The Reaction of Ozone with Bisulfide (HS−) in Aqueous Solution – Mechanistic Aspects

The ozone demand to oxidize HS^?/H₂S [pK_a(H₂S) = 6.9, k(HS^? + O₃) = 3 × 10⁹ M^?1 s^?1, k(H₂S + O₃) = 3 × 10⁴ M^?1 s^?1] to SO₄ ^2? is only 2.4 mol ozone per mol SO₄ ^2? formed, much lower than stoichiometric 4.0 mol/mol if a series of O-transfer reactions would occur. As primary step, the formation of an ozone adduct to HS^?, HSOOO^–, is suggested that decomposes into HSO^– and singlet oxygen (16%) or rearranges into peroxysulfinate ion, HS(O)OO^– (84%). Potential reactions of the above intermediates are discussed. Some of these can account for the low ozone demand.     

Redox chemistry of H2S oxidation by the British Gas Stretford Process Part. II: Electrochemical behaviour of aqueous hydrosulphide (HS−) solutions

Electrochemical techniques were used to study the oxidation of HS^– ions at pH 9.3. Voltammetry of gold electrodes in HS^– -containing solutions showed that multilayers of sulphur and soluble oxidation products were formed. As a known HS^– oxidation product, thiosulphate solutions were also studied voltammetrically, but found to be electro-inactive at mildly oxidising potentials. The voltammetric behaviour of polysulphide ions, S _n ^2– (n = 2 to 5), was similar to that of HS^– solutions on oxidation, though they could be reduced to HS^– ions at low potentials. Ring-disc electrode experiments, extending the HS^– concentration range that had been studied previously, confirmed that polysulphide ions were produced on reduction of anodically deposited elemental sulphur. This was demonstrated in both cyclic Volammetry and potential step experiments. By comparison of the charges passed producing polysulphides from sulphur and reducing them to HS^– ions, an average polysulphide chain length of 1.8 was calculated, indicating a mixture of species was produced. Ion chromatography confirmed that polysulphide solutions do contain a number of species, consistent with thermodynamic predictions.     

Synthesis and characterization of conducting poly(aniline‐co‐diaminodiphenylsulfone) copolymers

Polyaniline, poly(aniline‐co‐4,4′‐diaminodiphenylsulfone), and poly(4,4′‐diaminodiphenylsulfone) were synthesized by ammonium peroxydisulfate oxidation and characterized by a number of techniques, including infrared spectroscopy, ultraviolet–visible absorption spectroscopy, ¹H‐NMR, thermogravimetric analysis, and differential scanning calorimetry. These copolymers had enhanced solubility in common organic solvents in comparison with polyaniline. The conductivities of the HCl‐doped polymers ranged from 1 S cm^?1 for polyaniline to 10^?8 S cm^?1 for poly(4,4′‐diaminodiphenylsulfone). The copolymer compositions showed that block copolymers of 4,4′‐diaminodiphenylsulfone (r₁ > 1) and aniline (r₂ < 1) formed and that the reactivity of 4,4′‐diaminodiphenylsulfone was greater than that of aniline. The results were explained by the effect of the ? SO₂? group present in the polymer structure. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2337–2347, 2003     

Manipulation of polymer layer characteristics by electrochemical polymerization from mixtures of aniline and ortho‐phenylenediamine monomers

