共查询到20条相似文献,搜索用时 31 毫秒
1.
Isabel Brandariz José L. Barriada Teresa Vilari?o Manuel E. Sastre de Vicente 《Monatshefte für Chemie / Chemical Monthly》2004,343(6):1475-1488
Several reported procedures for calibrating glass electrodes in proton concentration are compared. Some recommendations for non-experts are also given. The examined procedures can be classified into two broad categories, namely: those based on direct potential difference measurements of solutions of known proton concentration and those that use one or several pH standards to calibrate the electrode and subsequently measure the pH of solutions containing known proton concentrations. With a single buffer, the two types of procedures lead to equivalent results. However, if two pH buffers are used, the slope of the calibration graph in proton concentration will differ from the real electrode slope to an extent proportional to the difference between the liquid junction potentials of the two buffers. Therefore, any other method is preferable under these circumstances. 相似文献
2.
This paper deals with the problem of defining, and measuring, the pH inside the water pool (which we define as pHwp) of reverse micelles, i.e. micelles formed by surfactants dissolved in apolar solvents in the presence of minimal amounts of water. The conceptual and experimental difficulties are discussed, and it is argued that no absolute determination of pHwp is possible, mostly because water in the water pools of reverse micelles is a new solvent, for which no standardization of acidity is available. The problem can be approached only on the basis of an empirical acidity scale. An empirical acidity scale for water pools in reverse micelles of bis (2-ethyl-hexyl) sodium sulfosuccinate (AOT) in isooctane has been defined by measuring the 31P-chemical shifts of phosphate buffers. The chemical shifts in bulk water were compared to those found in reverse micelles under the assumption that the pK of phosphate ion is the same in the two systems. It was found that in most cases there was little difference (less than 0.4 pH units) between pHwp and the pH of the starting buffer in bulk water (which we define as pHst). However, this difference between pHwp and pHst may become much larger in certain cases. The difference (pHwp–pHst) is measured under a variety of conditions, and this permits the determination of an operational acidity in the micelle water pools as a function of the pHst with which the aqueous micelles are prepared. The significance of such data for interpreting the behaviour of enzymes confined in the micelles water pool is discussed. Based on the pHwp scale, the apparent pKa of phenol-red and 4-nitrophenol were determined in reverse micelles containing different buffers and different water content. The pKa values obtained were rather sensitive to changes of both these factors, which was taken to signify that organic dies have only a very limited applicability to measure the acidity of the water pools of reverse micelles. 相似文献
3.
Predrag Djurdjević Ratomir Jelić Ljubinka Joksović Mirjana Cvijović 《Monatshefte für Chemie / Chemical Monthly》2006,137(6):717-735
Summary. Solution equilibria between aluminium(III) ion and L-aspartic acid were studied by potentiometric, 27Al, 13C, and 1H NMR measurements. Glass electrode equilibrium potentiometric studies were performed on solutions with ligand to metal concentration
ratios 1:1, 3:1, and 5:1 with the total metal concentration ranging from 0.5 to 5.0 mmol/dm3 in 0.1 mol/dm3 LiCl ionic medium, at 298 K. The pH of the solutions was varied from ca. 2.0 to 5.0. The non-linear least squares treatment of the data performed with the aid of the Hyperquad program, indicated
the formation of the following complexes with the respective stability constants log βp,q,r given in parenthesis (p, q, r are stoichiometric indices for metal, ligand, and proton, respectively): Al(HAsp)2+ (log β1,1,1 = 11.90 ± 0.02); Al(Asp)+ (log β1,1,0 = 7.90 ± 0.03); Al(OH)Asp0 (log β1,1,−1 = 3.32 ± 0.04); Al(OH)2Asp− (log β1,1−2 = −1.74 ± 0.08), and Al2(OH) Asp3+ (log β2,1,−1 = 6.30 ± 0.04). 27Al NMR spectra of Al3+ + aspartic acid solutions (pH 3.85) indicate that sharp symmetric resonance at δ∼10 ppm can be assigned to (1, 1, 0) complex. This resonance increases
in intensity and slightly broadens upon further increasing the pH. In Al(Asp)+ complex the aspartate is bound tridentately to aluminum. The 1H and 13C NMR spectra of aluminium + aspartic acid solutions at pH 2.5 and 3.0 indicate that β-methylene group undergoes the most pronounced changes upon coordination of aluminum as well as
α-carboxylate group in 13C NMR spectrum. Thus, in Al(HAsp)2+ which is the main complex in this pH interval the aspartic acid acts as a bidentate ligand with –COO− and –NH2 donors closing a five-membered ring. 相似文献
4.
