsequent decomposition to form lime and silica. This reaction mechanism predicts the rate of production of base during the hydration. The effect of various added ions is interpreted in terms of the proposed mechanism.Rate constants and activation energies for the various steps in the proposed mechanism are reported.


1973 ◽  
Vol 28 (1-2) ◽  
pp. 83-90
Author(s):  
Horst Mossmann ◽  
Dietrich K. Hammer

The reaction of bacteriophage T4 with 1-fluoro-2,4-dinitrobenzene resulted in a covalent binding of 2,4-dinitrophenyl (DNP) determinants to the phage. From the kinetics of inactivation reflecting the coupling process it is concluded that attachment of more than one DNP group to the critical site(s) of the phage is required for inactivation (multi-hit reaction). Contrary to this the neutralization of DNP-T4 by anti-DNP antibody turned out to be a first order reaction, until 80 %> neutralization fitting one-hit kinetics. If compared with native T4, the susceptibility of DNP-T4 to neutralization by anti-T4 antibody is considerably higher, indicating that attachment of DNP groups to T4 amplifies the sensitivity to neutralization by anti-T4. Comparing neutralization kinetics of DNP-T4 and native T4 by anti-DNP-T4 antibody it is suggested that native determinants and DNP groups, as well as determinants resulting from alteration due to the coupling process, all together may contribute as targets for neutralization. Three characteristics strengthen the view that the velocity of T4 conjugates in infecting the host strain is markedly decreased if compared with that of native T4: (a) considerable discrepancy between direct plating and decision technique (b) increasing variety of plaque size and (c) decreased velocity of the first step of reproduction. The kinetics of neutralization observed can be reconciled with a model proposed by Krummel and Uhr. The kinetics of reactivation of neutralized DNP-T4 by the presence cf DNP-BSA has been investigated and the problems involved in the reaction are discussed.


2000 ◽  
Vol 65 (12) ◽  
pp. 857-866
Author(s):  
Mladjen Micevic ◽  
Slobodan Petrovic

The alcoholysis of 1,2,2-trimethylpropyl-methylfluorophosphonate (soman) was examined with a series of alkoxides and in corresponding alcohols: methanol, ethanol, 1-propanol, 2-propanol, 2-methoxyethanol and 2-ethoxyethanol. Soman reacts with the used alkoxides in a second order reaction, first order in each reactant. The kinetics of the reaction between 1,2,2-trimethylpropyl-methylfluorophosphonate and ethanol in the presence of diethylenetriamine was also examined. A third order reaction rate constant was calculated, first order in each reactant. The activation energy, frequency factor and activation entropy were determined on the basis of the kinetic data.


1972 ◽  
Vol 18 (3) ◽  
pp. 263-265 ◽  
Author(s):  
John A Daly ◽  
Gerhard Ertingshausen

Abstract A direct method was developed for determining inorganic phosphate in serum, which requires only a single reagent addition. The method quantitates the unreduced phosphomolybdate heteropolyacid at 340 nm and is linear to at least 10 mg of phosphate per 100 ml. Only 10 µl of serum is required. The unique blanking capabilities of centrifugal analyzers permit the "on run" elimination of serum and reagent background absorbances, which are automatically subtracted. Data on precision, correlation, and recovery are presented. Kinetics of the reaction were studied, and theoretical limits of automatic blanking when applied to a first-order reaction are discussed.


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