Investigations of the inhibition of copper corrosion in nitric acid solutions by ketene dithioacetal derivatives

Ketene dithioacetal derivatives, namely 3-[bis(methylthio)methylene] pentane-2,4-dione (1), 3-(1,3-dithian-2-ylidene) pentane-2,4-dione (2) and 3-(1,3-dithiolan-2-ylidene) pentane-2,4-dione (3) were synthesized and their respective capacity to inhibit copper corrosion in 3 M HNO₃ was investigated by means of weight loss, potentiodynamic polarization, scanning electron microscopy (SEM) and energy dispersive X-ray fluorescence (XRF). The obtained results indicate that the addition of these compounds significantly decreases the corrosion rate. Potentiodynamic polarization studies clearly showed that the inhibition efficiency increases with increasing concentration of the investigated compounds at a fixed temperature, but decreases with increasing temperature. These results on the whole showed that the studied substances are good cathodic inhibitors for copper corrosion in nitric acid medium. SEM and energy dispersive X-ray (EDAX) examination of the copper surface revealed that these compounds prevented copper from corrosion by adsorption on its surface to form a protective film, which acts as a barrier to aggressive agents. The presence of these organic compounds adsorbed on the electrode surface was confirmed by XRF investigations.     

Electrochemical and theoretical investigation on the corrosion of aluminium in acidic solution containing some Schiff bases

The effect of newly synthesised three Schiff bases—2-[2-aza-2-(5-methyl(2-pyridly))vinyl]phenol, 2-[2-aza-2-(5-methyl(2-pyridly))vinyl]-4-bromophenol, 2-[2-aza-2-(5-methyl(2-pyridly))vinyl]-4-chlorophenol—on the corrosion behaviour of aluminium in 0.1 M HCl were investigated using potentiodynamic polarisation, electrochemical impedance spectroscopy and linear polarisation methods. Polarisation curves indicate that all studied Schiff bases were acting as mixed type inhibitors. All measurements show that inhibition efficiencies increase with increase in inhibitor concentration. This reveals that inhibitive actions of inhibitors were mainly due to adsorption on aluminium surface. Adsorption of these inhibitors follows Langmuir adsorption isotherm. Thermodynamic parameters of adsorption (K_ads, ΔG_ads) of studied Schiff bases were calculated using Langmuir adsorption isotherm. The variation in inhibition efficiency values depends on the type of functional groups substituted on benzene ring. It was found that the presence of bromine and chlorine atoms in the molecular structure of studied Schiff bases facilitate the adsorption of molecule on aluminium surface.The correlation between the inhibition efficiencies of studied Schiff bases and their molecular structure has been investigated using quantum chemical parameters obtained by MNDO semi-empirical SCF-MO methods. These results indicate that adsorption of studied Schiff bases depends on the charge density of adsorption centres and dipole moments.     

Potentiodynamic studies on corrosion of copper by chloride ions and its inhibition by inorganic and organic ions in aqueous buffer solution

Electrochemical oxidation of copper in aqueous phosphate buffer solution leads to the formation of passive films, which breakdown in the presence of aggressive chloride (Cl^?) ions. The addition of Cl^? ions in the medium causes shift in current and potential for both cathodic and anodic peaks. At low Cl^? ion concentrations, the corrosion current is greatly enhanced and continues to increase up to a certain concentration, after which it decreases. The effect of inorganic ions, chromate (CrO ₄ ^2? ) and tungstate (WO ₄ ^2? ), and organic ions, acetate (CH₃COO^?) and oxalate (C₂O ₄ ^2? ), on the formation and breakdown of passive films in aqueous buffer solution containing 0.10 M Cl^? ions have also been investigated. All of the ions inhibit corrosion of copper in the presence of aggressive Cl^? ions following the order of overall inhibition efficiency of CrO ₄ ^2? > C₂O ₄ ^2? > WO ₄ ^2? > CH₃COO^? under the experimental conditions.     