Mohammed M. Ghoneim Ibrahim S. El-Hallag Kamal Y. El-Baradie Hanaa S. El-Desoky Mona A. El-Attar 《Monatshefte für Chemie / Chemical Monthly》2006,137(3):285-299
Summary. The electrochemical behavior of some hydrazones derived from 6-chloro-2-hydrazinopyridine in the Britton-Robinson universal buffer of pH 2–11 containing 35% ethanol was investigated at the mercury electrode using dc-polarography, controlled-potential coulometry,
and cyclic voltammetry techniques. The examined hydrazones were reduced in solutions of pH < 9 in a single 4-electron diffusion-controlled irreversible step corresponding to both the saturation of –N=C< double bond
and cleavage of the –HN–NH– single bond of the hydrazone molecule via the consumption of two electrons for each center. Whereas the starting compound, 6-chloro-2-hydrazinopyridine, was reduced
in a single 2-electron diffusion-controlled irreversible step corresponding to cleavage of its –NH–NH2 single bond. The mechanistic pathway of the electrode reaction of the studied compounds was elucidated and discussed. The
pKa values of the examined hydrazones and the stoichiometry of their complexes in solution with some transition metal ions were
determined spectrophotometrically. The dissociation constants and the thermodynamic parameters of the investigated hydrazones,
and the stability constants of their metal complexes in solution were determined potentiometrically. 相似文献
5.
In this communication, a novel solid-state pH sensor based on WO3/MWNTs nanocomposite electrode will be reported. WO3 nanoparticles were homogeneously coated on vertically aligned MWNTs by magnetron sputtering. Potentiometric pH response of the WO3/MWNTs electrode in Britton–Robinson buffers revealed a linear working range from pH 2 to12 with a slope of about ?41 mV pH?1 and a response time less than 90 s. The stability of the electrode remained over a month. Moreover, the WO3/MWNTs electrode displayed excellent anti-interference property. Compared to conventional pH sensors, the pH sensor based on WO3/MWNTs nanocomposite electrode also showed excellent reproducibility, high stability and superb selectivity. 相似文献
6.
D. M. Sejmanović B. B. Petković M. V. Budimir S. P. Sovilj V. M. Jovanović 《Electroanalysis》2011,23(8):1849-1855
An all solid‐state Ag(I) ion‐selective electrode has been prepared by simply immersing a glassy carbon rod coated with PVCAc, which contained plasticizer and additive but no ionophore, into the AgNO3 solution. The response of the electrode was linear with a Nernstian slope of 60.25 mV/decade within the concentration range from 1×10?1 to 1×10?5 M and with a detection limit of 4.25×10?6 M. The stability as an effect of various cations was defined. The electrode is suitable for use in high acidic solutions (pH<1 to 7) and has successfully been applied for the determination of silver(I) concentrations in different samples. 相似文献
7.
Viktor Gutmann Gerhard Resch Wolfgang Kantner Wolfgang Linert 《Monatshefte für Chemie / Chemical Monthly》1989,120(1):11-20
Summary Plastic deformation of a copper electrode in an aqueous 10–4
M Cu(ClO4)2 solution leads to greater potential shifts, to smaller post strain effects and to greater relaxation rates as the ratio interfacial area: volume of copper is increased. It is suggested that its system organization is improved, as the interfacial area is increased. The system organization appears also to be improved as oxidic superstructures are developing at the interface, where the highest hierarchic levels of both electrode and electrolyte are in immediate contact. Further hints as to the system organization of the whole system Cu/CuSO4 solution are obtained from the fact that atpH=2 andc
Cu + +=10–1 mol/l the redox potential is independent of the pretreatment of the electrode and independent of the presence of oxidic superstructures. It is underlined that the passivity due to the presence of an oxidic superstructure is maintained only atpH >2, whereas at lowerpH-values copper is more readily dissolved. It is suggested that atpH=2 the system is in an optimal state of system organization (OSO), similar to those reported in the course of phase transformations, in extremely thin metal films and in solutions at the isokinetic temperature. 相似文献
8.
