A sensor for the in situ determination of acidity levels in concentrated sulfuric acid

A potentiometric method at imposed weak current between two paste electrodes, ferrocene and chloranil, permits the in situ determination of sulfuric acid concentrations (0.5–11.0 M). The different factors affecting the potential at imposed current as current intensity, temperature and H⁺ ion concentration are studied. The potentials measured between ferrocene and chloranil electrodes are directly linked to the acid concentration. The acidity R_i(H) function, which represents the determination of the H⁺ activity has been determined and compared to Strehlow R_o(H), Janata H_GF and Hammet H_o functions. R_i(H) is numerically equal to the thermodynamic R_o(H). Received: 19 October 1998 / Revised: 22 March 1999 / Accepted: 23 March 1999     

A sensor for the in situ determination of acidity levels in concentrated sulfuric acid

A potentiometric method at imposed weak current between two paste electrodes, ferrocene and chloranil, permits the in situ determination of sulfuric acid concentrations (0.5–11.0 M). The different factors affecting the potential at imposed current as current intensity, temperature and H⁺ ion concentration are studied. The potentials measured between ferrocene and chloranil electrodes are directly linked to the acid concentration. The acidity R_i(H) function, which represents the determination of the H⁺ activity has been determined and compared to Strehlow R_o(H), Janata H_GF and Hammet H_o functions. R_i(H) is numerically equal to the thermodynamic R_o(H). Received: 19 October 1998 / Revised: 22 March 1999 / Accepted: 23 March 1999     

Prediction of the acidity level of concentrated mineral acid mixtures

A method for calculating the acidity level of mixtures of concentrated acidic solutions is presented. The method is based on the concept of isoacidity and the Zdanovskii rule. The calculated acidity function R_o(H) for ternary mixtures of phosphoric, sulfuric and perchloric acid are in good agreement with the values determined experimentally by electrochemical measurements.     

On the E.S.R. spectra of intermediates generated during the electrochemical oxidation of triphenylacetic acid in acetonitrile

The acidity level and the fluoride ion activity are evaluated in anhydrous HF and in water+HF mixtures of HF content higher than 70% by means of R(H) and R(F) functions. For both functions, the potentials of the ferrocene/ferricinium or perylene⁺/perylene²⁺ systems are used as reference potentials. A hydrogen electrode is used for acidity level evaluation and it is shown that the R(H) function decreases (acidity increases) when HF content increases in the mixture; the value of R(H) is ?15.5 for anhydrous hydrogen fluoride (+KF 0.1 M). A lanthanum trifluoride monocrystal electrode is built and used for F^? activity evaluations and it is shown that the R(F) function increases (activity of fluoride ion decreases) when HF content increases, up to R(F)=13.6 for basic anhydrous HF (KF 0.1 M solution).     

Water-Phosphoric Acid Media: Electrochemical Properties

Abstract

Electroactivity ranges at polished Platinum, vitreous Carbon, and Mercury electrodes are determined in H₂O - H₃PO₄ mixtures (0.1 -14 M H₃PO₄). The Ferrocene system is considered as a comparison system. Ag⁺/Ag_s and AgCl/Ag_s systems are considered as reference systems. The R_o(H) acidity function is determined. It varies from -2.0 to -6.0 when H₃PO₄ varies from 5.5 to 11.5 M.     

Adsorption and inhibitive properties of aminobiphenyl and its Schiff base on mild steel corrosion in 0.5 M HCl medium

Electrochemical measurements were performed to investigate the effectiveness and adsorption behaviour of aminobiphenyl (Aph) and 2-(3-hydroxybenzylideneamino)biphenyl (Aph-S), as corrosion inhibitors for mild steel (MS) in 0.5 M HCl solution. Potentiodynamic polarization, linear polarization resistance (LP) and electrochemical impedance spectroscopy (EIS) techniques were applied to study the metal corrosion behaviour in the absence and presence of different concentrations of Aph and Aph-S. In order to gain more information about adsorption mechanism the AC impedance technique was used to evaluate the potential of zero charge (PZC) from polarization resistance (R_p) versus voltage (E) plot. Potentiodynamic polarization measurements showed that Aph act as cathodic type inhibitor where as Aph-S act mixed type. The inhibition efficiency (IE%) increases with increasing concentration of compounds and reached 92.6% for Aph and 97.2% for Aph-S at 5 × 10⁻³ M. Double layer capacitance (C_dl) and polarization resistance (R_p) values are derived from Nyquist plots obtained from AC impedance studies. The experimental data fit Langmuir isotherm for both Aph and Aph-S, and from the adsorption isotherm some thermodynamic data for the adsorption processes are calculated and discussed. The effect of exposure time on the corrosion behaviour of mild steel in the absence and presence of inhibitor over 168 h was also studied.     

