Chemical synthesis and characterization of some conducting polyaniline derivatives: Investigation of the effect of protonation medium

Poly(o‐toluidine) (POT) and poly(2‐chloroaniline) (P2ClAn) emeraldine salts were synthesized chemically by using formic (HCOOH), acetic (CH₃COOH), propionic (C₂H₅COOH), and boric (H₃BO₃) acids. Ultraviolet‐visible absorption spectra (UV–Vis) analysis results indicated that POT has the better protonation effects than P2ClAn. Among the POTs synthesized using the four different acids, POT(H₃BO₃) showed the least protonation effect. The conductivities of prepared polymers were measured by a four‐probe technique. The highest conductivities were obtained in POTs synthesized by using formic, acetic, and propionic acids. Magnetic susceptibility measurements of the polymer salts were analyzed by using Gouy scale and it was found that POT(CH₃COOH) and POT(C₂H₅COOH) salts are of bipolaron structure; other polymer salts are of polaron structure. The characterization of the polymers were investigated by Fourier infrared spectroscopy (FTIR), UV–Vis, thermogravimetric analysis, and scanning electron microscopy. It was observed from UV–Vis spectra of the emeraldine salt of POT that wavelengths belonging to π → π* transitions shifted to shorter wavelengths with increasing pKa values of acids. POT and P2ClAn synthesized in four different protonation media decomposed with three‐step and three‐ or two‐step weight loss, respectively. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1993–2000, 2002; DOI 10.1002/app.10487     

Dehydration of carboxylic acids on the MgO(100) surface

The interaction of formic and acetic acids with the MgO(100) surface has been studied under UHV conditions using XPS and TPD. Both acids dissociated heterolytically on the MgO surface, forming surface formate and acetate species respectively. The carboxylates decomposed at 520 K into dehydration products H₂O + CO from HCOO, and H₂O+CH₂CO from CH₃COOH.     

Acetone decomposition by water plasmas at atmospheric pressure

Decomposition of aqueous acetone was performed using a direct current (DC) plasma torch at atmospheric pressure. The torch can generate the plasma with water as the plasma-supporting gas in the absence of any additional gas supply system and cooling devices. The results indicated that 5 mol% acetone was drastically decomposed by water plasmas with energy efficiencies of 1.7×10^?7 mol J^?1. The major products in the effluent gas were H₂ (60–70%), CO₂ (5–16%), CO (6–16%), and CH₄ (0.2–0.9%). However, trace levels of formic acid (HCOOH) and formaldehyde (HCHO) were observed in the liquid effluent. Based on the experimental results and information from the literature, the following decomposition mechanism was proposed for acetone in water plasmas: first, electron dissociation in arc region generates acetyl (CH₃CO) and methyl (CH₃) radicals; then, chemical oxidation or reduction in plasma flow region forms CO and CH_x(x:1–3) radicals there. Finally, the generated intermediate species undergo complex reactions to form stable compounds such as CO in downstream region. However, if little oxygen is present, those intermediate species easily recombine with each other or are oxidized by OH to form unwanted by-products, such as HCOOH and HCHO.     

Stability constants of adipate complexes of copper(II), nickel(II), zinc(II), cobalt(II), uranyl(II) and thorium(IV) determined by electrophoresis

Stability constants of Copper(II), Nickel(II), Cobalt(II), Zinc(II), Uranyl(II) and Thorium(IV) adipates have been determined by paper electrophoresis. Adipic acid (0.005 mol dm^?3) was added to the background electrolyte: 0.1 mol dm^?3 HClO₄. The proportions of (CH₂)₄COOH COO^? and (CH₂)₄C₂O⁼₂ were varied by changing the pH of the electrolyte. These anions yielded the complexes Zn(CH₂)₄COOH COO⁺, Co(CH₂)₄COOH COO⁺, Ni(CH₂)₄COOH COO⁺, Th(CH₂)₄COOH COO³⁺, Th[(CH₂)₄COOH COO]₄, Cu(CH₂)₄ C₂O₄ and UO₂[(CH₂)₄(C₂O₄)]^2?₂, whose stability constants are found to be 10^2.8, 10^2.8, 10^3.2, 10^5.2, 10^15.3, 10^2.7 and 10^11.8 respectively (μ = 0.1, temp. 40°C).     

The electrochemical oxidation of organics using tungsten oxide based electrodes

High surface area tungsten oxide (WO_x) based electrodes containing centers of Pt, Sn or Ru were synthesized. The WO_x electrodes were found to display good capacitive behavior and relatively high specific capacitance values of up to 180 F g⁻¹. The oxidation behavior of particularly HCOOH and (COOH)₂, using the WO_x electrodes containing Pt and Sn centers (Pt/WO_x and Sn/WO_x, respectively), was studied in detail in aqueous solutions at high potentials, i.e. at which O₂ is evolved. Both HCOOH and (COOH)₂ appear to be oxidized following 1st order kinetics. The (COOH)₂ oxidation reaction is faster than the HCOOH reaction using otherwise the same experimental conditions. The reaction mechanism of both the HCOOH and (COOH)₂ oxidation was found to most likely involve the adsorptive interaction of the two organics with the anode surface. The WO_x based anodes appear to be promising catalysts for the anodic oxidation of both (COOH)₂ and HCOOH.     

