scholarly journals An LFER study of the protolytic equilibria of 4-aryl-2,4-dioxobutanoic acids in aqueous solutions

2007 ◽  
Vol 72 (12) ◽  
pp. 1201-1216 ◽  
Author(s):  
Tatjana Verbic ◽  
Branko Drakulic ◽  
Mire Zloh ◽  
Jovana Pecelj ◽  
Gordana Popovic ◽  
...  
Keyword(s):  
Ionic Strength ◽  
Aqueous Solutions ◽  
Parent Compound ◽  
Nmr Spectrum ◽  
Pka Values ◽  
Protolytic Equilibria ◽  
Tautomeric Forms ◽  
Ph Range ◽  
Semi Empirical

The protolytic equilibria of 13 4-aryl-2,4-dioxobutanoic acids (ADKs) were spectrophotometrically studied in aqueous solutions in the pH range 1-9 at 25?1 ?C and an ionic strength of 0.1 mol l-1 (NaCl), with the exception of the 4-OH-derivative which was also potentiometrically studied in the pH range 7-10 at 25?1 ?C and an ionic strength of 0.1 mol l-1 (NaCl). In solution, the compounds simultaneously exist in one diketo and two enolic forms; therefore, the determined acidity constants (pKa1 1.87-2.29, pKa2 6.63-8.13 and pKa3(4-OH-) 9.52) represent system macro constants. The 1H-NMR spectrum of the parent compound (4-phenyl- -2,4-dioxobutanoic acid) (25 ?C, pD 5.0) proved the existence of all tautomeric forms. Using the extended Hammett relation, the determined pKa values were correlated with literature ? values. The predicted pKa values were in fair accordance with the experimentally observed ones. Molecular, monoanionic and dianionic forms of the parent compound were optimized by the semi-empirical molecular orbital PM6 method using the implicit water solvation model (COSMO). The obtained geometries were used to explain the quality of the LFER models.

Formation and Properties of Americium Colloids in Aqueous Systems

1981 ◽  
Vol 6 ◽  
Author(s):  
U. Olofsson ◽  
B. Allard ◽  
K. Andersson ◽  
B. Torstenfelt
Keyword(s):  
Ionic Strength ◽  
Aqueous Solutions ◽  
Storage Time ◽  
Large Fraction ◽  
Average Charge ◽  
Particle Sizes ◽  
Aqueous Systems ◽  
Ph Range ◽  
And Storage ◽  
Solution Changes

ABSTRACTThe formation and sorption properties of colloidal americium in aqueous solutions have been studied with variations of pH (2–12), ionic strength (0.01–1.0 M NaClO4), americium concentration (10−7 −10−11 M) and storage time (6 h–6 months). A large fraction of the americium is sorbed on the container walls or on Al2O3 in the pH-range 7–11. Around pH 5–8 and at pH above 12 centrifugable fractions (particle sizes greater than 100 nm) are obtained. The fraction formed at pH above 12, which seems to be a true hydroxide colloid, migrates through an A12O3-filled column with very little retention. The average charge of americium species in solution changes from positive values at pH below 7–8 to negative values at pH above 10–11, as indicated from electromigration studies.

The Electroreduction of Periodate Anion in Alkaline Media

1971 ◽  
Vol 49 (16) ◽  
pp. 2657-2663 ◽  
Author(s):  
W. R. Fawcett ◽  
Y. C. Kuo Lee
Keyword(s):  
Ionic Strength ◽  
Aqueous Solutions ◽  
Double Layer ◽  
Mercury Electrode ◽  
Electrode Reaction ◽  
Alkaline Media ◽  
Dropping Mercury Electrode ◽  
Ph Range ◽  
Theoretical Developments

The electroreduction of periodate anion was studied at a dropping mercury electrode in aqueous solutions in the pH range 11–13.3 where the process is markedly affected by the double layer. The electrode reaction was found to be complex, its mechanism depending on both pH and ionic strength. The effects of the double layer on the component reactions are discussed with respect to current theoretical developments.

scholarly journals BUFFER SOLUTIONS BASED ON TAURINE

2021 ◽  
Vol 26 (1(77)) ◽  
pp. 48-64
Author(s):  
T. S. Ben’kovs’ka ◽  
R. E. Khoma ◽  
A. N. Chebotaryov ◽  
A. A.-A. Ennan ◽  
L. T. Osadchiy
Keyword(s):  
Ionic Strength ◽  
Aqueous Solutions ◽  
Buffer Capacity ◽  
Water System ◽  
Acid Base ◽  
Buffer Zones ◽  
Base Interaction ◽  
Temperature Range ◽  
Temperature Dependences ◽  
Ph Range

