scholarly journals Rates and equilibrium constants for the covalent hydration of 5-bromo-2(1H)-pyrimidinone in aqueous solution

1986 ◽  
Vol 64 (6) ◽  
pp. 1267-1272 ◽  
Author(s):  
Oswald S. Tee ◽  
Jana Pika ◽  
M. Judith Kornblatt ◽  
Michael Trani
Keyword(s):  
Aqueous Solution ◽  
Aqueous Solutions ◽  
Title Compound ◽  
Equilibrium Constants ◽  
Kinetic Studies ◽  
Kinetics Of

The kinetics of bromination of the title compound (1) have been measured in aqueous solutions of pH 0–6. The change in the order of reaction which occurs around pH 2.5 is explained by 1 reacting via its covalent hydrate, 3. Furthermore, there is sufficient 3 present at equilibrium that the kinetics of its equilibration with 1 were also measured. From these two studies the extent of covalent hydration of 1 is estimated to be 5%.Kinetic studies of the bromination of the dimethyl cation 5 and of its equilibration with the pseudobase 6 were also carried out for the purposes of comparison.The present results for 1, 3, 5, and 6 are compared to earlier results for 2-pyrimidinone and analogous derivatives.

THE DISSOCIATION OF α- AND β-LIPOVITELLIN IN AQUEOUS SOLUTION: PART I. EFFECT OF pH, TEMPERATURE, AND OTHER FACTORS

1962 ◽  
Vol 40 (3) ◽  
pp. 363-372 ◽  
Author(s):  
R. W. Burley ◽  
W. H. Cook
Keyword(s):  
Aqueous Solution ◽  
Ionic Strength ◽  
Aqueous Solutions ◽  
Thermodynamic Data ◽  
Equilibrium Constants ◽  
Effect Of Ph ◽  
Reversible Dissociation ◽  
Lipoprotein Concentration ◽  
Irreversible Aggregation ◽  
Increasing Temperature

The effect of pH, temperature, ionic strength, and lipoprotein concentration on the reversible dissociation of α- and β-lipovitellin in aqueous solutions above pH 6 has been examined by ultracentrifugal measurements. Under otherwise similar conditions α- and β-lipovitellin are 50% dissociated at pH 10.5 and 7.8, respectively. Both lipovitellins undergo an irreversible aggregation above about pH 11; β-lipovitellin is sometimes converted to a non-dissociable form upon aging. Dissociation of both lipovitellins decreases with increasing ionic strength and increasing temperature. Although the ultracentrifugal method has limitations, provisional equilibrium constants and thermodynamic data were obtained from it that are comparable with those obtained for certain protein systems.

Kinetics of the Decomposition of Sulphur Dicyanide in Aqueous Solution

1962 ◽  
Vol 15 (2) ◽  
pp. 211 ◽  
Author(s):  
W Kitching ◽  
RH Smith ◽  
IR Wilson
Keyword(s):  
Aqueous Solution ◽  
Aqueous Solutions ◽  
Nucleophilic Substitution ◽  
Perchloric Acid ◽  
Reaction Path ◽  
Acid Solutions ◽  
Kinetics Of

The kinetics and stoicheiometry of the decomposition of aqueous solutions of sulphur dicyanide have been studied at temperatures between 0-70 �C and in media ranging from dilute perchloric acid to pH 7. The predominant reaction is nucleophilic substitution at carbon, but in perchloric acid solutions an alternative reaction path has been revealed.

Tautomeric equilibria and pKa values for 'sulfurous acid' in aqueous solution: a thermodynamic analysis

1979 ◽  
Vol 57 (4) ◽  
pp. 454-457 ◽  
Author(s):  
J. Peter Guthrie
Keyword(s):  
Aqueous Solution ◽  
Free Energy ◽  
Aqueous Solutions ◽  
Equilibrium Constants ◽  
Acid Solutions ◽  
Sulfurous Acid ◽  
Free Energy Of Formation ◽  
Dilute Aqueous Solutions ◽  
Sulfite Ion ◽  
Energy Of Formation

The free energy of formation of dimethyl sulfite in aqueous solution can be calculated as −91.45 ± 0.79 kcal/mol; this calculation required measurement of the solubility of dimethyl sulfite. From this value and the pKa of SO(OH)2, using previously reported methods, the free energy of formation of SO(OH)2 can be calculated to be −129.26 ± 0.89 kcal/mol. Comparison of this value with the value obtained from the free energy of formation of 'sulfurous acid' solutions, calculated from the free energy of formation of sulfite ion and the apparent pKa, values, permits evaluation of the free energy of covalent hydration of SO2 as 1.6 + 1.0 kcal/mol, in agreement with earlier qualitative spectroscopic observations. From the apparent pKa and the anticipated pKa values for the tautomers (SO(OH)2, pK1 = 2.3; HSO2(OH), pK1 = −2.6) it is possible to calculate the free energy change for tautomerization of SO(OH)2 to H—SO2(OH) as +4.5 ± 1.2 kcal/mol. All equilibrium constants required for Scheme 1, describing the species present in dilute aqueous solutions of SO2, have been calculated. In agreement with previous Raman studies the major tautomer of 'bisulfite ion' is calculated to be H—SO3−.

scholarly journals Photocatalytic Degradation of Ampicillin Using PLA/TiO2 Hybrid Nanofibers Coated on Different Types of Fiberglass