Preparation of carboxylic acids from hydroxy compounds by oxidation with ozone

Various mono- and dicarboxylic acids were obtained with appreciable yields from saturated hydroxy compounds by oxidation in aqueous acetic acid with a mixture of ozone and oxygen followed with oxygen. The starting materials and the mono- and dicarboxylic acids obtained were as follows: Primary alcohols RCH₂OH → RCOOH; α,ω-glycols HOCH₂(CH₂)_nCH₂OH → HOOC(CH₂)_nCOOH; secondary alcohols and 12-hydroxyoctadecanoic acid R₁CH₂CH(OH)CH₂R₂ → R₁COOH + R₂CH₂COOH + R₁CH₂COOH + R₂COOH; alicyclic alcohols CH₂(CH₂)_nCHOH → HOOC(CH₂)_nCOOH; 9,10-dihydroxyoctadecanoic acid CH₃(CH₂)₇CH(OH)CH(OH) (CH₂)₇COOH → CH₃(CH₂)₇COOH + HOOC(CH₂)₇COOH. Small amounts of aldehydes, ketones, and carboxylic acids having fewer carbon atoms than those of the carboxylic acids formed as main products were also detected from some of the oxidation products.     

Synthesis and Characterization of Lauryl Trimethyl Ammonium Surfactants with New Counteranion Types

A new family of lauryl trimethyl ammonium surfactants of the general formula CH₃(CH₂)₁₁ N⁺(CH₃)₃X^? (X = CH₃OCOO, HCOO, CH₃COO, CH₃CHOHCOO) were prepared and characterized both structurally and as aqueous surfactants. Lauryl trimethyl ammonium mono-methyl carbonate was synthesized by using dimethyl carbonate (DMC) as the alkylating agent and lauryl dimethyl amine as the starting material. The latter compound was reacted with formic acid, acetic acid, and lactic acid, respectively, to give the corresponding quaternary ammonium salts with other counteranions. They were structurally characterized by IR, ¹H NMR, MS. Members of this family reduced the surface tension of water to 32–38 mN/m at concentration levels of 10^?2 mol/L.     

Effect of dye auxiliaries on the kinetics of advanced oxidation UV/H2O2 of Acid Orange 7 (AO7)

BACKGROUND: The effect of four dye‐auxiliary chemicals, typically employed in acid dyeing, on the performance of UV/H₂O₂ decolouration of the model non‐biodegradable dye C.I. Acid Orange 7 (AO7) was investigated. The initial concentration of AO7 was 0.150 g L^?1, while the concentration of the auxiliary compounds (NaCl, Na₂SO₄, Na₂CO₃ and CH₃COOH) was varied in the range 1–10 g L^?1. RESULTS: The negative influence of the presence of the dye‐auxiliary compounds studied on the decolouration rate of AO7 decreased in the following order: CH₃COOH > Na₂SO₄ > NaCl > Na₂CO₃. Results were quantified in terms of the observed kinetic rate constant, k_obs (s^?1), of AO7 decolouration as a function of dye auxiliary chemical concentration. The decolouration rate of AO7 decreased as the concentration of dye‐auxiliary compound increased in the range 1–5 g L^?1, while higher concentrations had a minor effect. Upon addition of 5 g L^?1 of CH₃COOH, NaCl and Na₂SO₄, the kinetic rate constant decreased by 39%, 30% and 12%, respectively. CONCLUSIONS: It was concluded that the presence of NaCl, Na₂SO₄ and above all of CH₃COOH should be considered in the design of the treatment of real dye‐bath effluents by UV/H₂O₂. Copyright © 2008 Society of Chemical Industry     

Novel Ni/polypyrrole and Cu/polypyrrole composites prepared in the presence of different acids: Synthesis and investigation of thermal stability

We report the synthesis and characterization of new organic/inorganic hybrid materials constituted of Ni(0) and Cu(0) nanoparticles and polypyrrole (PPy). Copper and nickel nanoclusters were synthesized by a chemical reduction of aqueous metal salt solutions by sodium borohydride. PPy/Ni(0) and PPy/Cu(0) composites were obtained in the presence of two different acids (H₃BO₃, CH₃COOH), by polymerizing pyrrole‐Ni and pyrrole‐Cu particles by using iron (III) chloride. The composites have been characterized by scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), and magnetic susceptibility techniques. Conductivity measurements of samples were taken using four‐probe devices. The PPy/Ni(0) and PPy/Cu(0) nanocomposites doped with different acids exhibited higher conductivity values than those of homopolymers. Among all samples, Ni/PPy‐H₃BO₃ has the highest conductivity (1.42 S cm^?1). Homopolymers and composites showed a stable and increasing conductivity with increasing temperature, except Ni(0). We observed that from TGA analysis of polymers, metal composites of PPy synthesized in two different media are more stable than those of PPy‐CH₃COOH and PPy‐H₃BO₃. The magnetic susceptibility values of homopolymers and Cu are negative, whereas the other samples are positive. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

