Inhibition of copper dissolution in water solutions of triazoles

The influence of the chemical structure of certain triazoles on the inhibition of copper dissolution in water solutions at pH 7.40 is studied by electrochemical and ellispometric means. It is established that adsorption of the studied triazoles on copper at potential E = 0.0 V relative to a normal hydrogen electrode is polymolecular, the first layer is described by the Frumkin equation with values of the free adsorption of energy values (?ΔG _a ⁰ ) = 50.5–70.1 kJ/mol. In addition, possible orientations of triazole molecules with respect to a surface of oxidized copper are revealed.     

Corrosion of Copper in Presence of Acetic Acid Derivatives

The anodic corrosion of copper in presence of acetic acid derivatives were determined by measuring the limiting current. It is found that the rate of corrosion increased by decreasing H₃PO₄ concentration and electrode height. The experimental results showed that the inhibition efficiency increased with increasing concentration of the investigated compounds at a fixed temperature, but decreases with increasing temperature. Values of activation energy indicate that the reaction is diffusion controlled. The isotherm Langmuir, Temkin, and Flory Huggins are applied. The values of free energy of adsorption (ΔG_ads) obtained indicate the spontaneous adsorption of the inhibitor. The overall mass transfer correlations under the present conditions have been obtained using dimensional analysis method. The results agreed with the previous studies of mass transfer to rotating cylinder in turbulent flow.At the end of the corrosion process the morphology of the specimens after experiment is monitored using scanning electron microscope (SEM). SEM examination of the copper surface revealed that these compounds inhibited copper from corrosion by adsorption on its surface to form protective film. The presence of these organic compounds adsorbed on the electrode surface was confirmed by SEM investigations.     

Study of electropolishing inhibition of steel using natural products as a green inhibitor in ortho-phosphoric acid

ABSTRACT

Anodic inhibition of steel in 8?mol?L^?1 H₃PO₄ was investigated in the absence and presence of different concentrations of extracts of Lawsonia inermis. An experimental measurement, including galvanostatic polarization studies, was done. The anodic corrosion rate and the inhibition efficiencies of the extract were calculated. The results obtained show that the inhibition was found to increase with increasing concentration of Lawsonia inermis extract. The inhibition actions of extracts are discussed on the basis of adsorption of Lawsonia inermis at the steel surface. Theoretical fitting of different isotherms were tested to clarify the nature of adsorption. Polarization curves revealed that Lawsonia inermis inhibitor acts as a corrosion inhibitor. The activation energy (E_a) as well as other thermodynamic parameters (ΔH*, ΔS*, ΔG*) for the inhibition process were calculated. These thermodynamic parameters show strong interaction between the inhibitor and the steel surface. The scanning electron microscope analysis study confirmed the adsorption of inhibitor molecules on the steel surface. The social organization and morphology of the extract were characterized by Fourier transform infrared spectroscopy.     

Inhibition Effect of N-(Pyridin-2-yl-Carbamothioyl) Benzamide on the Corrosion of C-Steel in Sulfuric Acid Solutions

N-(Pyridin-2-yl-carbamothioyl)benzamide (PCMB) was newly synthesized and tested as a corrosion inhibitor for C-steel in 0.5 M H₂SO₄ using chemical and electrochemical techniques. Polarization measurements showed that the synthesized compound acted as a mixed inhibitor. The inhibition efficiencies obtained from the different methods were in good agreement. The inhibitive action of this compound is discussed in terms of blocking the electrode surface by adsorption of the inhibitor according to the Langmuir isotherm. The effect of temperature on the corrosion behavior in the absence and presence of 2.5 × 10^?5 M of PCMB was studied (283–308 K). The associated activation energies (E _a) and the thermodynamic parameters (ΔH*, ΔS*, K _ads, ΔG°_ads) for the adsorption process were determined. The ΔG°_ads value is ?36.55 kJ/mol, which indicated that the adsorption mechanism of PCMB on C-steel in 0.5 M H₂SO₄ solution was combined between physisorption and chemisorption processes.     