Systematic theoretical investigation of structure and electronic properties of pure copper and lithium doped copper clusters

The pure copper and lithium-doped copper clusters are studied using the unbiased CALYPSO structure searching method and density function theory to understand the evolution of various structure and electronic properties. Theoretical results show the growth behaviours of doped clusters are organised as follows: Li capped Cu_n clusters or Li substituted Cu_n+1 clusters as well as Cu capped Cu_n-1Li clusters. Moreover, the lowest energy structures of Cu_nLi favour planar structures for n ≤ 3 and three-dimensional structures for n = 4–12. In addition, the calculated averaged binding energies, fragmentation energies and second-order difference of energies exhibit obvious odd–even alternations as cluster size increasing. At last, the highest occupied-lowest unoccupied molecular orbital gaps, molecular orbital energy, magnetic property, natural population analysis, natural electron configurations, electrostatic potential, electron density difference, Infrared and Raman spectra and density of states are also, respectively, operative for characterising and rationalising the electronic properties of doped clusters.     

An experimental and theoretical investigation of the valence shell photoelectron spectrum of cyanogen chloride

The valence shell photoelectron spectrum of cyanogen chloride has been studied using HeI and synchrotron radiation. In the outer valence region the molecular orbital model of ionization holds, and the main bands can be associated with single-hole states. However, in the inner valence region electron correlation effects become important, and these result in complex satellite structure being observed. Vertical ionization energies and spectral intensities have been computed using the Green's function approach, and the results have facilitated an interpretation of the experimental spectra. Photoelectron angular distributions and branching ratios have been measured and have been used to assess the bonding characteristics of the outer valence molecular orbitals. The experimental data for the 8σ orbital display an energy dependence which suggests that photoionization from this orbital may be influenced by the chlorine 3p Cooper minimum. The extent to which the 8σ orbital can be considered as a chlorine atom lone-pair is discussed. Vibrational structure has been observed in the [Xtilde] ²Π, Ã ²Σ⁺ and [Btilde] ²Π photoelectron bands recorded with HeI radiation, and has been assigned to progressions involving the ν⁺ ₁ and ν⁺ ₃ modes.     

Experimental and theoretical study for corrosion inhibition of mild steel in hydrochloric acid solution by some new hydrazine carbodithioic acid derivatives

The corrosion inhibition of mild steel in 0.5 M hydrochloric acid solutions by some new hydrazine carbodithioic acid derivatives namely N′-furan-2-yl-methylene-hydrazine carbodithioic acid (A), N′-(4-dimethylamino-benzylidene)-hydrazine carbodithioic acid (B) and N′-(3-nitro-benzylidene)-hydrazine carbodithioic (C) was studied using chemical (weight loss) and electrochemical (potentiodynamic and electrochemical impedance spectroscopy, EIS) measurements. These measurements show that the inhibition efficiency obtained by these compounds increased by increasing their concentration. The inhibition efficiency follow the order C > B > A. Polarization studies show that these compounds act as mixed type inhibitors in 0.5 M HCl solutions. These inhibitors function through adsorption following Langmuir isotherm. The electronic properties of these inhibitors, obtained using PM3 semi-empirical self-consistence field method, have been correlated with their experimental efficiencies using non-linear regression method.     

An electrochemical study for corrosion inhibition of iron by some organic phosphonium chloride derivatives in acid media

The inhibiting action of (chloromethyl) triphenyl phosphonium chloride (CTP), tetraphenyl phosphonum chloride (TP), triphenyl phosphine oxide (TPO), triphenyl (phenylmethyl) phosphonium chloride (TPM) and triphenyl phosphine (TPP) on the corrosion of iron in 1 M HCl solution was studied using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). Experimental results revealed that CTP, TP, TPO, and TPM act as inhibitors for iron in acid environments, while TPP is an accelerator. These compounds are mixed-type inhibitors and the inhibition efficiency increased with increasing concentrations. Equivalent circuits of the investigated systems are suggested.     

Adsorption and corrosion inhibition characteristics of strawberry fruit extract at steel/acids interfaces: experimental and theoretical approaches

Ionics - The adsorption and corrosion inhibition behavior of strawberry fruit extract at steel/1 M HCl and steel/0.5 M H2SO4 interfaces were investigated using gravimetric and...     