The acid-base interaction in the aminoethanesulfonic acid (taurine, Tau) – potassium aminoethanesulfonate – water system was studied by pH-, redox- and conductometric methods in the temperature range 293–313 K. The ion-molecular composition of NH2CH2CH2SO3H –NH2CH2CH2SO3K – H2O system was calculated. It is shown aminoethanesulfonic acid in aqueous solutions to exist at the ratio CKOH/QTau < 0.5 mainly in the zwitterion form similar to systems with glycine, aminomethanesulfonic acid and its N‑alkylated derivatives. The content of the aminoethanesulfonate anion is directly proportional to the CKOH/QGly ratio. The studied system ionic strength and acid-base dissociation constant for the second stage of the aminoethanesulfonic acid concentration and temperature dependences were determined. The ionic strength values at the isoelectric point (mi.p.)are directly proportional to С0Tau and practically do not depend on the temperature within the error for the same series С0Tau and С0KOH .The pH limits of the buffer action are determined and the buffer capacity of these systems is estimated. It has been established that effective buffer zones of Tau aqueous solutions can to maintain acidity in the higher then physiological pH range at temperature range 293–313 K. The buffer capacity of NH2CH2CH2SO3H – NH2CH2CH2SO3K – H2O system exceeds the analogous values of YNHCH2SO3H – YNHCH2SO3K – H2O (Y = H, CH3, CH2CH2OH, C(CH3)3 and C2H5C6H5) systems. The obtained data on the buffer capacity of the aminoethanesulfonic acid – potassium aminoethanesulfonate – water system can be used in chemical analysis, microbiological and biochemical studies, and the acidity data of the solutions studied can simulate the chemisorption of acid gases (carbon and sulfur dioxides).

scholarly journals Disproportionation and Polymerization of Plutonium(IV) in Dilute Aqueous Solutions

1983 ◽  
Vol 26 ◽  
Author(s):  
T. W. Newton ◽  
V. L. Rundberg
Keyword(s):  
Ionic Strength ◽  
Aqueous Solutions ◽  
Rate Constants ◽  
Second Order ◽  
Disproportionation Reaction ◽  
Reaction Products ◽  
Constant Ph ◽  
Low Concentrations ◽  
Dilute Aqueous Solutions ◽  
Ph Range

ABSTRACTThe rates of polymerization and disproportionation of Pu(IV) have been studied using low concentrations: (1.7 − 10) × 10−6M Pu, (0.8 − 12) × 10−4M HCI and 0.01M ionic strength. Osmium(II) complexes such as the tris−4,41−2,21−bipyridine complex were found to react rapidly with Pu(IV) but very slowly, if at all, with Pu(IV) polymer, Pu(lll), or Pu(V). Thus, it is possible to determine unreacted Pu(IV) in the presence of reaction products by using Os(II) complexes. Disproportionation reaction products, Pu(IlI) and Pu(V), were determined using their reactions with Ce(IV) sulfate. We find −d[Pu(IV)]/dt = k'[Pu(IV)]2 at constant pH. Log k1 varies from about 4.25 at pH 3 to about 7.0 at pH 4.1 (units for k1 are M−1min−1). The [H+] dependence varies from about −2 to −3 over the pH range studied. The measured rate is the sum of those for polymerization and disproportionation; the latter reaction amounts to about 75% of the total at pH 3 and 20% at pH 4. The second-order rate constants for disproportionation are very much larger than expected on the basis of extrapolation from 0.2 to 1.OM HClO, solutions. The products of the reaction do not affect the rate, but U(VI), aged Pu(IV) polymer, and CO2 increase the rate.

Sorption of Cadmium and Lead by Chelating Ion Exchangers Ostsorb OXIN, Ostsorb DETA, and Ostsorb DTTA

1994 ◽  
Vol 59 (6) ◽  
pp. 1311-1318 ◽  
Author(s):  
Ladislav Svoboda ◽  
Petr Vořechovský
Keyword(s):  
Ionic Strength ◽  
Aqueous Solutions ◽  
Sodium Perchlorate ◽  
Exchange Capacity ◽  
Chloride Ions ◽  
Point Of View ◽  
Alkaline Media ◽  
Ion Exchangers ◽  
Acidic Media ◽  
Cadmium And Lead

The properties of cellulose chelating ion exchangers Ostsorb have been studied in the sorption of cadmium and lead from aqueous solutions. The Cd(II) and Pb(II) ions are trapped by the Ostsorb OXIN and Ostsorb DETA ion exchangers most effectively in neutral and alkaline media but at these conditions formation of stable hydrolytic products of both metals competes with the exchange equilibria. From this point of view, Ostsorb DTTA appears to be a more suitable sorbent since it traps the Pb(II) and Cd(II) ions in acidic media already. Chloride ions interfere with the sorption of the two metals by Ostsorb DTTA whereas the ionic strength adjusted by the addition of sodium perchlorate does not affect the exchange capacity of this ion exchanger.

