Search results for "Potentiometric"
showing 10 items of 157 documents
Bisferrocenyl-functionalized pseudopeptides: access to separated ionic and electronic contributions for electrochemical anion sensing
2016
Pseudopeptidic receptors containing ferrocene fragments have been prepared and their response to a series of anions was measured by a voltammetry of microparticles methodology. Such water-insoluble compounds yield anion-assisted reversible solid-state oxidations differing in their open-circuit potential and their midpeak potential recorded in cyclic voltammetric measurements. The difference between those potentials provides the individual thermodynamic contributions of electron and proton transfer, revealing that the mechanism of an ion-sensitive electrode can differ in potentiometry and voltammetry. The studied receptors are potentially interesting for potentiometric sensing, showing relat…
A program for the simultaneous potentiometric determination of protonation constants and electrode calibration parameters
2005
A program for the potentiometric determination of the protonation constants of mononuclear polyprotic substances is described. A maximum of twelve parameters can be determined simultaneously, including up to six protonation constants, four electrode calibration parameters, the protolysis constant of the solvent and the titrant concentration. Optimization is carried out by using the non-simplified Newton-Raphson method, which is potentiated by the Marquardt algorithm and a distance speeding-up coefficient. A direct search method is also used to improve the initial set of values. Variances are calculated very accurately, since the real Hessian function is used. Statistical weights and ionic s…
Equilibrium and kinetic studies on complex formation and decomposition and the movement of Cu2+metal ions within polytopic receptors
2013
Potentiometric studies carried out on the interaction of two tritopic double-scorpiand receptors in which two equivalent 5-(2-aminoethyl)-2,5,8-triaza[9]-(2,6)-pyridinophane moieties are linked with 2,9-dimethylphenanthroline (L1) and 2,6-dimethylpyridine (L2) establish the formation of mono-, bi- and trinuclear Cu(2+) complexes. The values of the stability constants and paramagnetic (1)H NMR studies permit one to infer the most likely coordination modes of the various complexes formed. Kinetic studies on complex formation and decomposition have also been carried out. Complex formation occurs with polyphasic kinetics for both receptors, although a significant difference is found between bot…
Hydrolysis of methyltin(IV) trichloride in aqueous NaCl and NaNO3 solutions at different ionic strengths and temperatures
1999
The hydrolysis of methyltin(IV) trichloride (CH 3 SnCl 3 ) has been studied in aqueous NaCl and NaNO 3 solutions (0 < l/mol dm -3 ≤1), at different temperatures (15 ≤ T/°C ≤ 45) by potentiometric measurements (H + -glass electrode). By considering the generic hydrolytic reaction pCH 3 Sn 3+ + qH 2 O = (CH 3 Sn) p (OH) q 3p-q +qH + (logβ pq ), we have the formation of five species and logβ 12 = -3.36, logβ 13 = -8.99, logβ 14 = -20.27 and logβ 25 = -7.61. The first hydrolysis step is measurable only at very low pH values and was not determined: a rough estimate of the hydrolysis constant is logβ 11 = -1.5 (± 0.5). The dependence on ionic strength of logβ pq is quite different in NaNO 3 and N…
Mono- and polynuclear hydroxo complexes of monophenylthallium(III)
1974
Summary The hydrolysis of PhTl(OH)ClO4 has been studied in a medium 0.3 M in NaClO4 by a potentiometric technique. The complexes formed by the hydrolysis reactions together with their formation constants have been determined by the general minimizing computer programme LETAGROP. The hydrolysis species observed in the pH range 3–5 are the mononuclear [(PhTlOH)(OH)], the dinuclear [(PhTlOH)2(OH)]+ and the dimer [(PhTlOH)2(OH)2]. The formation constants are log *β11=−4.92±0.2, log *β21=−1.52±0.03 and log *β22=−6.11±0.05. Stepwise reactions are then postulated whose formation constants are respectively log (*β21/*β11)=3.40±0.25, log (*β22/*β21)=−4.59±0.08 and log (*β22/*β112)=3.73±0.09.