Experimental and theoretical investigation of third-harmonic generation in phase-matched dye solutions

The phase-matched third-harmonic light generation in dye solutions is studied experimentally and theoretically. In the experiments picosecond light pulses of a passive mode-locked Nd-glass laser are converted to the third-harmonic frequency. A third-harmonic conversion efficiency of up to 4×10^–4 was achieved for one of the dyes investigated (1,3,3,1,3,3-hexamethylindocarbocyanine iodide in hexafluoroisopropanol). The theoretical calculations determine the influence of various dye and solvent parameters on the conversion efficiency. The conversion efficiency is found to be limited by excited-state absorption of pump laser light and third-harmonic light from the S₁-state to higher singlet states. The S₁-state is mainly populated by two-photon absorption. Amplified spontaneous emission may reduce the limiting effects of excited-state absorption. Phase changes caused by the non-linear refractive index and the refractive index dispersion within the spectral bandwidth of the laser pulses reduce the conversion efficiency. Under ideal conditions conversion efficiencies up to 10% may be achieved.     

Vibrational investigation of 1-cyclopentylpiperazine: A combined experimental and theoretical study

FT-IR and Raman spectra of 1-cyclopentylpiperazine(1cppp)have been experimentally examined in the region of 4000–200cm-1.The optimized geometric parameters,conformational equilibria,normal mode frequencies and corresponding vibrational assignments of 1cppp(C9H18N2)are theoretically examined by means of B3LYP hybrid density functional theory(DFT)method together with 6-31++G(d,p)basis set.On the basis of potential energy distribution(PED)reliable vibrational assignments have been made and the thermodynamics functions,highest occupied and lowest unoccupied molecular orbitals(HOMO and LUMO)of 1cppp have been predicted.Calculations are employed for four different conformations in C1 and Cs point groups of 1cppp in gas phase.Comparison between the experimental and theoretical results indicates that B3LYP method is able to provide satisfactory results for predicting vibrational frequencies and the structural parameters,vibrational frequencies and assignments.Furthermore,C1(equatorial-axial)point group has been found as the most stable conformer of 1cppp.     

Volumetric, viscometric, acoustical, and optical studies of glutamic acid in aqueous zinc and copper chloride solutions

Ultrasonic velocity, density, viscosity and refractive index measurements of L-glutamic acid in aqueous zinc chloride and copper chloride solutions have been carried out at 303.15K. From these experimental data isentropic compressibility, acoustic impendence, relative association, free path length, apparent molar volume, apparent molar isentropic compressibility and molar refraction of L-glutamic acid in aqueous solutions of electrolytes are evaluated. These values have been used to explain molecular association, solutesolvent interaction through hydrogen bonding and solvation. Viscosity data have been analyzed in the light of Jones-Dole equation and the constants A and B have been estimated and interpreted in terms of ion-ion, ionsolvent and molecular interactions occurring in solutions.     

Mechanical properties of carbon nanotubes: theoretical predictions and experimental measurements

Mechanical properties of carbon nanotubes are discussed based on recent advances in both modeling and experiment. To cite this article: R.S. Ruoff et al., C. R. Physique 4 (2003).     

Electrochemical study and electrodeposition of copper in the hydrophobic tri-n-octylmethylammonium chloride ionic liquid media

The electrodeposition of metallic Copper in binary mixture ionic liquid/organic solvent (tri-n-octylmethylammonium chloride (TOMAC))/chloroform (CHCl₃) was investigated. The electrochemical behavior of Cu(II) in TOMAC/CHCl₃ at glassy carbon working electrode at room temperature was studied by cyclic voltammetry and spectroscopy impedance. The results from the cyclic voltammetry showed that the electrodeposition of metallic Cu in the binary mixture ionic liquid/organic solvent was an irreversible process and was controlled by the diffusion of Cu(II) on a glassy carbon working electrode. The average value of αn_α was found to be 0.23 at 25 °C and the diffusion coefficient (D₀) of Cu(II) was calculated to be 7.12 10^− 9 cm²/s at room temperature. The performance of TOMAC ionic liquid such as internal resistance has been investigated with electrochemical impedance spectroscopy (EIS). The scanning electron microscopy (SEM) micrographs was used to observe that the copper plating was moderately dense and contains fine crystallites with average sizes of about 1 μm at room temperature. Energy dispersive X-ray analysis (EDAX) profile showed that the obtained film was copper.     