Nucleophilic substitution reactions of acetylides on substituted tricarbonyl(η6-fluoroarene)chromium and reactions of tricarbonyl[η6-(2-trimethylsilylethynyl)toluene]chromium and tricarbonyl[η6-(p-ethynyl-phenylethynyl)benzene]chromium with dicobalt octacarbonyl

Nucleophilic substitution reactions of various acetylides on substituted tricarbonyl(η⁶-fluoroarene)chromiums were pursued. The reaction presumably underwent a more complicated mechanism rather than the direct substitution on the fluorine-bearing carbon. The organometallic compounds (η⁶-C₆H₃R¹R²R³)Cr(CO)₃ (R¹: CC–C₆H₄CH₃, R²: o-Me, R³: H (5a), R¹: CC–C₆H₄CH₃, R²: o-OMe, R³: H (6a), R¹: CC–C₆H₄CH₃, R²: m-OMe, R³: H (6b), R¹: CCPh, R²: o-Me, R³: o-OMe (8b), R¹: CCPh, R²: m-Me, R³: m-OMe (8c), R¹: CCSiMe₃, R²: o-Me, R³: H (9a), R¹: CC–C₆H₄CCH, R²: H, R³: H (12), R¹: CC–C₆H₄CCH, R²: o-Me, R³: H (13)) as well as the organometallic dimmer [{(η⁶-o-Me-C₆H₄)Cr(CO)₃(di-ethynyl)] (di-ethynyl: CC–C₆H₄CC (14)) have been synthesized from nucleophilic substitution reactions of tricarbonyl(η⁶-fluoroarene)(chromium) compounds with suitable acetylides. The products have been characterized by spectroscopic means. In addition, (8b) and (8c) were characterized by X-ray diffraction studies. Further reactions of (9a) and (12) with appropriate amount of Co₂(CO)₈ yielded μ-alkyne bridged bimetallic complexes, Co₂(CO)₆{μ-Me₃SiCC–(o-tolueneCr(CO)₃} (10) and (Co₂(CO)₆)₂{μ-HCC–C₆H₄–CC–(benzene)Cr(CO)₃)}(15), respectively. Both (10) and (15) were characterized by spectroscopic means as well as single crystal X-ray crystallography. The core of these molecules is quasi-tetrahedron containing a Co₂C₂ unit. A two-dicobalt-fragments coordinated di-enyls complex, (Co₂(CO)₆)₂{μ-HCC–C₆H₄–CC–H} (17), was synthesized from the reaction of 1,3-diethynylbenzene with Co₂(CO)₈. Crystallographic studies of (17) also show that it exhibits a distorted Co₂C₂ quasi-tetrahedral geometry.     

Empirical relations between σI, σoR and taft σ* values of alkyl,acyl, benzoyl and substituted phenyl groups

The X(X) values¹ of the halogens (which resemble the Pauling electronegativities) and of some oxa substituents can be interpreted in terms of the inductive and resonance parameters σ_I and σ^o_R according to the regression equation

and η*_R=η(X)?η(R) it is found that for some substituted methyl, phenyl and benzoyl groups [σ*]^X_R=αη^X_R where α equals ?10.6 and ?10.9 for R = Me and R = Ph, CHO and PhCO respectively. Thus [σ*]^X_Rand η^x_r represent Taft σ* and [σ_I(X)?σ_oR(X)] values relative to that of the parent R group. The hydroxyl frequencies of phenol, and benzoic, acrylic, acetic and formic acids measured in dilute carbon tetrachloride solutions correlate with σ_I(X) and σ^o_R(X) according to the equations v(OH) = ?423.0 σ_I(X) + 3654.7 v(OH) = ?270.0 σ⁰_R(X) + 3586.7 where X = Ph, PhCO, CH₂=CHCO, MeCO and HCO. From these results, it is inferred that the σ* values of substituents having an α sp² hybridized carbon atom are proportional to σ⁰_R according to the equation σ*(X) = 3.97 σ⁰_R(X) + 1 New σ_I σ^o_R and σ* values of some acyi, benzoyl and substituted phenyl groups are presented.     