In Situ Ammonium Profiling Using Solid-Contact Ion-Selective Electrodes in Eutrophic Lakes
2015
A promising profiling setup for in situ measurements in lakes with potentiometric solid-contact ion-selective electrodes (SC-ISEs) and a data processing method for sensor calibration and drift correction are presented. The profiling setup consists of a logging system, which is equipped with a syringe sampler and sensors for the measurement of standard parameters including temperature, conductivity, oxygen and photosynthetically active radiation (PAR). The setup was expanded with SC-ISEs in galvanically separated amplifiers. The potential for high-resolution profiling is investigated by deploying the setup in the eutrophic Lake Rotsee (Lucerne, Switzerland), using two different designs of am…
Proton and metal binding by cyclen-based highly rigid cryptands.
2010
The basicity properties of the two cryptands L1 and L2, featuring, respectively, a dibenzofuran or a diphenyl ether moiety bridging the 1,7 positions of a 1,4,7,10-tetraazacyclododecane macrocycle (cyclen) have been studied by means of potentiometric, UV-vis and fluorescence emission measurements. Both ligands show a high basicity in the first protonation step, the first basicity constant of L1 being too high to be measured in aqueous solution. The crystal structure of {[HL1]L1}(+) shows that the NH(2)(+) group is involved in an intramolecular hydrogen bonding network, which justifies the observed high basicity in solution. (1)H, (13)C NMR, UV-vis and fluorescence emission measurements show…
Interaction of Zn(II) and Cd(II) with Large Polyazacycloalkanes in dmso/H2O (80:20 vol./vol.). A potentiometric Study.
1990
Abstract A potentiometric study on the interaction at 25 °C and 0.15 mol dm −3 between large polyazacycloalkanes of the series [3 k ]aneN k and Zn(II) and Cd(II) ions in dmso:H 2 O (80:20 vol./vol.) is reported. The protonation behavior of the free macrocycles and coordination trends are compared with those previously observed in aqueous solution. The main features observed in the mixed solvent are: similar protonation behavior of the free polyamines, greater tendency to form binuclear and protonated complexes and a lower tendency to bear hydrolytic reactions.
>3 + 1 = 6 + 2> In Cu(ii) coordination chemistry of 1H-pyrazole aza cryptands
2015
A polyazamacrocycle formed from two tris(2-aminoethyl)amine units connected by 1H-pyrazole units shows unique hexanuclear Cu(ii) complexes by combination of two binuclear Cu(ii) cryptand complexes through pyrazolate moieties belonging to both cryptands. The formation of these dimeric entities has been proven both in solution by potentiometric studies and mass spectroscopy and in the solid state by X-ray diffraction of crystals of three different batches of formulae [Cu6(H-3L)2(H2O)2](TsO)6·22H2O (2), [Cu6(H-3L)2(NO3)2](NO3)4·2H2O (3) and [Cu6(H-3L)2Cl2]Cl4·(C4H5N3O2)2·14.35H2O (4). The hexanuclear unit in 2 and 4 can be viewed like three magnetically independent binuclear complexes with J =…
Hydrolysis and chemical speciation of (C2H5)2Sn2+, (C2H5)3Sn+ and (C3H7)3Sn+ in aqueous media simulating the major composition of natural waters
2001
The hydrolysis of (C 2 H 5 ) 2 Sn 2+ , (C 2 H 5 ) 3 Sn + and (n-C 3 H 7 ) 3 Sn + has been studied, by potentiometric measurements ([H + ]-glass electrode), in NaNO 3 , NaCl, NaCl/Na 2 SO 4 mixtures and in a synthetic seawater (SSWE), as an ionic medium simulating the major composition of natural seawater, at different ionic strengths (0 ≤ I ≤ 5 mol dm -3 ) and salinities (15 ≤ S ≤ 45), and at t = 25 °C. Five hydrolytic species for (C 2 H 5 ) 2 Sn 2+ , three for (C 2 H 5 ) 3 Sn + and two for (C 3 H 7 ) 3 Sn + are found. Interactions with the anion components of SSWE, considered as single-salt seawater, are determined by means of a complex formation model. A predictive equation for the calcul…