M. M. Ghoneim R. M. Issa R. A. Mahmoud 《Monatshefte für Chemie / Chemical Monthly》1981,112(3):293-299
The polarographic reduction of phenol red, chlorophenol red and bromophenol red has been investigated in buffered aqueous solutions and alcohol-water water mixtures over a widepH range (2–12). The results show that the three depolarizers are reduced through two irreversible one-electron waves of equal heights at allpH values. The two waves represent the reduction of the triphenylmethane carbon centre. The nature of the waves and the kinetics of the electrode reaction are discussed.
Elektroreduktion von Phenolrot, Chlorphenolrot und Bromphenolrot an der Quecksilbertropfelektrode
Zusammenfassung Die polarographischen Reduktionen wurden in gepufferten wäßrigen Lösungen und in Alkohol—Wasser-Mischungen über einen weitenpH-Bereich (2–12) durchgeführt. Es zeigte sich, daß in allen drei Fällen die Reduktion über zwei irreversible Ein-Elektron-Wellen gleicher Höhen bei allenpH-Werten vor sich ging. Die Kinetik der Elektrodenreaktion wird diskutiert.相似文献
9.
Andrei Blasko Alana Leahy-Dios William O. Nelson Steven A. Austin Robert B. Killion Gary C. Visor Ian J. Massey 《Monatshefte für Chemie / Chemical Monthly》2001,132(7):789-798
Summary. The kinetic and thermodynamic solubilities of Roche (Ro) pharmaceutical compounds were determined by HPLC, titrimetry, and UV/Vis spectroscopy in aqueous buffers and in non-buffered
systems. For kinetic solubility, a turbidimetric method that allows the rapid determination of solubilities using small amounts
of compounds (5–50 mg) was used. Two types of precipitation were observed during the kinetic solubility determinations: i) a disperse precipitation where the solution became foggy with very small particles uniformly distributed in the solution,
and ii) discrete precipitation characterized by formation of crystals that rapidly sediment. The thermodynamic solubility was determined
by shake flask and titrimetrically using a pH-STAT. The pH-STAT titrimetric method for the pH-thermodynamic solubility profile determination eliminates the buffer species and represents a new way to approach the solubility
characterization of pharmaceutical compounds. The strengths of the turbidimetric method for determining the kinetic solubility
are its rapidity, minimal compound requirements, and suitability for high throughput screening. The limitations are that the
maximum solubility is limited to less than 100 mg · cm−3, and the precipitation of trace impurities cannot be distinguished from precipitation of the analyte. The pH-STAT titrimetric approach for the thermodynamic solubility has a lower throughput and is suitable for the characterization
of the lead candidate. It is not limited in its solubility range and provides a common basis for the comparison of the solubility
values at different pH values in contrast to traditional buffered systems.
Received August 21, 2000. Accepted (revised) February 5, 2001 相似文献
10.
Raafat M. Issa Ahmed M. Hindawey Yousry M. Issa Farouk M. Issa 《Monatshefte für Chemie / Chemical Monthly》1978,109(4):961-973
The polarographic behaviour of solochrome violet RS is investigated in buffer solutions of varying pH in the absence and presence of surfactants (triton 100-X and dodecylbenzene-sulphonate). The reduction proceeds irreversibly along a single wave in acid solutions and two waves in alkaline ones. The electrode reaction corresponds to four electrons in media of pH<2.5 and pH>8.0; in media of pH 4 5.5 two electrons are consumed. In solution of pH 2.5 4 or 5.5–8.0, both reactions contribute in varying magnitudes. The addition ofSAS causes the inhibition of reduction beyond the 2-electrons stage in acid solutions; the polarograms comprise one wave in case ofDBS and two waves of equal height in presence of triton. In alkaline media the polarogram comprises three waves due to the splitting of the main reduction wave. The kinetic parameters of the electrode reaction are also determined. 相似文献
11.