The influence of adding ortho‐phenylenediamine (OPDA) during the polymerization of aniline on the characteristics of the resulting polymer film was examined. When using a platinum electrode, the deposits were obtained from solutions containing 0.1 mol dm^?3 aniline and 1, 5, or 10 mmol dm^?3 OPDA. The deposits were also prepared from solutions containing 0.5 mol dm^?3 aniline and 5, 10, or 50 mmol dm^?3 OPDA. In both cases, 3 mol dm^?3 phosphoric acid solution was used as a supporting electrolyte. The characteristics of the obtained layers were investigated through the catalytic effect of different polymer layers on hydroquinone/quinone (H₂Q/Q) test redox system. The results obtained confirm the earlier established catalytic effect on the potential of the redox reaction by shifting it to more reversible values. However, as the concentration of OPDA was increased, the resulting limiting current decreased, thus indicating in the presence of OPDA a lower population of the available active centers necessary for the catalytic reaction to proceed. The influence of OPDA on polymer characteristics was also studied by using scanning electron microscopy as well as electrochemical impedance spectroscopy. The polymer was synthesized on a stainless steel electrode (13% Cr) from a solution containing 0.5 mol dm^?3 aniline and 5, 10, or 50 mmol dm^?3 OPDA. The layers were tested in chloride‐containing solutions by monitoring the open circuit potential. The results obtained suggest that, by increasing the concentration of OPDA, the time of OCP in the passive region of stainless steel is prolonged. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of self‐doped poly(aniline‐co‐aminonaphthalene sulfonic acid) nanotubes

Self‐doped poly(aniline‐co‐aminonaphthalene sulfonic acid) (PANI‐ANSA) was synthesized by the copolymerization of 5‐aminonaphthalene‐2‐sulfonic acid (ANSA) and aniline. Scanning electron microscopy and transmission electron microscopy showed that the morphology of PANI‐ANSA synthesized at a high molar ratio of aniline to ANSA was nanotubular, but at a low molar ratio, only a granular morphology formed. A possible formation mechanism for nanotubes was proposed. PANI‐ANSA had better thermal stability than HCl‐doped polyaniline; the highest onset decomposition temperature was as high as 340°C because of ? SO₃H linked with the polymer backbone by a covalent bond. PANI‐ANSA was partially soluble in basic solutions, and its conductivity was between 10^?2 and 10^?4 S/cm, depending on the sulfonation degree. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1297–1301, 2003     

Isothermal Reaction Kinetics of Kraft Delignification of Douglas-Fir

Kraft delignification of Douglas-fir (Pseudotsuga menziesii) wood meal was carried out under an instantaneous isothermal condition with a liquor-to-wood ratio of 50 to investigate the effects of reaction temperature and chemical concentration on the rate of delignification. The temperatures studied were in the range of 120 to 175°C. Three levels of [HO^?l] and three levels of [HS^?l] concentrations were investigated. In each case an efficient mechanical agitation of the pulping liquor was maintained and the delignification was extended to reach its completion. Using a nonlinear regression analysis on the delignification results, a single kinetics equation was resolved to describe the effect of temperature and chemical concentration on the rates of delignification for the initial, bulk, and final phases. This equation also revealed that the amounts of lignin removed due to the chemical reactions in the initial, bulk, and final phases were 18.8, 71.4, and 3.8%, respectively. About 6% of the total lignin was dissolved into the pulping solution before any significant chemical reaction occurred to the lignin core. The activation energies of delignification reactions in the initial, bulk, and final phases were 85.8, 123.8, and 110.0 kJ/mole, respectively. The Ln(pre-exponential factors) were 22.5, 30.5, and 23.4 m^?l1 for the initial, bulk, and final phases, respectively. The rate of delignification was strongly affected by the presence of [HO^?l] in the bulk and final phases. Whereas, [HS^?l] had a significant effect on the rate of delignification only in the bulk phase. These chemical effects were also quantified.     

Electrochemistry of polysulphide ions in dimethylacetamide: basic properties and oxidation in acid medium

Basicity and oxidation of S₈^2? and S₃^2? polysulphide ions in dimethylacetamide (DMA), prepared by electrochemical reduction of sulphur, have been studied by voltammetry coupled with visible absorption spectrophotometry. The protonation os S₃^.? radical anion is not observed in DMA. The pK_A value of HS₈^? stands between 7 and 9. pK_A values of HS₃^? and HS₄^? are higher than 13. For each S₈^2?, S₄^2? and S₃^2? ions, protonation and oxidation are simultaneously observed from the same acidity level.     

