Polymerization of acrylonitrile initiated by peroxomonosulphate-thiols redox systems

1990 ◽  
Vol 55 (8) ◽  
pp. 2001-2007
Author(s):  
Gurusamy Manivannan ◽  
Pichai Maruthamuthu
Keyword(s):  
Ionic Strength ◽  
Thermodynamic Parameters ◽  
Thermal Polymerization ◽  
Reaction Scheme ◽  
Degree Of Polymerization ◽  
Reducing Agent ◽  
Redox Systems ◽  
Temperature Range ◽  
Rate Of Polymerization

Aqueous thermal polymerization of acrylonitrile (AN) initiated by peroxomonosulphate (HSO5-, PMS)-thiolactic acid (TLA) and PMS-thiomalic acid (TMA) redox systems has been carried out in the temperature range 30-50 °C. The effect of concentration of monomer, initiator, reducing agent, H+, and ionic strength on rate of polymerization, Rp, has been investigated under deaerated conditions. The Rp has been found to depend on, Rp ~ [AN]01.5 [PMS]0.5 [TLA]0.5 in PMS-TLA system and, Rp ~ [AN]02.0 [PMS]1.0 [TMA]0 in PMS-TMA system. The degree of polymerization (Xn) values and thermodynamic parameters have been evaluated. Suitable reaction scheme has been proposed and expressions for Rp and Xn have been obtained.

Adsorption of organics on thermally treated solids obtained from colloidal silica

1987 ◽  
Vol 52 (3) ◽  
pp. 572-581 ◽  
Author(s):  
Miroslav M. Kopečni ◽  
Slobodan K. Milonjic ◽  
Wladyslaw Rudzinski ◽  
Jacek Jagiello
Keyword(s):  
Gas Chromatography ◽  
Thermodynamic Parameters ◽  
Adsorption Isotherms ◽  
Colloidal Silica ◽  
Adsorption Properties ◽  
Thermal Pretreatment ◽  
Lateral Interactions ◽  
Adsorbed Molecules ◽  
Temperature Range ◽  
Thermally Treated

Adsorption isotherms of three adsorbates on the solid beads obtained from colloidal silica were determined by means of gas chromatography at low surface coverages, when lateral interactions between the adsorbed molecules are negligible. The influence of thermal pretreatment on the adsorption properties of the solids was investigated in the temperature range from 343 to 423 K, while the solids were heated between 523 K and 1 223 K. The thermodynamic parameters of adsorption have been determined and used to discuss the adsorbate-adsorbent interactions.

Thermochromism of Metal Exchange Reaction between Zinc(II) and Mercury(II) Porphyrins

1995 ◽  
Vol 50 (4) ◽  
pp. 545-550 ◽  
Author(s):  
Masaaki Tabata ◽  
Masahiro Ide ◽  
Kentaro Kaneko
Keyword(s):  
Aqueous Solution ◽  
Exchange Reaction ◽  
Thermodynamic Parameters ◽  
Distribution Curve ◽  
Equilibrium Constants ◽  
Metal Exchange ◽  
Free Base ◽  
Temperature Range ◽  
Base Form ◽  
Metal Exchange Reaction