《Analytical letters》2012,45(5):711-724
Abstract A flow injection potentiometric procedure is proposed for the determination of acidity of several samples using an antimony/ antimony oxide electrode. The ΔE/pH curve in phosphate buffer solutions in the pH range from 1.58 to 12.00 showed a linear sub-Nernstian behavior with an operational slope S =-42.1mV/pHc and a conditional standard potential of 264.8mV. This flow potentiometric electrode responds linearly to low acidity variations of dilute acetic acid solutions from 3.16 to 100mM with a slope of 30.1mV/dec and analytical frequency of 23 results/h. Good reproducibility and an average standard deviation of ±0.5% was obtained. The application of this sensor for the determination of coke acidity and acetic acid in vinegar is reported. 相似文献
12.
The kinetics of many electrode reactions, especially those involving the consumption/production of H+/OH?, show significant pH dependence. Systematic studies of the pH effect over a wide pH range can provide very useful information about their reaction mechanism(s) and help figure out the optimum reaction conditions. For fast electrode reactions in solutions of medium pH and low buffer capacity, correcting the effects induced from the shift of local pH near the electrode?electrolyte interface (pHs) is a prerequisite for unraveling the intrinsic kinetics and its pH dependence. In this review, recent progress on how to estimate the pHs, how to eliminate the effect induced by pHs shift and how to deduce the pH dependent intrinsic reaction kinetics are summarized. Mechanistic and kinetic implication of pH effect on electrocatalytic processes will be discussed by taking formic acid/formate oxidation at Pt electrode as an example. 相似文献
13.
I. S. Shehatta A. M. Hassanein E. M. Mabrouk 《Monatshefte für Chemie / Chemical Monthly》1995,126(8-9):851-862
Summary UV spectra, dc polarograms, cyclic voltammetry and coulometry measurements of salicylaldehyde-4-(2-pyridyl)-3-thiosemicarbazone (H2
SPT) were recorded inBritton-Robinson buffer solutions ofpH 2–12. The dissociation constants of H2
SPT evaluated spectrophotometrically and potentiometrically in a 5% (v/v)DMF-water mixture are concordant. The dc-polarograms in solutions ofpH<8.5 exhibit a single 4-electron diffusion-controlled polarographic wave, whereas in solutions ofpH>8.5 two waves are observed. The cyclic voltammograms give a single cathodic peak in acidic and neutral solutions, whereas two cathodic peaks can be identified in alkaline ones. An electrode mechanism is proposed and discussed. The effect of temperature on the dissociation constants and the polarographic data was also investigated; the corresponding thermodynamic parameters were derived and are discussed.
Thermodynamische und voltammetrische Untersuchungen an Salicylaldehyd-4-(2-pyridyl)-3-thiosemicarbazon
Zusammenfassung UV-Spektroskopische, dc-polarographische, voltammetrische und coulometrische Messungen an Salicylaldehyd-4-(2-pyridyl)-3-thiosemicarbazon (H2 SPT) inBritton-Robinson-Pufferlösungen (pH 2–12) wurden durchgeführt. Die spektrophotometrisch und potentiometrisch ermittelten Dissoziationskonstanten von H2 SPT in 5% (v/v)DMF/Wasser stimmen überein. In Lösungen mit einempH-Wert unter 8.5 zeigen die dc-Polarogramme eine einzelne diffusionskontrollierte polarographische Welle (4e–), während in Lösungen mit einempH-Wert von über 8.5 zwei Wellen zu beobachten sind. Die cyclischen Voltammogramme weisen in sauren und neutralen Lösungen einen, in basischen Lösungen hingegen zwei kathodische Peaks auf. Ein Elektrodenmechanismus wird vorgeschlagen und diskutiert. Der Effekt der Temperatur auf die Dissoziationskonstanten und die polarographischen Ergebnisse wurde ebenfalls untersucht. Die entsprechenden thermodynamischen Größen wurden bestimmt und werden diskutiert.相似文献
14.
Yassein M. Temerk 《Monatshefte für Chemie / Chemical Monthly》1979,110(1):139-147
The polarographic behaviour of the title compound in buffer solution ofpH 2–21 is discussed. The two observed waves in alkaline media (pH9.5) are assigned to the formation of hydrazo and the bishydrazo derivatives, whereas in acid solutions the reduction leads to cleavage of both two azo groups. The nature of the waves is investigated and a general mechanism for the reduction process in alkaline and acid media is suggested. The values of the kinetic parameters for the electrode reactions are reported.