Substituted benzotriazoles as inhibitors of copper corrosion in borate buffer solutions

The adsorption of substituted 1,2,3-benzotriazoles (R-BTAs) onto copper is measured via ellipsometry in a pure borate buffer (pH 7.4) and satisfactorily described by Temkin’s isotherm. The adsorption free energy (?ΔG _a ⁰ ) values of these azoles are determined. The (?ΔG _a ⁰ ) values are found to rise as their hydrophobicity, characterized by the logarithm of the partition coefficient of a substituted BTA in a model octanol–water system (logP), grows. The minimum concentration sufficient for the spontaneous passivation of copper (C _min) and a shift in the potential of local copper depassivation with chlorides (E _pt) after an azole is added to the solution (i.e., ΔE = E _pt ⁱⁿ ? E _pt ^backgr characterizing the ability of its adsorption to stabilize passivation) are determined in the same solution containing a corrosion additive (0.01М NaCl) for each azole under study. Both criteria of the passivating properties of azoles (logC _min and ΔE) are shown to correlate linearly with logP, testifying to the role played by surface activity of this family of organic inhibitors in protecting copper in an aqueous solution.     

Anticorrosive property of Spiraea Cantoniensisis extract as an eco-friendly inhibitor on mild steel surface in acid medium

Abstract

The inhibitive performance of methanolic extract of eco-friendly green inhibitor Spiraea cantoniensis (S. cantoniensis) on inhibiting corrosion of mild steel (MS) in 1?M HCl was studied by weight loss, AC-impedance, Fourier transform infrared spectroscopy (FT-IR), Raman, x-ray diffraction (XRD), ultraviolet-visible (UV-Vis), atomic absorption spectroscopy (AAS), and scanning electron microscopy (SEM) analysis. The results showed that the corrosion rate significantly decreased in the presence of the S. cantoniensis inhibitor with a gradual increase in inhibition efficiency at an increased inhibitor concentration. The temperature studies were conducted which included activation energy (E_a), change in enthalpy (ΔH°_ads), change in entropy (ΔS°_ads), change in free energy (ΔG°_ads) and heat of adsorption (Q_ads). These calculations were helpful to determine the reaction mechanism and proved it as a physisorption type following the Langmuir adsorption isotherm. The analysis of the protective film using FT-IR, Raman, XRD, and SEM analysis clearly showed the potentiality of S. cantoniensis in blocking the MS surface to prevent corrosion by 1?M HCl. The solution analysis via AAS and UV-Vis showed the inhibitive effect of the inhibitor (S. cantoniensis) in both inhibitive and the uninhibitive solution exhibiting the adsorption of the phytochemical molecules on the MS surface.     

Experimental and theoretical studies of acridine orange as corrosion inhibitor for copper protection in acidic media

The corrosion process commonly limits the use of copper in practical applications. The use of corrosion inhibitors is one of the effective methods to reduce the corrosion rate of copper. In this research, the inhibition effect of acridine orange (3,6-bis(dimethylamine)acridine) (AcO) for the protection of copper in 0.5 ?M ?H₂SO₄ solution was studied. For this aim, the change of open circuit potential with exposure time (E_ocp-t), electrochemical impedance spectroscopy (EIS), linear polarization resistance (LPR), anodic and cathodic potentiodynamic polarization measurements (PP) and chronoamperometry (CA) techniques were used. Some quantum chemical parameters (E_HOMO, E_LUMO and dipole moment) were calculated and discussed. The AcO film formed over the copper surface was examined by SEM, EDX, AFM and contact angle measurements. The electrochemical data showed that AcO is an effective corrosion inhibitor even at low concentrations (ranging between 99.1% and %99.4 ?at concentrations from 0.01 ?mM to 1 ?mM). The corrosion rate of copper decreases in the presence of the inhibitor by reducing both anodic and cathodic rates, which is depended on its concentration. This compound behaves as mixed-type corrosion inhibitors with predominantly cathodic type. Its adsorption on the copper surface obeys Langmuir adsorption isotherm. The value of adsorption equilibrium constant (K_ads) and the standard free energy of adsorption were ΔG_ads 1.298 x 10³ ?M^?1 and -27.71 ?kJ/mol in the case of 0.5 ?M ?H₂SO₄ solution containing 1.0 ?mM AcO, which shows the adsorption is high and spontaneous. The adsorbed inhibitor film over the metal increase contact angle of the surface, which suggests the more hydrophobic properties of the surface are increasing coming from the orientation of hydrophobic sites to the electrolyte. The zero charge potential (E_pzc) studies showed that the surface charge of the metal is positive in the corrosive media containing the inhibitor. Quantum chemical calculations showed that the binding of inhibitor molecules to the metal surface takes place through N atoms of the inhibitor.     

