Studies on metal hydroxy compounds. X. Thermal analyses, decomposition kinetics, and infrared spectra of lead halide (Cl, Br, I) derivatives

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.

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.


1973 ◽  
Vol 51 (23) ◽  
pp. 3882-3888 ◽  
Author(s):  
Ah-Dong Leu ◽  
Palepu Ramamurthy ◽  
Etalo A. Secco

Studies were carried out on two series of mixed metal hydroxy chloride compounds of the type xMe(OH)2•yMCl2 where Me = Cd, Cu and M = Mn, Co, Ni, Cu, Zn, Cd, Mg, or Ca.Thermal analyses for the Cd–M series reveal that the initial mode of decomposition involves a dehydroxylation step with a concomitant metathetical reaction between MCl2 and CdO. The compound CdCl2•2CdO is formed and decomposes at higher temperature leading to the eventual volatilization of CdCl2. The kinetics of thermal decomposition follow a simple first-order rate equation. The sole exception to this general pattern of behavior is the Cd–Zn compound.The initial mode of thermal decomposition of the Cu–M series compounds follows a parallel pattern described for the Cd–M series. The kinetic data for the Cu–M series are fitted into three groups: (i) phase boundary control embracing the contracting sphere and contracting plate model equations, (ii) A-E type equation with n = 2, and (iii) first-order rate equation.


1963 ◽  
Vol 41 (1) ◽  
pp. 231-237 ◽  
Author(s):  
G. R. Williams

The kinetics of reduction of ferricytochrome c by hydroquinone have been studied. The reaction does not conform to a simple second-order rate equation and it is demonstrated that the deviations are brought about by the presence of p-quinone, one of the products of the reaction. The accelerating effect of p-quinone is explained tentatively on the basis of an involvement of the semi-quinone. The effects on the reaction of pH, ionic strength, and temperature are reported and used to suggest features of the reaction mechanism.


1963 ◽  
Vol 41 (1) ◽  
pp. 231-237 ◽  
Author(s):  
G. R. Williams

The kinetics of reduction of ferricytochrome c by hydroquinone have been studied. The reaction does not conform to a simple second-order rate equation and it is demonstrated that the deviations are brought about by the presence of p-quinone, one of the products of the reaction. The accelerating effect of p-quinone is explained tentatively on the basis of an involvement of the semi-quinone. The effects on the reaction of pH, ionic strength, and temperature are reported and used to suggest features of the reaction mechanism.


Cellulose ◽  
2007 ◽  
Vol 15 (2) ◽  
pp. 193-203 ◽  
Author(s):  
Paolo Calvini ◽  
Andrea Gorassini ◽  
Antonio Luigi Merlani

1975 ◽  
Vol 53 (12) ◽  
pp. 1842-1848 ◽  
Author(s):  
Anthony Poë ◽  
Carol Vuik

The kinetics of base hydrolysis of the complexes trans-[Rh(en)2(OH)X]+ (X = Br or Cl) follow the pseudo first order rate equation kobs = k1 + k2[OH−]. The small contribution of the [OH−]-dependent term is due to lower values of ΔS2≠ − ΔS1≠ than are observed for the complexes cis-[Rh(en)2(OH)Cl]+ and [Rh(NH3)5X]2+ (X = Cl, Br, or I ). The values of ΔH1≠ are used to obtain new values of the intrinsickinetictrans-effect (i.k.t.e.) of hydroxide that agree with that determined from aquation of trans.-[Rh(en)2(OH)I]+ and place hydroxide in the i.k.t.e. series [Formula: see text] The new data also allow hydroxide to be placed in a thermodynamic trans-effect (t.t.e.) series I > OH > NH3 > Br > Cl > OH2, and the different position of hydroxide in the two series is discussed.


Author(s):  
Meghmala R. Sangvikar ◽  
Gayatri M. Phadnaik ◽  
Omprakash S. Chavan

The kinetics of DMSO (dimethylsulphoxide) assisted one pot cyclocondensation of bisanilino disulphide and 1,3-dicarbonyls has been investigated using spectral method. The kinetic measurements have been carried by varying media, temperature and concentration of the reactants. The assistance of DMSO is investigated. The order of reaction, effects of substituents with dicarbonyls on the rates and thermodynamic parameters has also been reported. First time reaction conditions are optimised for performing the cyclocondensation conveniently and rapidly. Probably mechanism has been proposed and order of reaction was determined on the basis of rate expression and was in agreement with second order rate equation, used for the determination of rate constants.


2013 ◽  
Vol 13 (1) ◽  
pp. 33 ◽  
Author(s):  
Audy D Wuntu ◽  
Vanda S Kamu

KINETICS OF GASEOUS TOLUENE ADSORPTION ON CANDLENUT SHELL ACTIVATED CARBON ABSTRACT Adsorption kinetics of gaseous toluene on activated carbon prepared from candlenut shell had been studied. The research was performed by examining adsorption data, which was obtained in previous research, over several rate equations, which were: (1) Lagergren’s pseudo first order rate equation, (2) Ho’s pseudo second order rate equation, (3) Elovich’s equation, and (4) persamaan Ritchie’s equation. The result showed that the data of toluene adsorption on candlenut shell activated carbon fits the Ho’s pseudo second order rate equation and, hence, the model is the most applicable model for the adsorption. Calculation from linear regression of Ho’s pseudo second order rate equation gave the equilibrium adsorption capacity value of 56,069 mg g-1, second order rate constant of 3,54x10–4 g mg-1 min-1, and initial adsorption rate of 1,112 mg g-1 min-1. Keywords: adsorption, candlenut, activated carbon, toluene KINETIKA ADSORPSI GAS TOLUENA PADA KARON AKTIF TEMPURUNG KEMIRI ABSTRAK Studi mengenai aspek kinetika adsorpsi toluena pada arang aktif yang terbuat dari tempurung kemiri telah dilakukan. Penelitian dilakukan dengan menguji data adsorpsi yang telah diperoleh pada penelitian terdahulu menggunakan empat persamaan laju adsorpsi, yaitu (1) persamaan laju pseudo order pertama Lagergren, (2) persamaan laju pseudo order kedua Ho, (3) persamaan Elovich, dan (4) persamaan Ritchie. Hasil kajian menunjukkan bahwa model kinetika dengan persamaan laju pseudo order kedua Ho adalah yang paling sesuai diaplikasikan untuk adsorpsi gas toluena pada arang aktif tempurung kemiri. Dari persamaan linear untuk model kinetika pseudo order kedua Ho diperoleh nilai kapasitas adsorpsi pada kesetimbangan sebesar 56,069 mg g-1, konstanta adsorpsi sebesar 3,54x10–4 g mg-1 menit-1, dan laju adsorpsi awal sebesar 1,112 mg g-1 menit-1. Kata kunci: adsorpsi, kemiri, karbon aktif, toluena


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