Untersuchungen an Bisazo-Verbindungen I. Polarographisches Verhalten von 1-[4-(4-Natriumsulfonato-phenylazo)-3-natriumsulfonato-phenylazo]-2-naphthol in Lösungen mit verschiedenem pH an der tropfenden Quecksilber-Elektrode Polarographic behaviour of 1-[4-(4-sodiumsulfonato-phenylazo)-3-sodiumsulfonato-phenylazo]-2-naphthol in solutions of varyingpH at the dropping mercury electrode
Zusammenfassung Es wird das polarographische Verhalten der Titelverbindung in Pufferlösungen vompH 2–12 diskutiert. Die zwei im alkalischen Bereich (pH9,5) beobachteten Wellen werden der Bildung der Hydrazo- bzw. Bishydrazo-Derivate zugeordnet, im sauren Bereich führt die Reduktion zur Spaltung beider Azo-Gruppen. Die Natur der Wellen wird untersucht, und ein genereller Mechanismus für die Reduktion im alkalischen und sauren Bereich wird vorgeschlagen. Die kinetischen Parameter der Elektrodenreaktionen werden angegeben.相似文献
15.
白杨素在汞电极上的电化学行为及其消除超氧阴离子自由基能力研究 总被引:2,自引:0,他引:2
The electrochemical behavior of chrysin in pH 2.0-9.0 Britton-Robinson (B-R) buffer solutions was studied by the means of linear sweep voltammetry and cyclic voltammetry at a static mercury drop electrode. In different pH range of B-R buffer solutions, chrysin could cause four reduction waves. In pH 2.0-5.8 B-R buffer solutions, wave P1 yielded by chrysin is a one-electron reduction wave, and wave P1 caused by further reduction of the products of wave P1 in pH〈3.0 B-R buffer solution is also a one-electron reduction wave. But in 3.0〈pH〈5.8 B-R buffer solution wave P1 was overlapped by the hydrogen wave. Between pH 5.8 and 9.0, chrysin could yield two reduction waves P2 and P3- The former is an irreversible adsorptive wave of ionized chrysin involving one electron and the latter is also an irreversible adsorptive wave of reduction intermediate radical of chrysin involving one electron and one proton. And a linear relationship between ip3 and the concentration of chrysin can be established from 1.0×10^-6 to 4.0×10^-5 mol·L^-1 (r=0.9924) with the detection limit of 5×10^-7 mol·L^-1. In addition, the antioxidant ability of chrysin was investigated by linear sweep voltammetry (LSV). The determination result of IC50 of chrysin showed that chrysin is a good antioxidant. 相似文献
16.
Summary. Isopseudohypericin is formed from pseudohypericin in an alkaline, alcohol/water environment. The conditions for this conversion are specified, showing that these two compounds are in equilibrium at pH values of 5–10; pseudohypericin is stable below pH 5, and isopseudohypericin is stable above pH 10. It is also shown that the HPLC behavior of isopseudohypericin is dependent on the pH of the mobile phase: pH determines both the retention time and the UV-Vis spectrum characteristics of the corresponding peak analyzed using a diode array detector. Finally, different extraction conditions yield extracts containing different proportions of isopseudohypericin: it is suggested that this isopseudohypericin may be an artefact of extraction conditions and/or it may correspond to the compound cyclopseudohypericin, discussed by other experts but never formally characterized. 相似文献
17.
o-Phthalic acid is proposed as a standard substance for buffer solutions of known hydrogen ion concentration (I ? 0.2 M KCl, p[H+] = 3.0–5.4, 25°C). Its crystallinity, purity and slightly wide buffer range afford advantages over acetic acid. Empirical relationships between measured pH (pHm) and calculated [H+] were derived for sequences of buffer solutions at several ionic strengths: pHm - Mp[H+] + C. These calibration lines were parallel and of unit slope as required by theory. A table of p[H+] values for o-phthalic acid buffer solutions at I = 0.1 M (KCl) is presented and the method of calculation of p[H+] values for a buffer series generated by additions of potassium hydroxide is outlined. 相似文献
18.