Equilibrium and kinetics studies on adsorption of Cu(II) from aqueous solutions onto a graft copolymer of cross-linked starch/acrylonitrile (CLSAGCP)

A synthetic graft copolymer of cross-linked starch/acrylonitrile was used as an adsorbent for the removal of Cu(II) ions from an aqueous solution of copper nitrate hexahydrate Cu(NO₃)₂ · 6H₂O at different temperatures and fixed pH. The amount adsorbed increased with increasing concentration of Cu(II) ions and decreasing temperature. The length of time taken to reach equilibrium of the adsorption of Cu(II) ions was the same at all temperatures tested. Kinetics studies showed that the adsorption process obeyed first-order reversible kinetics and the adsorption isotherms followed the Freundlich model. Furthermore, the thermodynamic parameters, i.e. standard free energy (ΔG^∘), standard enthalpy (ΔH^∘), and standard entropy (ΔS^∘), of the adsorption process were calculated and the results are discussed in detail.     

Adsorption of hydrogen on reduced copper chromite

Temperature programmed desorption and volumetric methods in static conditions were used to study hydrogen adsorption on the surface of metallic copper particles produced by the partial reduction of copper chromite CuCr₂O₄ with hydrogen. In the temperature range 300-573 K and in the range of medium surface coverages by hydrogen, the main state of adsorbed hydrogen reveals the heat of adsorption q= 78 kJ/mol and activation energy of adsorption E _a = 69 kJ/mol. In the temperature range 77-300 K, an adsorption state with lower heat and activation energy was found, indicating a non-uniformity of the copper surface within ca. 8% of the total number of surface sites. This revised version was published online in June 2006 with corrections to the Cover Date.     

Factors influencing the mechanism of surfactant catalyzed reaction of vitamin C-ferric chloride hexahydrate system

The kinetics of vitamin C by ferric chloride hexahydrate has been investigated in the aqueous ethanol solution of basic surfactant viz. octadecylamine (ODA) under pseudo-first order conditions. The critical micelle concentration (CMC) of surfactant was determined by surface tension measurement. The effect of pH (2.5–4.5) and temperature (15–35°C) in the presence and absence of surfactant were investigated. Activation parameters, ΔE _a, ΔH ^#, ΔS ^#, ΔG ^≠, for the reaction were calculated by using Arrhenius and Eyring plot. Surface excess concentration (Γ_max), minimum area per surfactant molecule (A _min), average area occupied by each molecule of surfactant (a), surface pressure at the CMC (Π_max), Gibb’s energy of micellization (ΔG _M°), Gibb’s energy of adsorption (ΔG _ad°), were calculated. It was found that the reaction in the presence of surfactant showed faster oxidation rate than the aqueous ethanol solution. Reaction mechanism has been deduced in the presence and absence of surfactant.     