Free‐standing aniline oligomer functionalized multiwalled carbon nanotube films from a filtration method

High electrochemical active free‐standing multiwalled carbon nanotube (MWNT) films have been synthesized from aniline oligomer functionalized MWNTs (MWNT‐AO), by using filtration of the acidic phosphate ester (APE) doped MWNT‐AO dispersions. The homogeneously distributed MWNTs endowed APE/MWNT films automatically releasing from the filter membrane. The sheet resistivity of MWNT‐AO (850 Ω sq^?1) showed a lower value than that of carboxyl MWNTs (1273 Ω sq^?1), due to the doping effect of MWNT on aniline oligomer, confirmed by the N1s X‐ray photoelectron spectrum. However, it showed a higher sheet resistivity value of 1526 Ω sq^?1 after further doped by APE, because of the presence of unreacted dopant. After removing the residual insulating dopant by the vacuum filtration, the resultant APE/MWNT films showed the sheet resistivity value as low as 131 Ω sq^?1. Thermogravimetric analysis showed that the MWNT loading in the film can be over than 77%, which showed the specific capacitance as high as 249 F g^?1. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40259.     

Influence of H+ and Cl− ions on inhibitive performance of poly(aniline) for iron corrosion in acid

The inhibition effect of poly(aniline) on pure iron corrosion in 1M HCl and with various H⁺ ions and Cl^? ions concentrations was investigated by the polarization and electrochemical impedance spectroscopy methods. The results showed that poly(aniline) suppressed both cathodic and anodic processes of iron dissolution in 1M HCl by its adsorption on the iron surface according to Langmuir's adsorption isotherm. The inhibition efficiency of poly(aniline) was found to increase with the inhibitor concentrations. Further, it was observed that, there was no significant variation in corrosion potential (E_corr) values in the presence of inhibitors suggesting that, this polymer behaved as mixed type inhibitor. Similar studies for the inhibitor at 500 ppm in various concentrations of H⁺ and Cl^? ions, have shown that the inhibition efficiency decreases with decrease in concentrations of H⁺ ions and Cl^? ions in aqueous solution. It reveals that, the adsorption of inhibitor on iron surface is by more cationic form of inhibitor and higher efficiency at higher H⁺ and Cl^? ions is due to enhanced adsorption of cat ionic form of inhibitor molecules. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Compressive and thermal characterization of syntactic foams containing hollow silicon carbide particles with porous shell

Silicon carbide hollow particle (SiC_HS) reinforced vinyl ester matrix syntactic foams are prepared and characterized for compressive properties and coefficient of thermal expansion (CTE). Two types of SiC_HS were utilized in 60 vol % to prepare syntactic foams. These SiC_HS had ratio of inner to outer radius of 0.91 and 0.84 for the thin and thick walled particles. The specific compressive strength values were 33.4 and 38.8 kPa/kg/m³ and the specific compressive modulus values were 0.8 MPa/kg/m³ and 0.6 MPa/kg/m³ for the thin and thick walled SiC_HS‐filled syntactic foams, respectively. The shell of the hollow particles contained microporous voids, and the porosity was estimated as 16.6% and 24.8% in the walls of the thin and thick walled particles, respectively. The shell porosity adversely affected the specific compressive strength and the modulus of the syntactic foam. However, the SiC_HS‐filled syntactic foams exhibited low CTE values (26.7 and 15.9 × 10^?6/°C). These CTE values were 65.1% and 79.3% lower than the CTE of the neat resin. Such properties can be useful for applications where syntactic foams are exposed to high temperatures and dimensional stability is important. A theoretical model is used to estimate the porosity level in the SiC shells and estimate the effective mechanical properties of the porous SiC material that forms the particle shell. Such analysis can help in using the models as predictive tools to estimate the mechanical properties of syntactic foams. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40689.     