Thermochromism was observed for an aqueous solution containing zinc(II) and mercury( II) cations and N-p-nitrobenzyl-5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin anion (NO2Bz(Htpps)4-) in the temperature range 10 to 70 °C. The equilibrium constants and the thermodynamic parameters of Zn(NO2Bztpps)3- and Hg(NO2Bztpps)3- have been determined spectrophotometrically to elucidate the thermochromism at 10, 15, 20, 25 and 30 °C in 0.1 mol dm-3 NaNO3. The protonation and metalation constants of NO2Bz(Htpps)4- are defined as K2 = [H2P][H+]-1[HP]-1, K3 = [H3P][H+]-1[H2P]-1 and KMP = [M P][H+][M2+]-1[HP]-1, where HP and MP denote the free base form of the prophyrin and the metalloporphyrins of zinc(II) and mercury(II), respectively. Charges of the prophyrin and metalloporphyrins are omitted for simplicity. The following values were found: logK2 = 7.75 ±0.02 (25 °C), ΔH°/kJmol-1 = -21.2±0.5 and ΔS°/Jmol-1K-1 = 77±1, logK3 = 2.55±0.02 (25 °C), ΔH°/kJmol-1 = -25±0.8 and ΔS°/Jmol-1K-1 = -35±3 and log KZnP = 0.63±0.03 (25 °C), ΔH°/kJmol-1 = 31.0±0.8 and ΔS°/Jmol-1K-1 = 116±3, logKHgP = 6.22±0.03 (25 °C), ΔH°/kJmol-1 = 4.5±0.7 and ΔS°/Jmol-1K-1 = 134±2. The distribution curve calculated from the thermodynamic parameters sufficiently agrees with the observed metal exchange reaction between the metalloporphyrins.

scholarly journals Potentiometric and spectrophotometric studies of the complexation of Schiff-base hydrazones containing the pyrimidine moiety

2003 ◽  
Vol 68 (10) ◽  
pp. 729-749 ◽  
Author(s):  
H.S. Seleem ◽  
B.A. El-Shetary ◽  
S.M.E. Khalil ◽  
M. Shebl
Keyword(s):  
Schiff Base ◽  
Ionic Strength ◽  
Thermodynamic Parameters ◽  
Stability Constants ◽  
Elemental Analysis ◽  
Mass Spectra ◽  
Dissociation Constants ◽  
The Stability ◽  
Pyrimidine Moiety ◽  
Metal Ligand

Three Schiff-base hydrazones (ONN ? donors) were prepared by condensation of 2-amino-4-hydrazino-6-methylpyrimidine with 2-hydroxyacetophenone 2-methoxybenzaldehyde and diacetyl to yield 2-OHAHP, 2-OMeBHPand DHP respectively. The structures of these ligands were elucidated by elemental analysis, UV, IR, 1H-NMR and mass spectra. The metal?ligand stability constants of Mn2+, Fe3+,Co2+,Ni2+,Cu2+, Zn2+,Cd2+,UO22+ and Th4+ chelates were determined potentiometrically in two different media (75%(v/v) dioxane?water and ethanol?water) at 283, 293, 303 and 313 K at an ionic strength of 0.05 M (KNO3). The thermodynamic parameters of the 1:1 and 1:2 complexes were evaluated and are discussed. The dissociation constants of 2-OHAHP, 2-OMeBHP and DHPligands and the stability constants of Co2+, Ni2 and Cu2+ with 2-OHAHP were determined spectrophotometrically in 75 % (v/v) dioxane?water.

scholarly journals Proteolytic removal of three C-terminal residues of actin alters the monomer-monomer interactions

1993 ◽  
Vol 289 (3) ◽  
pp. 897-902 ◽  
Author(s):  
M Mossakowska ◽  
J Moraczewska ◽  
S Khaitlina ◽  
H Strzelecka-Golaszewska
Keyword(s):  
Electron Microscopy ◽  
Steady State ◽  
Ionic Strength ◽  
Rate Constants ◽  
Initial Rate ◽  
Critical Concentration ◽  
Rate Of Polymerization ◽  
Low Ionic Strength ◽  
Hydrolysis Of

Homogeneous preparations of actin devoid of the three C-terminal residues were obtained by digestion of G-actin with trypsin after blocking proteolysis at other sites by substitution of Mg2+ for the tightly bound Ca2+. Removal of the C-terminal residues resulted in the following: an enhancement of the Mg(2+)-induced hydrolysis of ATP in low-ionic-strength solutions of actin; an increase in the critical concentration for polymerization; a decrease in the initial rate of polymerization; and an enhancement of the steady-state exchange of subunits in the polymer. Electron microscopy indicated an increased fragility of the filaments assembled from truncated actin. The results suggest that removal of the C-terminal residues increases the rate constants for monomer dissociation from the polymer ends and from the oligomeric species.