Physicochemical Properties and Surface Tension Prediction of Mixed Surfactant Systems: Triton X‐100 with Dodecylpyridinium Bromide and Triton X‐100 with Sodium Dodecylsulfonate

Dependences of the surface tension of aqueous solutions of ionic (dodecylpyridinium bromide, sodium dodecylsulfonate) and nonionic (Triton X‐100) surfactants and their mixtures on total surfactant concentration and solution composition were studied, and the surface tension of the mixed systems were predicted using different Miller's model. It was found that how to select the model for calculation of ω is corresponding to the degree of the deviation from the ideality during the adsorption of mixed surfactants. The compositions of micelles and adsorption layers at air‐solution interface as well as parameters (β^m, β^ads) of headgroup‐headgroup interaction between the molecules of ionic and nonionic surfactants were calculated based on Rubingh model. The parameters (B₁) of chain‐chain interaction between the molecules of ionic and nonionic surfactants were calculated based on Maeda model. The free energy of micellization calculated from the phase separation model (ΔG ₂ ^m ), and by Maeda's method (ΔG ₁ ^m ) agree reasonably well at high content of nonionic surfactant. The excess free energy ΔG _ads ^E and ΔG _m ^E (except α=0.4) for TX‐100/SDSn system are more negative than that TX‐100/DDPB system. These can be probably explained with the EO groups of TX‐100 surfactant carrying partial positive charge.     

Synthesis and Properties of Novel Cationic Triazolium Gemini Surfactants

New type of triazolium Gemini surfactants were synthesized by reaction of epichlorohydrine with long-chain fatty alcohols namely cetyl alcohol and oleyl alcohol furnishing product 2-(alkoxymethyl)oxirane followed by the their subsequent treatment with triazole resulting in the formation of 1-(1,2,4-triazole)-3-alokoxypropane-2-ol which on reaction with 1,6-dibromohexane resulted in the formation of triazolium-based cationic Gemini surfactant. Their formation was confirmed by IR spectroscopy. Surface tension values were used to determine the critical micelle concentration (CMC), minimum area per molecule (A_min) at air?water interface, Gibbs free energy of adsorption (ΔG_ads), the maximum surface excess concentration (Γ_max), and other parameters. The inhibition behavior of dimeric surfactant on the corrosion of carbon steel (CS) in 1 N H₂SO₄ aqueous medium was studied at 30°C. Performance tests like dispersion capability, foaming power and stability, emulsifying power, and wetting ability were determined. The obtained results show that dispersion capability, foaming power, foaming stability, and emulsifying ability are very good. The wetting power of synthesized surfactants is quite better.     

Effect of metal nature on energy of specific adsorption of chloride ions from dimethyl formamide solutions

The specific adsorption of chloride ions on the renewable liquid (Cd–Ga) electrode from mixed [0.1_m М LiCl + 0.1(1–_m) М LiBF₄] solutions in dimethyl formamide (DMF) is studied with an ac bridge at the following fractions of surface-active anion m: 0, 0.01, 0.02, 0.05, 0.1, 0.2, 0.5 and 1. It is found that the data on the specific adsorption of Cl^– anion in the system can be quantitatively described by Frumkin’s isotherm. The free adsorption energy of Cl^– (ΔG _ads) is a quadratic function of electrode charge. The results are compared with the corresponding data for the Ga/DMF and (In–Ga)/DMF interfaces. It is shown that the adsorption energy of Cl–anions at the metal/DMF interface depends on the metal nature and increases in the series (In–Ga) ≈ (Cd–Ga) < Ga. The energy of metal–DMF chemisorption interaction, which hampers ion adsorption, increases in the same series. The analysis of the data uniquely indicates that the free energy of metal–Cl^– interaction (ΔG _M-CL-) increases in the series (In–Ga) ≈ (Cd–Ga) < Ga. Thus, in the series of electrodes studied, the variations in the energies of metal–Cl^– and metal–DMF specific interaction are correlated: the higher the energy of metal–DMF chemisorption interaction, the higher the energy of metal interaction with Cl^–.     

