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1.
The inhibition behavior of 6-methyl-4,5-dihydropyridazin-3(2H)-one (MDP) on corrosion of mild steel in 1 M HCl and 0.5 M H2SO4 was investigated using weight loss, potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS) measurements. The results indicated that the corrosion inhibition efficiency depends on concentration, immersion time, solution temperature, and the nature of the acidic solutions. It is also noted that MDP is at its the most efficient in 1 M HCl and least in 0.5 M H2SO4. The effect is more pronounced with MDP concentration. It is found that the inhibition efficiency attains 98 % at 5 × 10?3 M in 1 M HCl and 75 % at 5 × 10?2 in 0.5 M H2SO4. Polarization measurements showed that the MDP acts as a mixed inhibitor. EIS diagrams showed that the adsorption of MDP increases the transfer resistance and decreases the capacitance of the interface metal/solution. From the temperature studies, the activation energies in the presence of MDP were found to be superior to those in uninhibited medium. Finally, a mechanism for the adsorption of MDP was proposed and discussed.  相似文献   

2.
The kinetics of oxidation of tartaric acid (TAR) by peroxomonosulfate (PMS) in the presence of Cu(II) and Ni(II) ions was studied in the pH range 4.05–5.20 and also in alkaline medium (pH ~12.7). The rate was calculated by measuring the [PMS] at various time intervals. The metal ions concentration range used in the kinetic studies was 2.50 × 10?5 to 1.00 × 10?4 M [Cu(II)], 2.50 × 10?4 to 2.00 × 10?3M [Ni(II)], 0.05 to 0.10 M [TAR], and µ = 0.15 M. The metal(II) tartarates, not TAR/tartarate, are oxidized by PMS. The oxidation of copper(II) tartarate at the acidic pH shows an appreciable induction period, usually 30–60 min, as in classical autocatalysis reaction. The induction period in nickel(II) tartarate is small. Analysis of the [PMS]–time profile shows that the reactions proceed through autocatalysis. In alkaline medium, the Cu(II) tartarate–PMS reaction involves autocatalysis whereas Ni(II) tartarate obeys simple first‐order kinetics with respect to [PMS]. The calculated rate constants for the initial oxidation (k1) and catalyzed oxidation (k2) at [TAR] = 0.05 M, pH 4.05, and 31°C are Cu(II) (1.00 × 10?4 M): k1 = 4.12 × 10?6 s?1, k2 = 7.76 × 10?1 M?1s?1 and Ni(II) (1.00 × 10?3 M): k1 = 5.80 × 10?5 s?1, k2 = 8.11 × 10?2 M?1 s?1. The results suggest that the initial reaction is the oxidative decarboxylation of the tartarate to an aldehyde. The aldehyde intermediate may react with the alpha hydroxyl group of the tartarate to give a hemi acetal, which may be responsible for the autocatalysis. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 620–630, 2011  相似文献   

3.
An inorganic film of ruthenium hexachloroplatinate (RuPtCl6), deposited on the surface of a glassy carbon electrode, exhibits electrocatalytic activity in the oxidation of purine bases, such as adenine and guanine. Appropriate working conditions are found for fabricating a polymer film on the surface of glassy carbon and for recording the maximum electrocatalytic effect for the modified electrode. A method is developed for the selective voltammetric determination of guanine and adenine in their simultaneous presence on an electrode modified by a RuPtCl6 film. A procedure is proposed for the amperometric detection of purine bases with this modified electrode under the conditions of flow-injection analysis. The dependence of the analytical signal on the concentration of guanine and adenine is linear up to 5 × 10?6 and 5 × 10?7 M in the stationary mode and to 5 × 10?7 and 5 × 10?8 M under flow conditions, respectively. The proposed method was tested in the analysis of calf thymus DNA for the concentrations of guanine and adenine.  相似文献   

4.
The aim of this work is the phytochemical study of the butanolic extract of the aerial parts of Veronica rosea. Four compounds 14 have been isolated using different chromatographic methods. The structures of these compounds were determined by NMR spectral analysis and mass spectroscopy. The adsorption and anticorrosion effects of this extract were investigated towards the corrosion of copper in 1 M HNO3 aqueous by the weight loss technique and potentiodynamic polarization. The results showed that the butanolic extract is a good inhibitor and the inhibition efficiency increases with increasing of concentration of the inhibitor. The adsorption of this extract on the copper specimen surface was spontaneous and obeyed the Langmuir’s adsorption isotherm. Large value of adsorption equilibrium Constant (K ads = 35 L g?1) was obtained. The polarization experiments confirmed the data obtained by gravimetric weight-loss. Tafel plot of polarization curves indicates that the extract acts as a mixed type inhibitor.  相似文献   