Adhesion measurement of thin films by a modified laser spallation technique: theoretical analysis and experimental investigation

Laser driven shocks can lead to a dynamic failure, called film spallation. Here, we use a modified laser spallation set-up to measure the dynamic adhesion of thin films and we propose a novel diagnostic technology. Based on correlation theory, new spallation criteria for characterizing the progressive damage at the interface between the film and the substrate are established, such as interface delamination, film spallation and film expulsion. With the help of the theory, the degree of damage and the dimension of damage (i.e. fracture), such as the minimum width of delamination radius, the thickness of the film etc., are estimated. Experiments are carried out on epoxy/stainless steel and epoxy/Al, and the experimental results show that their dynamic bonding strengths are about 25 MPa and 20 MPa, respectively. The detailed results, analyses and discussions are presented in this paper. Received: 6 February 2001 / Accepted: 3 December 2001 / Published online: 11 February 2002     

Field emission properties of capped carbon nanotubes doped by alkali metals:a theoretical investigation

The electronic structures and field emission properties of capped CNT55 systems with or without alkali metal atom adsorption were systematically investigated by density functional theory calculation.The results indicate that the adsorption of alkali metal on the center site of a CNT tip is energetically favorable.In addition,the adsorption energies increase with the introduction of the electric field.The excessive negative charges on CNT tips make electron emittance much easier and result in a decrease in work function.Furthermore,the inducing effect by positively charged alkali metal atoms can be reasonably considered as the dominant reason for the improvement in field emission properties.     

Caffeine as non-toxic corrosion inhibitor for copper in aqueous solutions of potassium nitrate

Different electrochemical methods were employed in order to confirm the ability of caffeine (1,3,7-trimethylxanthine) to inhibit the corrosion processes of copper in aqueous potassium nitrate solutions in the absence and in the presence of chloride. Some experiments were repeated in potassium perchlorate in order to compare the influence of the medium. The interaction between the organic compound and the electrode surface occurs independently of the electrode potential. However, maximum interaction was observed at 0.0 V (Ag/AgCl) in aerated solutions, and at −0.25 V (Ag/AgCl) in deaerated solutions.The presence of the organic compound adsorbed on the electrode surface was confirmed by comparing the voltammograms of copper electrode in the absence and presence of 1.5 mmol L⁻¹ of dissolved caffeine. The same results were observed by comparing polarization curves in the absence and in the presence of caffeine.Anodic currents decrease noticeably in the presence of the organic compound. Chronoamperometric experiments were conclusive to prove the inhibitor capability of caffeine to decrease the corrosion dissolution processes of copper under anodic polarization.     

Enhanced corrosion resistance of mild steel in normal sulfuric acid medium by 2,5-bis(n-thienyl)-1,3,4-thiadiazoles: Electrochemical, X-ray photoelectron spectroscopy and theoretical studies

The inhibitive action of some thiadiazole derivatives, namely 2,5-bis(2-thienyl)-1,3,4-thiadiazole (2-TTH) and 2,5-bis(3-thienyl)-1,3,4-thiadiazole (3-TTH) against the corrosion of mild steel in 0.5 M H₂SO₄ solution has been investigated using weight loss measurements, Tafel polarisation and electrochemical impedance spectroscopy (EIS) techniques. The experimental results obtained revealed that these compounds inhibited the steel corrosion in acid solution. The protection efficiency increased with increasing inhibitors concentration and the ability of the molecule to adsorb on the steel surface was dependent on the position of the sulphur atom on the thienyl substituent. Inhibition efficiency values obtained from various methods employed were in reasonable agreement. Potentiodynamic polarisation studies clearly showed that 2-TTH and 3-TTH acted as mixed inhibitors. Adsorption of these inhibitors on steel surface obeyed to Langmuir adsorption isotherm. X-ray photoelectron spectroscopy and the thermodynamic data of adsorption showed that inhibition of steel corrosion in normal sulphuric solution by n-TTH is due to the formation of a chemisorbed film on the steel surface. Molecular modelling was used to gain some insight, about structural and electronic effects in relation to the inhibiting efficiencies.