The influence of aniline and its derivatives on the corrosion behaviour of copper in acid solution

The inhibiting action of aniline and its derivatives on the corrosion of copper in hydrochloric acid has been investigated, with emphasis on the role of substituents. With this purpose five different anilines were selected: aniline, p-chloro aniline, p-nitro aniline, p-methoxy and p-methyl aniline. The electrochemical and gravimetric results, obtained in the absence and presence of different concentrations of inhibitors, revealed that aniline reduces the corrosion of copper, with a critical concentration of 10^–2 M. Furthermore, the interaction energy calculated as G_ads gave a value of 4.2 kcal mol^–1 indicating physisorption of the organic compound at the copper surface. The results have also shown that substituents, either electron donors (–CH₃, –OCH₃) or, electron acceptors (–NO₂, –Cl) in para position, decrease the inhibition action of aniline. A theoretical study using molecular mechanic and ab initio Hartree Fock methods, to model the adsorption of aniline on copper (100) showed results in good agreement with the experimental data. Aniline adsorbs parallel to the copper surface, showing no preference for a specific adsorption site. On the other hand, from ab initio Hartree Fock calculations, an adsorption energy between 2 kcal/mol and 5 kcal/mol is obtained, which is close to the experimental value, confirming that the adsorption of aniline on the metal substrate is rather weak. In view of these results, the orientation of the aniline molecule with respect to the copper surface is considered to be the dominant effect.     

嘧啶衍生物对钢在盐酸溶液中的缓蚀作用

采用失重法、动电位极化曲线、电化学阻抗谱(EIS)、量子化学计算研究了两种嘧啶衍生物(2-羟基嘧啶(HP)和2-巯基嘧啶(MP))在1.0-5.0 mol·L^-1 HCl溶液中对冷轧钢(CRS)的缓蚀作用. 结果表明: HP和MP在1.0 mol·L^-1 HCl溶液中对冷轧钢具有良好的缓蚀作用, 且在钢表面的吸附符合Langmuir吸附等温式. 缓蚀率随缓蚀剂浓度的增加而增大, 但随盐酸浓度的增加而减小.求出了相应的吸附热力学参数(吸附平衡常数(K),吸附自由能(ΔG⁰))和腐蚀动力学参数(表观活化能(E_a)、指前因子(A)、腐蚀速率常数(k)、动力学常数(B)), 并根据这些参数讨论了缓蚀作用机理. 动电位极化曲线表明, MP和HP均为混合抑制型缓蚀剂; EIS谱呈单一容抗弧,电荷转移电阻随缓蚀剂浓度的增加而增大. 两种嘧啶化合物的缓蚀率排序为MP>HP. 量子化学计算结果表明,MP比HP更具吸附活性,缓蚀性能的理论计算和实验结果相一致.     

Thermodynamics and kinetics of adsorption of Cu(II) from aqueous solutions onto a new cation exchanger derived from tamarind fruit shell

A novel cation exchanger (TFS-CE) having carboxylate functionality was prepared through graft copolymerization of hydroxyethylmethacrylate onto tamarind fruit shell (TFS) in the presence of N,N′-methylenebisacrylamide as a cross-linking agent using K₂S₂O₈/Na₂S₂O₃ initiator system, followed by functionalisation. The TFS-CE was used for the removal of Cu(II) from aqueous solutions. At fixed solid/solution ratio the various factors affecting adsorption such as pH, initial concentration, contact time, and temperature were investigated. Kinetic experiments showed that the amount of Cu(II) adsorbed increased with increase in Cu(II) concentration and equilibrium was attained at 1 h. The kinetics of adsorption follows pseudo-second-order model and the rate constant increases with increase in temperature indicating endothermic nature of adsorption. The Arrhenius and Eyring equations were used to obtain the kinetic parameters such as activation energy (E_a) and enthalpy (ΔH^#), entropy (ΔS^#) and free energy (ΔG^#) of activation for the adsorption process. The value of E_a for adsorption was found to be 10.84 kJ · mol^?1 and the adsorption involves diffusion controlled process. The equilibrium data were well fitted to the Langmuir isotherm. The maximum adsorption capacity for Cu(II) was 64 · 10 mg · g^?1 at T = 303 K. The thermodynamic parameters such as changes in free energy (ΔG^°), enthalpy (ΔH^°), and entropy (ΔS^°) were derived to predict the nature of adsorption process. The isosteric heat of adsorption increases with increase in surface loading indicating some lateral interactions between the adsorbed metal ions.     