Self‐assembled centimetre‐sized rods obtained in the oxidation of o‐phenylenediamine and aniline

Morphologically well‐defined rods of approximately 1 cm in length are effectively and economically obtained by mixing ortho‐phenylenediamine (30 mmol L^?1) with ammonium persulfate (12.5 mmol L^?1) in an acidic solution (0.37 mol L^?1 HCl) at room temperature with and without the presence of 50 mmol L^?1 aniline. These self‐assembled, morphologically uniform products can be potentially scaled up and used as morphological templates to fabricate well‐defined structures of other materials such as conducting polymers. The products were characterized using Raman, UV‐visible, high‐resolution NMR (¹H and ¹³C) and mass spectroscopies, X‐ray diffraction, scanning electron microscopy and elemental analysis. Apart from certain differences in visual appearance and in X‐ray diffractograms, other analytical data suggest that there are no structural changes upon addition of aniline into the reaction mixture. NMR and mass spectra imply that all syntheses carried out either with or without aniline result in a mixture of two products, attributed to 2,3‐phenazinediamine and 3‐aminophenazin‐2‐ol. A formation mechanism based on hydrogen bonding and π–π stacking has been proposed. © 2015 Society of Chemical Industry     

Simple chemical polymerization method for the deposition of a conducting polyaniline on the surface of acrylonitrile–butadiene–styrene. II. Treatment in organic free solvent

We developed a simple method for the deposition of a uniform layer of polyaniline (PANI) on the surface of acrylonitrile–butadiene–styrene (ABS). The method consisted of two steps: the soaking of ABS samples in a water‐based aniline solution stabilized by surfactants followed by the oxidative polymerization of the adsorbed and absorbed monomer. The three types of surfactants (molecular N,N‐dimethyl‐octalamine‐N‐oxide, anionic sodium dodecyl sulfate, and cationic hexadecyl trimethyl ammonium bromide) were used to prepare and stabilize the aniline emulsions in water. After treatment, the ABS surface was completely covered by PANI (as seen with scanning electron microscopy). The surface conductivity after PANI coating reached values between 10^?3 and 10^?4 S/□ in the best developed conditions. The chemical nature of the surfactant affected the particular setting of the aniline/surfactant emulsion preparation (time of ultrasonification = 15–30 min), its optimal concentration (2–10 wt % aniline and 0.1–0.2M surfactant), and other parameters of treatment, such as time (10 s to 20 min) and temperature (20–60°C) of soaking. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1752–1758, 2004     

Redox chemistry of H2S oxidation by the British gas Stretford process part V: Aspects of the process chemistry

Stretford processes use air to oxidize H₂S in process and natural gases to elemental sulphur, by absorption in aqueous solution at about pH 9 and reaction of the resulting HS^– ions with dissolved oxygen, in the presence of anthraquinone disulphonates (AQDS) and vanadium (v) species, which act as catalysts. Kinetic measurements of the reactions (AQ27DS + HS^– ions), (V(v) + HS^– ions) and (AQ27DSH^– + O₂), primarily used stopped flow spectrophotometry, as reported here, following papers on the electrochemical behaviour of the individual redox couples in Stretford Processes. The course of reaction (AQ27DS + HS^– ions) was also followed with a gold bead indicator electrode, the potential of which was determined essentially by the AQ27DS/AQ27DSH^– couple as the former species were reduced to the latter. Attempts to use⁵¹V NMR to characterize aqueous vanadium-sulphur complexes were inconclusive. A possible mechanism for Stretford Processes is postulated, involving polysulphide (S _n ^2–) ions as intermediates, which are oxidized to elemental sulphur by another intermediate, H₂O₂, formed by reaction of AQ27DSH^– ions and dissolved oxygen.     