scholarly journals How Good Is the STW Sensor? An Account from a Larger Shipping Company

2021 ◽  
Vol 9 (5) ◽  
pp. 465
Author(s):  
Angelos Ikonomakis ◽  
Ulrik Dam Nielsen ◽  
Klaus Kähler Holst ◽  
Jesper Dietz ◽  
Roberto Galeazzi
Keyword(s):  
High Frequency ◽  
Additional Data ◽  
Empirical Method ◽  
Influential Factor ◽  
Sensor Data ◽  
Sea State ◽  
Shipping Company ◽  
Frequency Sensor ◽  
Semi Empirical

This paper examines the statistical properties and the quality of the speed through water (STW) measurement based on data extracted from almost 200 container ships of Maersk Line’s fleet for 3 years of operation. The analysis uses high-frequency sensor data along with additional data sources derived from external providers. The interest of the study has its background in the accuracy of STW measurement as the most important parameter in the assessment of a ship’s performance analysis. The paper contains a thorough analysis of the measurements assumed to be related with the STW error, along with a descriptive decomposition of the main variables by sea region including sea state, vessel class, vessel IMO number and manufacturer of the speed-log installed in each ship. The paper suggests a semi-empirical method using a threshold to identify potential error in a ship’s STW measurement. The study revealed that the sea region is the most influential factor for the STW accuracy and that 26% of the ships of the dataset’s fleet warrant further investigation.

scholarly journals Investigations of ternary complexes of Co(II) and Ni(II) with thiodiacetate anion and 1,10-phenanthroline or 2,2’-bipyridine in aqueous solutions

2014 ◽  
Vol 13 (1) ◽  
Author(s):  
Dariusz Wyrzykowski ◽  
Joanna Pranczk ◽  
Dagmara Jacewicz ◽  
Aleksandra Tesmar ◽  
Bogusław Pilarski ◽  
...  
Keyword(s):  
Aqueous Solutions ◽  
Substitution Reactions ◽  
Experimental Conditions ◽  
Kinetic Measurements ◽  
Hydroxo Complexes ◽  
Binary Complexes ◽  
Vis Spectroscopy ◽  
Potentiometric Titration Method ◽  
The Stability ◽  
Ph Range

AbstractA potentiometric titration method (PT) and a stopped-flow kinetic technique monitored by a UV−Vis spectroscopy have been used to characterize the stability of series of Co(II)- and Ni(II)-thiodiacetato complexes, M(TDA), in the presence of 1,10-phenanthroline (phen) or 2,2’-bipyridine (bipy) in aqueous solutions. The stability constants of the binary (1:1), ternary (1:1:1) as well as the resulting hydroxo complexes were evaluated and compared to the corresponding oxydiacetate complexes. Based on the species distribution as a function of pH the relative predominance of the species in the system over a pH range was discussed. Furthermore, the kinetic measurements of the substitution reactions of the aqua ligands to phen or bipy in the coordination sphere of the binary complexes M(TDA) were performed in the 288–303 K temperature range, at a constant concentration of phen or bipy and at seven different concentrations of the binary complexes (0.2–0.5 mM). The kinetic stability of the M(TDA) complexes was discussed in relation to the experimental conditions and the kind of the auxiliary ligands (phen/bipy). Moreover, the influence of the type of primary ligand (thiodiacetate/oxydiacetate) on the substitution rate of the auxiliary ligands was also compared.

Chemilumineszenz der SO2-Oxidation / Chemiluminescence of SO2-Oxidation

1978 ◽  
Vol 33 (3) ◽  
pp. 293-299 ◽  
Author(s):  
Joachim Stauff ◽  
Wolfgang Jaeschke
Keyword(s):  
Aqueous Solutions ◽  
Spectral Region ◽  
Time Course ◽  
Light Emission ◽  
Analog Computer ◽  
Reaction Scheme ◽  
So2 Oxidation ◽  
Recombination Product ◽  
Electronically Excited ◽  
Ph Range

Abstract The reactions of diluted aqueous solutions of SO2 resp. HSO3-ions with MnO4-or Ce4+ ions in the pH range 1-4 produce chemiluminescence in the spectral region of 450-600 nm. Measurements of the time course of the light emission and their simulation on an analog computer led to a reaction scheme in which a recombination product of primarily formed HSO3 radicals -of a lifetime of about 1 second -appears as precursor of electronically excited SO2 molecules. The participation of singlet oxygen can be excluded because at least the reaction with Ce4+ ions proceeds also in the absence of oxygen.

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