5.
The effect of adding 2-phenylimidazo[1,2-a]pyridine-3-carbaldehyde derivative named (P2), newly synthesized on the electrochemical behavior of C38 steel in molar hydrochloric acid was investigated by using the weight-loss method, potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS) measurements. EIS results show that the transfer resistance increases with the increase of concentration of P2 and it also had an inhibiting effect on C38 steel corrosion in HCl solutions. Weight-loss essays confirm that the corrosion rate decreases as the P2 concentration increases. The inhibition efficiency for this compound studied increased with the increase in the inhibitor concentrations to attain 91.7 % at the 10?3 M of P2. The potentiodynamic polarization curves indicated that P2 acted as a mixed-type inhibitor in hydrochloric acid.  相似文献   

6.
This work presents a sol‐gel based biosensor for atrazine determination which has been obtained by introducing the enzyme polyphenol oxidase from apple tissue in a sol‐gel matrix. Apple tissue acts as a molecular recognition element. Atrazine is an inactive compound electrochemically; redox coupling of dopamine was used for studying atrazine behavior. Atrazine was determined by monitoring the inhibition power of polyphenol oxidase activity. The measurements were performed in 0.1 M KH2PO4‐NaOH buffer (pH 7.5). The effect of various experimental parameters such as pH, concentration of buffer, concentration of dopamine, incubation time and matrix composition has been investigated for optimum analytical performance. The biosensor consisted of 10.3% (w/w) of apple tissue. The bioelectrode exhibits a linear response for dopamine and atrazine concentrations in the range of 5.66 × 10?6?2.27 × 10?3M and 1 × 10?5 ?1 × 10?4 M with a detection limit of 4.2 × 10?6 and 5.5 × 10?6 M, respectively. A correlation coefficient of 0.9945 and a relative standard deviation (R.S.D.) of 3.29% for dopamine, 0.9944 and 3.69% for a trazine were achieved.  相似文献   

7.
The effect of cefazolin (CZ) and cefotaxime (CT) as corrosion inhibitors for carbon steel in 0.5 M H2SO4 solution was investigated by use of potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), electrochemical frequency modulation (EFM), and scanning electron microscopy (SEM). CZ and CT acted as mixed-type inhibitors. Inhibition increased with increasing inhibitor concentration and decreased with increasing temperature. Adsorption of the inhibitors obeyed the Langmuir adsorption isotherm. SEM confirmed inhibition by the inhibitors. Inhibition by 5 × 10?4 M CZ and 7 × 10?4 M CT approached 99.6 % and 90.9 %, respectively. The EIS and EFM results were in good agreement with the potentiodynamic data.  相似文献   

8.
The inhibiting efficiency of 2-mercapto-1-methylimidazole (MMI) on copper corrosion in sulfuric acid was investigated at 30 °C. Its effectiveness was assessed through electrochemical impedance spectroscopy, potentiodynamic polarization and gravimetric measurements. The results of study reveal that the inhibition efficiency of MMI depends on its concentration and attains approximately 81% at 10?4 M. The inhibitor was adsorbed on the copper surface according the Langmuir adsorption isotherm model. The value of standard free energy of adsorption was calculated from this isotherm.  相似文献   

9.
The influence of dissolved cupric and ferric ions on the photocatalytic degradation of phenol in aqueous dispersions of titanium dioxide was investigated. At pH 3.5 both ion species enhanced the TiO2 photocatalytic activity until an optimum metal concentration was reached (1×10?3 M for Cu2+ and 7×10?6 M for Fe3+). Beyond these values the activity was observed to decrease, what was mainly attributed to precipitation of metal derivatives. A mechanism based in the formation of a complex between the metal and the organic compound adsorbed onto the titania surface is proposed to explain the observed positive effect of copper and iron ions addition.  相似文献   

10.
Some triazole-type organic compounds were tested as corrosion inhibitors for copper in 0.5 M HCl solution at 20°C. Electrochemical (potentiodynamic polarization and polarization resistance measurements) and gravimetric methods were used for this study. The obtained results showed that 3-amino-1,2,4 triazole (ATA) and 3,5 diamino-1,2,4 triazole (DTA) effectively reduce the corrosion rate of copper. The inhibition efficiency (E%) of these compounds increases with their concentrations and attains maximum values at 10−3M and 10−4 for ATA and DTA, respectively. The variation of efficiency with logC shows that these inhibitors are adsorbed on the metallic surface according to the Frumkin adsorption isotherm model.  相似文献   