Gallium(III) halide complexes with phosphines,arsines and phosphine oxides – a comparative study

The phosphine oxide complexes [GaX₃(Me₃PO)] and [(GaX₃)₂{μ-o-C₆H₄(CH₂P(O)Ph₂)₂}] have been prepared and characterised by microanalysis, IR and multinuclear NMR (¹H, ¹³C{¹H}, ³¹P{¹H} and ⁷¹Ga) spectroscopy. The structures of [GaCl₃(Me₃PO)], [(GaBr₃)₂{μ-o-C₆H₄(CH₂P(O)Ph₂)₂}] and of the ionic product [GaI₂(Me₃PO)₂][GaI₄] have been determined and show that the Lewis acidity of the gallium halides towards phosphinoyl ligands diminishes as the halogen becomes heavier. The [GaX₃(Ph₃E)] (X = Cl, Br or I; E = P or As) and [(GaX₃)₂{μ-o-C₆H₄(CH₂PPh₂)₂}] (X = Br or I) have been prepared and their structural and spectroscopic properties compared with those of the phosphinoyl complexes. The results, and competitive solution NMR studies, show that Ga(III) binds the hard R₃PO in preference to the softer phosphine or arsine ligands. Hydrolysis of gallium(III) phosphines is shown to lead to [R₃PH][GaX₄], but in contrast to some other p-block halides, GaX₃ do not promote air-oxidation of R₃P to R₃PO.     

Quasi-tautomerism of 5-hydroxy-5-phenyl-5H-pyrido[2,3-b]chromenes in sulfuric acid

The existence of a quasi-tautomeric equilibrium in solutions of 5-hydroxy-5-phenyl-5H-pyrido[2,3-b]chromenes in sulfuric acid, which was confirmed by a linear dependence of the logarithms of the indicator ratios on acidity function H_R — H_O with a slope close to unity, was established. The pK values of this equilibrium correlate with the _p ^o and _R. ^o substituent constants.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 753–755, June, 1984.     

Corrosion resistance of molybdenum silicides in aqueous solutions

The corrosion performance of Mo-22Si and Mo-25Si alloys in 0.5 M sodium chloride (NaCl) and 0.5 M sodium hydroxide (NaOH) solutions, at room temperature, was evaluated using electrochemical techniques. In 0.5 M NaCl, additionally, the effect of solution pH (3, 7 and 10) and concentration (0.1, 0.5 and 1.0 M) was studied using techniques such as potentiodynamic polarization curves, linear polarization resistance and electrochemical noise in current. The alloy contained either -Mo or Mo₅Si₃ phases in a Mo₃Si matrix. Polarization results showed that only the alloys containing 22Si developed a passive film in 0.5 M NaOH solution, whereas the alloy containing 25Si was passivated only in 0.5 M NaCl, pH 10 solution. In 0.5 M NaCl, pH 7 and 0.5 M NaOH solutions, the alloy with 25Si was the one with the highest corrosion rate, whereas the one containing 22Si was the most corrosion resistant. In NaCl solutions, the alloys exhibited a localized type of corrosion, but not in NaOH solutions. Alkaline NaCl solutions increased the corrosion rate of the 75Mo-25Si alloy with respect to acidic or neutral solutions, whereas diluted (0.1 M) or concentrated (1.0 M) NaCl solutions produced lower corrosion rates than the 0.5 M NaCl solution. Some localized type of corrosion occurred in the NaCl solutions, due to a selective corrosion of the -Mo and Mo₅Si₃ phases with respect to the Mo₃Si matrix.     