Preparation of PAA‐g‐PEG/PANI polymer gel electrolyte and its application in quasi solid state dye‐sensitized solar cells

A microporous hybrid polymer of poly(acrylic acid)‐g‐poly(ethylene glycol)/polyaniline (PAA‐g‐PEG/PANI) is synthesized by a two‐step solution polymerization method. The influence of aniline concentration on the conductivity of PAA‐g‐PEG/PANI gel electrolyte is discussed, when the concentration of aniline is 0.66 wt%, the conductivity of PAA‐g‐PEG/PANI gel electrolyte is 11.50 mS cm^?1. Using this gel electrolyte as host, a quasi solid state dye‐sensitized solar cell (QS‐DSSC) is assembled. The QS‐DSSC based on this gel electrolyte achieves a power conversion efficiency of 6.38% under a simulated solar illumination of 100 mW cm^?2 (AM 1.5). POLYM. ENG. SCI., 55:322–326, 2015. © 2014 Society of Plastics Engineers     

Synthesis and characterization of N‐ and O‐alkylated poly[aniline‐co‐N‐(2‐hydroxyethyl) aniline]

Poly[aniline‐co‐N‐(2‐hydroxyethyl) aniline] was synthesized in an aqueous hydrochloric acid medium with a determined feed ratio by chemical oxidative polymerization. This polymer was used as a functional conducting polymer intermediate because of its side‐group reactivity. To synthesize the alkyl‐substituted copolymer, the initial copolymer was reacted with NaH to obtain the N‐ and O‐anionic copolymer after the reaction with octadecyl bromide to prepare the octadecyl‐substituted polymer. The microstructure of the obtained polymers was characterized by Fourier transform infrared spectroscopy, ¹H‐NMR, and X‐ray diffraction. The thermal behavior of the polymers was investigated by thermogravimetric analysis and differential scanning calorimetry. The morphology of obtained copolymers was studied by scanning electron microscopy. The cyclic voltammetry investigation showed the electroactivity of poly [aniline‐co‐N‐(2‐hydroxyethyl) aniline] and N and O‐alkylated poly[aniline‐co‐N‐(2‐hydroxyethyl) aniline]. The conductivities of the polymers were 5 × 10^?5 S/cm for poly[aniline‐co‐N‐(2‐hydroxyethyl) aniline] and 5 ×10^?7 S/cm for the octadecyl‐substituted copolymer. The conductivity measurements were performed with a four‐point probe method. The solubility of the initial copolymer in common organic solvents such as N‐methyl‐2‐pyrrolidone and dimethylformamide was greater than polyaniline. The alkylated copolymer was mainly soluble in nonpolar solvents such as n‐hexane and cyclohexane. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Poly(2‐) and (3‐aminobenzoic acids) and their copolymers with aniline: Synthesis,characterization, and properties

Poly(2‐aminobenzoic acid) and poly(3‐aminobenzoic acid) were synthesized by chemical polymerization of the respective monomers with aqueous 1M hydrochloric acid and 0.49M sodium hydroxide, using ammonium persulfate as an oxidizing agent. In addition, polymerization in an acid medium was carried out in the presence of metal ions, such as Cu(II), Ni(II), and Co(II). Poly(2‐aminobenzoic acid‐co‐aniline) and poly(3‐aminobenzoic acid‐co‐aniline) were synthesized by chemical copolymerization of aniline with 2‐ and 3‐aminobenzoic acids, respectively, in aqueous 1M hydrochloric acid. The copolymers were synthesized at several mole fractions of aniline in the feed and characterized by UV–visible and FTIR spectroscopy, the thermal stability, and the electrical conductivity. Metal ions, such as Cu(II), Ni(II), and Co(II), were incorporated into homo‐ and copolymers by the batch method. The percentage of metal ions in the polymers was higher in the copolymers than in the homopolymers. The thermal stability of the copolymers increased as the feed mole fraction of aniline decreased and varied with the incorporation of metal ions in the polymers. The electrical conductivity of the homo‐ and copolymers was measured, which ranged between 10^?3 and 10^?10 S cm^?1. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2641–2648, 2003     

Synthesis of cellulose/reduced graphene oxide/polyaniline nanocomposite and its properties

A series of conductive nanocomposites cellulose/reduced graphene oxide/polyaniline (cellulose/RGO/PANi) were synthesized via in situ oxidative polymerization of aniline on cellulose/RGO with different RGO loading to study the effect of RGO on the properties of nanocomposites. The results showed that when RGO is inserted into cellulose/PANi structure, its thermal stability and conductivity are increased. So that adding of only 0.3 wt% RGO into the cellulose/PANi structure, its conductivity is increased from 1.1 × 1 10^?1 to 5.2 × 110^?1 S/cm. Scanning electron microscopy results showed that the PANi nanoparticles are formed a continuous spherical shape over the cellulose/RGO template; this increases the thermal stability of nanocomposite.     