11.
In the presence of purine, the copper(II)/copper(Hg) couple splits into copper(II)/copper(I) and copper(I)/copper(Hg) couples, which form two well-separated systems of peaks under voltammetric conditions. The copper(I)/purine complex adsorbs on the electrode surfacer and can be deposited on the electrode surface by electroreduction of copper(II) ions at the HMDE or by electro-oxidation of the hanging copper amalgam drop electrode (HCADE). The deposit can be stripped either cathodically or anodically over the pH range 2–9. The cathodic stripping variant at the HCADE, in solution with pH 2, offers the best results, with linear response for the range 5 × 10?9–1.5 × 10?7 mol dm?3 purine after an accumulation time of 3 min. The detection limit found with the HMDE in the presence of copper(II) ions is higher.  相似文献   

12.
A voltammetric study of the oxidation of Ceftazidime (CEFT) has been carried out at the glassy carbon electrode by cyclic, differential pulse (DPV) and square wave (SWV) voltammetry. The oxidation of CEFT was irreversible and exhibited diffusion controlled process depending on pH. The oxidation mechanism was proposed and discussed. According to the linear relationship between the peak current and concentration, DPV and SWV voltammetric methods for CEFT assay in pharmaceutical dosage forms and human urine were developed. For analytical purposes, a well resolved diffusion controlled voltammetric peak was obtained in 0.1 M H2SO4 at 1.00 and 1.02 V for differential pulse and square wave voltammetric techniques, respectively. The linear response was obtained within the range of 4 × 10?6?8 × 10?5 M with a detection limit of 6 × 10?7 M for differential pulse and 4 × 10?6–2 × 10?4 M with a detection limit of 1 × 10?6 M for square wave voltammetric technique. The determination of CEFT in 0.1 M H2SO4 was possible over the 2 × 10?6–1 × 10?4 M range in urine sample for both techniques. The standard addition method was used for the recovery studies.  相似文献   

13.
Kinetics of silver electrodeposition in the presence of sulfide ions is studied on electrodes renewed by cutting off a thin surface layer, at a controlled time of contact of the “fresh” surface with the electrolyte. Solutions containing 10?2 M AgNO3, 0.1 M thiocarbamide, 0.5 M HClO4, and from 2 × 10?6 to 1.5 × 10?5 M Na2S are studied. It is shown that under the studied conditions, the effect of silver electrodeposition on the surface concentration of sulfide ions is insignificant. As the concentration of sulfide ions in solution and their coverage on the electrode surface θ increase, the cathodic polarization decreases. Tafel curves plotted for θ = const are used in estimating the exchange current i 0 and the transfer coefficient α. It is shown that α ≈ 0.5 and weakly depends on θ, whereas the exchange current increases with the increase in θ by an approximately linear law from 10?5 A/cm2 at θ ? 0 to 10?4 A/cm2 at θ = 0.43. The obtained data are compared with the results of kinetic studies of silver anodic dissolution in similar solutions.  相似文献   

14.
The influence of hydrogen phosphate (HPO42−) and molybdate ions (MoO42−) on the behavior of tin corrosion in 0.2 M maleic acid was compared using experimental and theoretical techniques. The experimental studies consisted of the electrochemical investigations (potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS)), along with the surface analytical techniques (SEM and EDX). Additionally, the theoretical analysis (the chemical quantum computations at MP4/SDD level of theory in the aqueous phase), was conducted. The experimental outcomes illustrated that the inhibition efficiency (η%) increases with the concentration of the inhibitors, reaching 88 % and 81 % at 2×10−2 M concentration of MoO42− and HPO42−, respectively. The potentiodynamic polarization curves revealed that HPO42− performance is a cathodic-type inhibitor, while MoO42− shows a mixed-type behavior. The increase in temperature decreased the η% values of both inhibitors. Based on surface analysis and thermodynamic study, the presence of the two inhibitors formed protective films on the tin surface through a physisorption mechanism. The chemical quantum computations using the complete fourth-order Møller Plesset perturbation theory (MP4 with SDD basis) method results outlined the favorable affinity of the investigated inorganic inhibitors to interact with the tin surface, which interprets the well-observed inhibition efficiencies.  相似文献   

15.
7-Cchloro-3-(4-methoxystyryl)quinoxalin-2(1H)-one (CMOSQ) and 7-chloro-2-(4-methoxyphenyl)thieno(3.2-b)quinoxaline (CMOPTQ) have been investigated for mild steel corrosion in 1 M HCl at different concentrations using weight loss measurements, potentiodynamic polarization curves and electrochemical impedance spectroscopy methods. Generally, inhibition efficiency of the investigated compounds was found to depend on inhibitor concentration and their structures. Comparitive results showed that CMOPTQ was the best inhibitor and the inhibition efficiency increased with increasing the concentration and attained 86 and 87 % at 10?3 M of CMOPTQ and 10?3 M of CMOSQ, respectively. Potentiodynamic polarization studies clearly reveal that these inhibitors act essentially as cathodic-type inhibitors. The inhibition efficiency increases with immersion time and reaches 95 % CMOPTQ at 24 h. The electrochemical impedance spectroscopy result showed that these compounds act by formation of film.  相似文献   