Assessment of corrosion resistance of surface-coated galvanized steel by analysis of the AC impedance spectra measured on the salt-spray-tested specimen

In the present work, corrosion resistance of surface-coated galvanized steel was quantitatively determined by an analysis of the alternating current (AC) impedance spectra measured on the salt-spray-tested specimen. To evaluate the corrosion resistance of the surface-coated galvanized steel, AC impedance spectroscopy was performed on the salt-spray-tested specimen previously exposed to salt-sprayed corrosive environment. From the analysis of the impedance spectra, the area fraction transient of white rust θ ₂(t) was theoretically derived from the equivalent circuit equation by using two fitting parameters. The values of the two fitting parameters were determined by fitting the empirical transient equations to the area fraction of the resin coating layer and to the total resistance obtained from the impedance spectra measured, respectively. From the analyses of θ ₂(t) for four kinds of surface-coated galvanized steels with various resin coating layers, it is indicated that as the values of the two fitting parameters decrease in the order of CP, GI, OD and OM (commercial trade names) specimens, the corrosion resistance increases in that order as well. Furthermore, from the quantitative comparison of the two fitting parameters with the polarization resistance of the upper resin coating layer R _p determined from the potentiodynamic polarization curve, it is suggested that the two fitting parameters decrease in value as well with increasing R _p.     

Adsorption Behavior and Inhibition Corrosion Effect of Sodium Carboxymethyl Cellulose on Mild Steel in Acidic Medium

The effect of sodium carboxymethyl cellulose (Na-CMC) on the corrosion behavior of mild steel in 1.0 mol·L⁻¹ HCl solution has been investigated by using weight loss (WL) measurement, potentiodynamic polarization, linear polarization resistance (LPR), and electrochemical impedance spectroscopy (EIS) methods. These results showed that the inhibition efficiency of Na-CMC increased with increasing the inhibitor concentration. Potentiodynamic polarization studies revealed that the Na-CMC was a mixed type inhibitor in 1.0 mol·L⁻¹ HCl. The adsorption of the inhibitor on mild steel surface has been found to obey the Langmuir isotherm. The effect of temperature on the corrosion behavior of mild steel in 1.0 mol·L⁻¹ HCl with addition of 0.04% of Na-CMC has been studied in the temperature range of 298–328 K. The associated apparent activation energy (E^*_a) of corrosion reaction has been determined. Scanning electron microscopy (SEM) has been applied to investigate the surface morphology of mild steel in the absence and presence of the inhibitor molecules.     

Acidities of Hydrochloric Acid in Water/Acetic Acid and in Water/Acetic Acid/Formaldehyde Mixtures: Investigations with the indicator method and with the nmr method. 31st communication on investigations in textile chemistry

The NMR. chemical shift (δ_H) of the acidic proton in the systems HCl/H₂O and HCl/H₂O/HOAc was correlated with the acidity function (H_o)_I determined by the indicator method. By using three indicators it could be shown that, except for solutions with very low concentrations of hydrochloric acid, the acidity function (H_o)_I correlates with δ_H in a way which can be rationalized. Addition of 7,5% (W) formaldehyde to these systems changes (H_o)_I and δ_H very significantly, particularly in systems with low water content. Logarithmic rate constants of cellulose formal formation in HCl/H₂O/HOAc systems which do not show a linear relationship with (H_o)_I, measured without presence of formaldehyde, do so if (H_o)_I is measured with formaldehyde present. For these systems, however, δ_H is not a suitable acidity parameter.     

Fourier transform-ion cyclotron resonance study of the gas-phase acidities of germane and methylgermane; Bond dissociation energy of germane

An accurate gas-phase acidity for germane (enthalpy scale, equivalent to the proton affinity of GeH₃ ^?), ΔH _acid ^o(GeH₄) = 1502.0 ± 5.1 kJ mol^?1, is obtained by constructing a consistent acidity ladder between GeH₄, and H₂S by using Fourier transform-ion cyclotron resonance spectrometry, and 0 and 298.15 K values for the first bond dissociation energy of GeH₄ are proposed: D₀ ^o(H₃Ge-H) = 352 ± 9 kJ mol^?1; D ^o(H₃Ge-H) = 358 ± 9 kJ mol^?1, respectively. These results are compared with experimental and theoretical data reported in the literature. Methylgermane was found to be a weaker acid than germane by approximately 35 kJ mol^?1: ΔH _acid ^o = 1536.6 kJ mol^?1.     