Water ◽  
2020 ◽  
Vol 12 (1) ◽  
pp. 176 ◽  
Author(s):  
Constantin Bobirică ◽  
Liliana Bobirică ◽  
Maria Râpă ◽  
Ecaterina Matei ◽  
Andra Mihaela Predescu ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Aqueous Solutions ◽  
Photocatalytic Degradation ◽  
Kinetic Studies ◽  
Electrospinning Technique ◽  
Edge Type ◽  
Photocatalytic Reactor ◽  
Hybrid Nanofibers ◽  
Different Types ◽  
Fiberglass Fabric

New photocatalytic membranes based on polylactic acid (PLA)/TiO2 hybrid nanofibers deposited on fiberglass supports were prepared and tested for the removal of ampicillin from aqueous solutions. The electrospinning technique was used to obtain hybrid nanofibers that were deposited on three types of fiberglass with different structures, resulting in three distinct photocatalytic membranes namely fiberglass fabric plain woven-type membrane, fiberglass mat-type membrane, and fiberglass fabric one-fold edge-type membrane. The results of the photocatalytic tests showed that the highest efficiency of ampicillin removal from aqueous solution is obtained with the fiberglass fabric plain woven-type membrane. Although it has been shown that the rate of photocatalytic degradation of ampicillin is high, being practically eliminated within the first 30 min of photocatalysis, the degree of mineralization of the aqueous solution is low even after two hours of photocatalysis due to the degradation of PLA from the photocatalytic membrane. The instability of PLA in the reactive environment of the photocatalytic reactor, evidenced by morphological, mineralogical and spectroscopic analyzes as well as by kinetic studies, is closely related to the structure of the fiberglass membrane used as a support for PLA/TiO2 hybrid nanofibers.

Kinetics of Reactive Extraction of Pyruvic Acid Using Tributylamine Dissolved in n-Butyl Acetate

2015 ◽  
Vol 13 (1) ◽  
pp. 63-69 ◽  
Author(s):  
Dharm Pal ◽  
Amit Keshav
Keyword(s):  
Aqueous Solution ◽  
Rate Constant ◽  
Pyruvic Acid ◽  
Butyl Acetate ◽  
Volume Ratio ◽  
Kinetic Studies ◽  
Extraction Process ◽  
Reactive Extraction ◽  
Kinetic Measurements ◽  
Kinetics Of

Abstract Studies have been made on the kinetics accompanied with mass transfer for the pyruvic acid/tributylamine (TBA)/n-butyl acetate system to investigate the effectiveness of reactive extraction for the separation of pyruvic acid from the aqueous solution. In the present work, kinetic studies, needed for the design of a recovery unit, were carried out using aqueous solution of pyruvic acid. TBA (conc. range 0.420–2.099 kmol/m3) dissolved in n-butyl acetate (conc. range 50–90%) was used as an extractant. The effect of reactant concentration, the effect of stirring speed and the effect of phase volume ratio on the extraction process were investigated. The kinetic parameters such as reaction order and rate constant were calculated. Kinetic measurements showed that the reaction is of second order occurring in the diffusion film and was found to be independent of hydrodynamic conditions. Rate constant was evaluated to be $0.419\,{{\rm{m}}^3}{\rm{mo}}{{\rm{l}}^{- 1}}{{\rm{S}}^{- 1}}$ .

Kinetics and mechanism of gold(III) incorporation into tetrakis(1-methylpyridium-4-yl)porphyrin in aqueous solution

2004 ◽  
Vol 08 (11) ◽  
pp. 1269-1275 ◽  
Author(s):  
Ahsan Habib ◽  
Masaaki Tabata ◽  
Ying Guang Wu
Keyword(s):  
Aqueous Solution ◽  
Rate Constants ◽  
Kinetic Data ◽  
Ph Dependence ◽  
Equilibrium Constants ◽  
Hydroxyl Group ◽  
Net Charge ◽  
First Order ◽  
Kinetics Of ◽  
Hydrolysis Of

The kinetics of the reaction of the tetrakis(1-methylpyridium-4-yl)porphyrin tetracation, [ H 2( TMPyP )]4+, with gold(III) ions were studied along with equilibria of gold(III) species in aqueous medium at 25°C, I = 0.10 M ( NaNO 3). The equilibrium constants for the formation of [ AuCl 4-n( OH ) n ]- ( n = 0,…,4), defined as β n = [ AuCl 4- n ( OH ) n ]- [ Cl -] n / [ AuCl 4-][ OH -] n were found to be that log β1 = 7.94 ± 0.03, log β2 = 15.14 ± 0.03, log β3 = 21.30 ± 0.05 and log β4 = 26.88 ± 0.05. The overall reaction was first order with respect to each of the total [ Au (III)] and [ H 2 TMPyP 4+]. On the basis of pH dependence on rate constants and the hydrolysis of gold(III), the rate expression can be written as d [ Au ( TMPyP )5+]/ dt = ( k 1[ AuCl 4-] + k2[ AuCl 3( OH )-] + k3[ AuCl 2( OH )2-] + k4[ AuCl ( OH )3-])[ H 2 TMPyP 4+], where k1, k2, k3 and k4 were found to be (2.16 ± 0.31) × 10-1, (6.56 ± 0.19) × 10-1, (1.07 ± 0.24) × 10-1, and (0.29 ± 0.21) × 10-1 M -1. s -1, respectively. The kinetic data revealed that the trichloromonohydroxogold(III) species, [ AuCl 3( OH )]-, is the most reactive. The higher reactivity of [ AuCl 3( OH )]- is explained by hydrogen bonding formation between the hydroxyl group of [ AuCl 3( OH )]- and the pyrrole hydrogen atom of [ H 2( TMPyP )]4+. Furthermore, applying the Fuoss equation to the observed rate constants at different ionic strengths, the apparent net charge of [ H 2( TMPyP )]4+ was calculated to be +3.5.

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