16.
The effect of sodium sulfide additions (from 5 × 10?6 to 2 × 10?5 M) on the kinetics of gold dissolution in cyanide solutions of the following composition, M: 0.1 KCN, 0.02 KAu(CN)2, 0.5 K2SO4, pH 10–13 is studied. Hydrosulfide ions are shown to exert a strong catalytic effect on the dissolution kinetics of this metal in a potential range where their adsorption is accompanied by the formation of polysulfides (?0.2 < E < 0.4 V). The reaction acceleration depend on the potential and is 100-fold for E ? 0.1 V. The effect becomes more pronounced as the concentration of hydrosulfide ions increases to 10?4 M and is almost pH-independent in the pH range from 10 to 13. An attempt to explain the found relationships is undertaken.  相似文献   

17.
《Electroanalysis》2005,17(19):1746-1754
Highly selective poly(vinyl chloride) (PVC) membrane electrodes based on recently synthesized mercury complexes including Hg(Nmpntb)2 and Hg(Npdntb)2 as new carriers for iodide‐selective electrodes by incorporating the membrane ingredients on the surface of graphite electrodes are reported. The effect of various parameters including the membrane composition, pH and possible interfering anions were investigated on the response properties of the electrodes. Both sensors exhibited Nernstian responses toward iodide over a wide concentration range of 7×10?7 to 0.1 M and 1×10?6 to 0.1 M, with slopes of 59.6±0.8 and 58.9±0.9 mV per decade of iodide concentration and detection limit of 3×10?7 M and 7×10?7 for Hg(Npdntb)2 and Hg(Nmpntb)2, respectively, over a wide pH range of 3–11. The sensors have response times of ≤5 s and can be used for at least 2 months without any considerable divergence in their potential response. The proposed electrodes show good ability to discriminate iodide over several inorganic and organic anions. The electrodes were successfully applied to direct determination of iodide in synthetic mixture, waste water and drinking water and as indicator electrodes in precipitation titrations.  相似文献   

18.
The inhibition effect of 1-methyl pyrazole (MPA) on the acidic corrosion of iron in 1.0 M HCl was studied at different concentrations (10?3–10?2 M) by potentiodynamic polarization and electrochemical impedance spectroscopy, and EIS measurements. It is found from the polarization studies that methyl pyrazole (MPA) behaves mainly as anodic inhibitor in HCl. Values of polarization resistance (Rp) and double layer capacitance (Cdl) in the absence and presence of MPA in 1.0 M HCl are determined. The adsorption of MPA on iron surface from HCl is found to obey Temkin adsorption isotherm.  相似文献   

19.
The effect of TlNO3 additions in the concentration (c 1) range from 5 × 10?6 to 1 × 10?4 M on the anodic dissolution of gold in sodium thiosulfate solutions with the concentration (c 2) from 0.005 to 0.2 M is studied by voltammetry on the electrode surface renewed by cutting off a thin metal layer immediately in solution and also by the quartz-crystal microbalance method. For c 2 = 0.2 M, as c 1 increases from 5 × 10?6 to 1 × 10?4 M, the gold anodic dissolution rate is observed to increase from 0.02 (in the absence of TlNO3) to 0.75 mA/cm2 for c 1 = 7.5 × 10?5 M according to a nearly linear law. The dissolution accelerates because the effective values of the transfer coefficient and the exchange current density increase from 0.2 and 4 ??A/cm2 (in the absence of TlNO3 admixtures) to 0.47 and 35 ??A/cm2 (for c 1 = 1 × 10?4), respectively. Experiments with the renewal of the electrode surface in the course of electrolysis suggest that the gold dissolution is catalyzed in the presence of thallium ions by the adsorption mechanism and also as the result of the mixed kinetics of their adsorption on the electrode surface.  相似文献   

20.
The electrochemical behaviours of a brass alloy in 0.1 M nitric acid, including the hyamine inhibitor with concentrations between 2.5 × 10?4 M and 1.0 × 10?5 M, were studied. For this purpose, potentiodynamic polarisation, electrochemical impedance spectroscopy (EIS), linear polarisation resistance (LPR) techniques, and flame atomic absorption spectroscopy (FAAS) were utilised. The inhibitor molecules adsorbed on the brass surface were calculated to be in good agreement with the Langmuir adsorption isotherm and the standard free enthalpy of adsorption (??G ads ° ). Hyamine effectively improved the corrosion inhibition of brass and acted as a mixed-type inhibitor on alloy surfaces. The surface morphology of the alloy was also clarified by optical microscopic and SEM techniques. A theoretical study of the corrosion inhibition efficiency of hyamine molecule was carried out using density functional theory (DFT) at the B3LYP/6-311G(d,p) basis set level.  相似文献   

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