Phytochemical compounds and anti-corrosion activity of Veronica rosea

The aim of this work is the phytochemical study of the butanolic extract of the aerial parts of Veronica rosea. Four compounds 1–4 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.     

Adsorption of acid red 114 and reactive black 5 in aqueous solutions on dendrimer‐conjugated magnetic nanoparticles

The adsorption of the dyes Acid Red 114 and Reactive Black 5 in aqueous solutions on polyhydroxyl dendrimer magnetic nanoparticles (Fe₃O₄@SiO₂‐TRIS) was studied in a batch system. The Fe₃O₄@SiO₂‐TRIS NPs were characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, and transmission electron microscopy. Experiments were performed under different conditions such as the initial dye concentration, adsorbent dose, and pH. The pseudo‐second‐order model provided a very good fit for the two anionic dyes. The Langmuir and Freundlich adsorption models were used to describe the equilibrium isotherms at different temperatures, and the former agreed very well with the experimental data. However, the adsorption capacity of Fe₃O₄@SiO₂‐TRIS NPs was reduced during surface modification, which could be due to the dye occupying the binding sites of the dendrimer. Thermodynamic parameters, namely the change in free energy (ΔG⁰), enthalpy (ΔH⁰), and entropy (ΔS⁰), were also determined.     

Removal of Thiram from Aqueous Solutions

In this study activated carbon was used for the removal of thiram from aqueous solutions. Adsorption experiments were carried out as a function of time, initial thiram concentration and temperature. Equilibrium data fitted well to the Freundlich and Langmuir equilibrium models in the studied concentration range. Adsorption kinetics followed a pseudo second‐order kinetic model rather than pseudo first‐order model. The results from kinetic experiments were used to describe the adsorption mechanism. Both boundary layer and intraparticle diffusion played important role in the adsorption mechanism of thiram. Thermodynamic parameters (ΔG₀, ΔH₀, and ΔS₀) were determined and the adsorption process was found to be an endothermic one. The negative values of ΔG⁰ at different temperatures were indicative of the spontaneity of the adsorption process.     

CETYLPYRIDINIUM CHLORIDE + TETRADECYLTRIMETHYLAMMONIUM BROMIDE MIXED MICELLES IN POLYETHYLENE GLYCOL 1000 + WATER MIXTURES*

The conductances of cetylpyridinium chloride (CPyCl) + tetradecyltrimethylammonium bromide (TTAB) mixtures over the entire mole fraction range of CPyCl (x_CPyCl) were measured in aqueous binary mixtures of polyethylene glycol 1000 (PEG 1000) containing 0.5, 1, 2, 5 and 10 wt% of PEG 1000 at 30°C. From the conductivity data, the critical micellar concentration (cmc), degree of counter ion association (χ) and the standard free energy of micelle formation (ΔG^o _M ) of CPyCl and TTAB were computed. The DG^o _M value is further divided into the hydrophobic contribution of free energy of transfer of the surfactant hydrocarbon chain from the medium to the micelle (ΔG^o _HP ), and the energy associated with the surface contributions (ΔG^o _s ) consisting of electrostatic interactions between the head groups and counter ions. Both contributions show a linear dependence on the amount of PEG additive. These results have been explained on the basis of the medium effects of aqueous PEG.

The mixed micelle formation by CPyCl+TTAB show non-ideal behavior which is quite similar in the absence, as well as in the presence, of PEG additive as evaluated by using the regular solution theory. The interaction parameter, b, is always negative and remains almost constant with respect to the amount of PEG additive. This indicates that the mixed micelle formation occurs mainly due to the synergistic interactions between the unlike surfactant monomers only.