A tungsten wire covered with Na0.75WO3 acts in potentiometry as a reversible pH electrode having a pH dependent open-circuit potential Eocp with nernstian slope. The mid-peak potential Emp of cyclic voltammograms also depends on pH. At low pH (e.g., pH 2) and slow scan rates (e.g., 2 mV s–1) the voltammetric response is almost completely reversible. At higher pH and faster scan rates, the voltammetric systems exhibit features of increasing irreversibility. Under the conditions of reversibility, the Eocp and Emp differ significantly. Eocp is determined by the proton transfer at the electrode surface; whereas Emp is determined by the electron transfer equilibrium tungsten(VI)/tungsten(V) and the proton transfer at the electrode surface. The difference between Eocp and Emp provides the individual thermodynamic contributions of electron and proton transfer to the overall pH dependent redox electrode. This is the first time that both contributions can be separated for an insertion electrochemical system (thin surface layer). It is also shown for the first time that the mechanism of an ion-sensitive electrode can differ in potentiometry and voltammetry. 相似文献
19.
Predrag Djurdjevi? Ratomir Jeli? Ljubinka Joksovi? Mirjana Cvijovi? 《Monatshefte für Chemie / Chemical Monthly》2006,12(2):717-735
Solution equilibria between aluminium(III) ion and L-aspartic acid were studied by potentiometric, 27Al, 13C, and 1H NMR measurements. Glass electrode equilibrium potentiometric studies were performed on solutions with ligand to metal concentration
ratios 1:1, 3:1, and 5:1 with the total metal concentration ranging from 0.5 to 5.0 mmol/dm3 in 0.1 mol/dm3 LiCl ionic medium, at 298 K. The pH of the solutions was varied from ca. 2.0 to 5.0. The non-linear least squares treatment of the data performed with the aid of the Hyperquad program, indicated
the formation of the following complexes with the respective stability constants log βp,q,r given in parenthesis (p, q, r are stoichiometric indices for metal, ligand, and proton, respectively): Al(HAsp)2+ (log β1,1,1 = 11.90 ± 0.02); Al(Asp)+ (log β1,1,0 = 7.90 ± 0.03); Al(OH)Asp0 (log β1,1,−1 = 3.32 ± 0.04); Al(OH)2Asp− (log β1,1−2 = −1.74 ± 0.08), and Al2(OH) Asp3+ (log β2,1,−1 = 6.30 ± 0.04). 27Al NMR spectra of Al3+ + aspartic acid solutions (pH 3.85) indicate that sharp symmetric resonance at δ∼10 ppm can be assigned to (1, 1, 0) complex. This resonance increases
in intensity and slightly broadens upon further increasing the pH. In Al(Asp)+ complex the aspartate is bound tridentately to aluminum. The 1H and 13C NMR spectra of aluminium + aspartic acid solutions at pH 2.5 and 3.0 indicate that β-methylene group undergoes the most pronounced changes upon coordination of aluminum as well as
α-carboxylate group in 13C NMR spectrum. Thus, in Al(HAsp)2+ which is the main complex in this pH interval the aspartic acid acts as a bidentate ligand with –COO− and –NH2 donors closing a five-membered ring. 相似文献
20.
The underlying metal was observed to corrode when a ruthenium dioxide-coated titanium electrode was anodized in an aqueous methanol solution. With a similarly coated platinum electrode peaks were observed on the voltammogram below 1.0 V which were attributed to methanol oxidation on the underlying metal. This effect was more pronounced when the electrode was subjected during cycling to potentials close to 0 V. Rapid oxidation of methanol on RuO2 was observed at potentials above 1.0 V, the rate at a given potential increasing in an approximately linear manner with increasing alcohol concentration. The rate of reaction also increased with increasing temperature and increasing surface roughness. Tafel slope values were rather high (>100 mV decade?1) and a mechanism involving anodically generated species such as OHads was proposed to account for these results. The variation of activity with pH was similar to that reported earlier for oxygen evolution at these anodes and this was again explained in terms of partial deactivation of the surface due to a combination of proton loss and phosphate ion adsorption at intermediate pH values. The release of carbon dioxide from aqueous solutions of higher alcohols at 25°C confirmed the high oxidizing power of RuO2 anodes. 相似文献