Optical,electrical and morphological properties of transparent binary doped polyaniline thin films synthesized by in situ chemical bath deposition

The development of polymeric thin films has attracted attention in the optoelectronics field due to their transparency. The aim of the research presented was to obtain transparent polyaniline thin films by easy in situ oxidative polymerization of aniline with ammonium persulfate in the presence of a binary doping agent–poly(vinyl alcohol) mixture. Poly(acrylic acid), 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid or sodium dodecylsulfate were mixed with hydrochloric acid to form the binary doping agents. Polyaniline thin films were produced during aniline polymerization on Corning glass slides immersed in the mixture in order to study their optical, electrical and morphological properties. The optical absorption coefficient and the energy band gap were evaluated by optical transmission of the films in the UV‐visible spectral region. The optical absorption coefficient of all polyaniline films was of the order of 10⁴ cm^?1 with a maximum transmittance up to 80% at 550 nm. In order to investigate the effect of the mixture on the surface morphology and roughness of the films, atomic force microscopy was used. In general, surface roughness was reduced threefold by adding a mixture and optical transmission was increased by 20–30% without significantly affecting the absorption coefficient and the band gap of polyaniline. Islands and needle‐like structures on the film surfaces were obtained from various mixtures affecting the conductivity; for example, 0.17 S cm^?1 was obtained from needle‐like morphology, while 1.9 × 10^?4 S cm^?1 was obtained from island morphology. Raman spectroscopy studies confirmed the presence of poly(vinyl alcohol) in the thin films. Copyright © 2011 Society of Chemical Industry     

Preparation and antibacterial activity of C2-benzaldehyde-C6-aniline double Schiff base derivatives of chitosan

C₂-benzaldehyde-C₆-aniline double Schiff base derivatives of chitosan were synthesized with positioning protection method for the first time. The structures and properties of the new synthesized products were characterized by Fourier transform infrared spectroscopy, ¹³C nuclear magnetic resonance, scanning electron microscope image, X-ray diffraction, and elemental analysis. The elemental analysis results indicated that the degrees of substitution of the products were from 39.6% to 48.2%. The synthesized compounds exhibited an excellent solubility in organic solvents. The antibacterial activities of all of the derivatives were tested in the experiment, and the results showed that the prepared chitosan derivatives had significantly improved antibacterial activity of chitosan and C₂-benzaldehyde Schiff bases of chitosan toward Staphylococcus aureus (ATCC 25923) and Escherichia coli (ATCC 35218). Antibacterial activity of the Schiff bases against E. coli differs from the substituent at the same position of different anilines and increases as the sequence aniline?>?p-toluidine?>?o-toluidine, and the antibacterial activity of the Schiff bases against S. aureus increases as the sequence p-toluidine?>?aniline?>?o-toluidine. The I_C50 of the C₂-benzaldehyde-C₆-aniline double Schiff base derivatives of chitosan against E. coli and S. aureus is 0.0035 and 0.0031?mg?L^?1, respectively, much lower than that of chitosan (0.0064?mg?L^?1) and C₂-benzaldehyde Schiff bases of chitosan (0.0054?mg?L^?1). The cytotoxicity test showed that compared with chitosan and C₂-benzaldehyde Schiff bases of chitosan, the prepared chitosan derivatives had lower cytotoxicity against SCG-7901. This paper provided a new method for the synthesis of Schiff bases of chitosan, which was enlightening.