Thermal polymerization of arylacetylenes: spectroscopic and thermal studies

1994 ◽  
Vol 6 (4) ◽  
pp. 347-383 ◽  
Author(s):  
Marie-Florence Grenier-Loustalot
Keyword(s):  
Thermal Properties ◽  
Reaction Mechanisms ◽  
Thermal Studies ◽  
Thermal Polymerization ◽  
Temperature Range ◽  
H Nmr ◽  
Kinetics Of ◽  
Competing Reactions

The reaction mechanisms and kinetics of endcapped ethynyl polyethers were studies in the temperature range 150-220C. The results obtained by '3C and 'H NMR, FrTIR, HPLC and DSC indicate reactivity differences and competing reactions. These materials were cured and their thermal properties evaluated.

Insights into cationic methyl violet 6B dye–kaolinite interactions: kinetic, equilibrium and thermodynamic studies

Clay Minerals ◽  
2013 ◽  
Vol 48 (1) ◽  
pp. 85-95 ◽  
Author(s):  
İ. Sargin ◽  
N. Ünlü
Keyword(s):  
Experimental Data ◽  
Ionic Strength ◽  
Adsorption Capacity ◽  
Thermodynamic Parameters ◽  
Adsorption Kinetics ◽  
Adsorption Process ◽  
Methyl Violet ◽  
Order Type ◽  
Kinetic And Thermodynamic Parameters ◽  
Initial Ph

AbstractIn this study, adsorption and adsorption kinetics of methyl violet dye from aqueous solutions onto kaolinite were investigated. The effects of adsorbent dosage, pH, ionic strength, contact time, temperature and initial dye concentration were studied. Kinetic and thermodynamic parameters were determined using experimental data. Adsorption capacity decreased with increasing ionic strength. Changes in the initial pH of the dye solution in a range close to the dye's natural pH (i.e. ∼ pH 5.0) values affected adsorption capacity slightly, indicating that adsorption studies could be carried out at the dye's natural pH. The adsorption process followed the Freundlich-type adsorption isotherms and pseudo-second order type adsorption kinetics. However, an intraparticle diffusion process was found to have effects in adsorption processes. Thermodynamic parameters were calculated from the experimental data and enthalpy of the adsorption, ΔH0, was found to be –6.82 kJ mol–1, indicating physisorption nature of the adsorption. Other thermodynamic parameters, ΔS0 and DG0, were also calculated. Negative values of ΔG0 indicated that the adsorption process for methyl violet on kaolinite is spontaneous.

Kinetics and Mechanism of the Reaction of Dichlorotetraaquaruthenium(III) and Thiols

2012 ◽  
Vol 65 (2) ◽  
pp. 113 ◽  
Author(s):  
Suprava Nayak ◽  
Gouri Sankhar Brahma ◽  
K. Venugopal Reddy
Keyword(s):  
Electron Transfer ◽  
Ionic Strength ◽  
Equilibrium Constants ◽  
Activation Parameters ◽  
Kinetics And Mechanism ◽  
Intermediate Complex ◽  
Mechanism Of Formation ◽  
Temperature Range ◽  
Temperature Reduction ◽  
Mechanism Of The Reaction

The formation of an intermediate ruthenium(iii) thiolate complex by the interaction of thiols, RSH (R = glutathione and l-cysteine) and dichlorotetraaquaruthenium(iii), [RuIIICl2(H2O)4]+, is reported in the temperature range 25–40°C. The kinetics and mechanism of formation of the intermediate complex were studied as a function of [RuIIICl2(H2O)4]+, [RSH], pH, ionic strength and temperature. Reduction of the intermediate complex takes place slowly and results in the corresponding disulfides RSSR and [RuIICl2(H2O)4]+. The results are interpreted in terms of a mechanism involving a rate-determining inner-sphere one-electron transfer from RSH to the oxidant used in the present investigation and a comparison of rate and equilibrium constants is presented with activation parameters.

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