Electrochemical corrosion behavior of nanocrystalline zinc coatings in 3.5% NaCl solutions

The corrosion behavior of electrodeposited nanocrystalline (NC) zinc coatings with an average grain size of 43 nm was investigated in 3.5% NaCl solutions in comparison with conventional polycrystalline (PC) zinc coatings by using electrochemical measurement and surface analysis techniques. Both polarization curve and electrochemical impedance spectroscopy (EIS) results indicate that NC and PC coatings are in active state at the corrosion potentials, and NC coatings have much higher corrosion resistance than PC ones. The corrosion products on both coating surfaces are mainly composed of ZnO and Zn₅(OH)₈Cl₂·H₂O, but the corrosion products can form a relatively more protective layer on NC coating surfaces than on PC coatings. The EIS characteristics and corrosion processes of PC and NC zinc coatings during 330 h of immersion were discussed in detail.     

Anodic dissolution of osmium in acid media

The anodic dissolution of Os in acidic solutions was studied under potentiostatic conditions. The results show high dissolution rates that increase markedly at rising potential. The presence of chloride ions and to a greater extent the increase in acidity of the solutions inhibit the anodic corrosion process. The nature of the dissolution products did depend on the solution pH and the concentration of the complexing anion. Thus, in HClO₄ acid and in chloride solutions at low concentration or acidity, Os goes into solution as OsO₄; in concentrated HCl solution, tetraoxide and chloro-osmyl anions are formed. No OsCl₆^2? complex was detected in solution even at high HCl concentration.     

The effect of 2-aminoquinoline-6-carboxylic acid on the corrosion behavior of mild steel in hydrochloric acid

The inhibitive effect of 2-aminoquinoline-6-carboxylic acid (AQC) against mild steel corrosion in 1?M HCl solutions was investigated using conventional weight loss, potentiodynamic polarization, linear polarization and electrochemical impedance spectroscopy methods. The weight loss results showed that AQC is an excellent corrosion inhibitor since its efficiency increased with the concentration to attain 91.8?% at 500?mg?l^?1. Electrochemical polarization measurements revealed that AQC acted as a mixed-type inhibitor and the results of electrochemical impedance spectroscopy have shown that the change in the impedance parameters, charge transfer resistance and double layer capacitance, with the change in concentration of the inhibitor is due to the adsorption of the molecule leading to the formation of a protective layer on the surface of mild steel. The adsorption was assumed to occur on the steel surface through the active centers of the molecule. The inhibition action of AQC was discussed in view of Langmuir adsorption isotherm. Density functional theory calculations of quantum parameters were used to explain efficiency in relation with molecular structure.     

Titanium(IV) complexes containing mono‐cyclopentadienyl and bulky trityloxy mixed ligands: synthesis and polymerization activity

Eight new R¹CpTiCl₂(OC(C₆H₄R²)Ph₂) complexes were synthesized by the reaction of R¹CpTiCl₃ with Ph₂(R²C₆H₄)COH (R²C₆H₄ = phenyl or o‐methyl‐phenyl) in the presence of Et₃N in good yield and characterized by ¹H NMR, elemental analysis, IR and mass spectrometry. A suitable single crystal of complex 2 (R¹: CH₃, R²: H) was obtained and the structure determined by X‐ray diffraction. When activated by methylaluminoxane (MAO), all complexes were active for the polymerization of ethylene and styrene. The effect of variation in temperature, catalyst concentration and MAO/catalyst molar ratio was also studied. Complex 5 (R¹: n‐C₄H₉, R²: H) showed a moderate conversion (37.4%) for the polymerization of methyl methacrylate. Copyright © 2005 John Wiley & Sons, Ltd.     

Flow properties of poly(methyl methacrylate) solutions

Viscosity and normal stress behavior were measured for poly(methyl methacrylate) samples of various average molecular weights in diethyl phthalate solution at 30 and 60°C. All samples conformed approximately to the most probable distriution (M?_w/M?_n = 2). Concentrations ranged from 0.113 to 0.38 g/ml, and M?_w from 53,800 to 1,620,000. Despite considerable evidence in the literature of unusual linear viscoelastic behavior for this polymer, its nonlinear properties appear to be rather conventional. The viscosity–shear rate master curve was similar to that found earlier for concentrated solutions of polystyrene and poly(vinyl acetate) of comparable molecular-weight distribution. The viscosity time constant τ_o parallels τ_R, the characteristic time of the Rouse model, although the residual dependence of τ_o/τ_R on concentration and molecular weight appears to be slightly different from that for polystyrene and poly(vinyl acetate). Similar conclusions apply to the recoverable compliance J_e,^o estimated from the normal stress behavior of each solution, and its relationship to the Rouse model compliance J_R.