On the electrochemical behaviour of the anodic oxide film on tungsten in HCOOH and CH3COOH solutions

The electrochemical behaviour of the anodic oxide film on tungsten during, or after, interruption of current flow was studied in HCOOH and CH₃COOH solutions by galvanostatic and capacitance techniques. The results show the conditions under which enhancement of film growth occurs as revealed from its formation and dissolution characteristics. The results also show the possibility of the electrochemical oxidation of formic acid by the thick oxide film on tungsten. The importance of this electrocatalytic process is the occurrence of the oxidation process without appreciable oxygen evolution. The galvanostatic oxidation of tungsten in HCOOH as a reducing agent can be considered as a novel method for the preparation of a class of oxides; oxidation with simultaneous partial reduction.     

Aqueous-Phase Processing of Bio-oil Model Compounds Over Pt–Re Supported on Carbon

The aqueous-phase processing (APP) of biomass-derived bio-oil model compounds such as ethanol, acetaldehyde, formic acid and acetic acid over Pt?CRe/C was examined. For the APP of ethanol at 250?°C, the product distribution was determined and quantified. H₂, CO₂, CH₄, C₂H₆, acetaldehyde, ethyl ether, ethyl acetate, acetic acid were found to be primary products and C₃H₈, methanol, butanol and acetal were found to be minor products. By also exploring the product distributions of acetaldehyde, acetic acid and formic acid under APP conditions with the Pt?CRe/C, the reaction network associated with the APP conversion of ethanol was determined. Using this reaction network, flux analysis was performed on the ethanol reaction system to determine the reaction pathway and relative rates (v₁?Cv₈) for each step. From this analysis, it was found that the dehydrogenation of the ethanol was the most active reaction in the reaction system.     

Experimental Evaluation of the Adsorption,Diffusion, and Separation of CH4/N2 and CH4/CO2 Mixtures on Al-BDC MOF

Adsorption equilibrium, thermodynamics, and kinetics of CH₄, N₂, and CO₂ were investigated by volumetric-chromatographic and inverse gas chromatographic (IGC) methods on the Al-BDC MOF. The binary adsorption data from the volumetric-chromatographic experiments represents that the Al-BDC MOF has a high CO₂/CH₄ selectivity ca. 11 and a CH₄/N₂ selectivity ca. 4.3 at 303 K, and appears to be a good candidate for the CH₄ separation. The initial adsorption heats of CH₄, N₂, and CO₂ on the Al-BDC MOF were determined to be 15.3, 11.5, and 32.2 kJmol^?1 by IGC method, respectively. Moreover, the micropore diffusivities of N₂, CH₄ and CO₂ in the Al-BDC MOF at 303 K were also estimated to be 1.58 × 10^?7 cm²/s, 7.04 × 10^?8 cm²/s, and 3.95 × 10^?9 cm²/s, respectively. The results indicate that micropores play a crucial role in the adsorptive separation of the CH₄/N₂ and CH₄/CO₂ mixtures, and the IGC method is a validity manner to estimate the thermodynamic and kinetic parameters of MOF adsorbents.     

Atmospheric Gas-Aerosol Equilibrium II. Analysis of Common Approximations and Activity Coefficient Calculation Methods

The gas-aerosol equilibrium model, SCAPE, presented in Part I is used to evaluate the sensitivity of thermodynamic calculations of aerosol composition to common approximations and the choice of activity coefficient estimation method. The treatment of weak electrolytes, associated ammonia, NH₃(aq), and bisulfate ion, HSO₄ ^?, is analyzed. Comparisons of the three multi-component activity coefficient estimation methods are carried out with a variety of data. On the basis of the sensitivity analysis results, recommendations are provided for treating these electrolytes and for selecting an activity coefficient estimation method in atmospheric gas-aerosol equilibrium calculations. The two gas-aerosol equilibrium models, SCAPE and AIM, are compared. Remaining questions in gas-aerosol equilibrium are highlighted.     

An Eddy-Covariance System for the Measurement of Surface/Atmosphere Exchange Fluxes of Submicron Aerosol Chemical Species—First Application Above an Urban Area

Until now, micrometeorological measurements of surface/ atmosphere exchange fluxes of submicron aerosol chemical components such as nitrate, sulfate or organics could only be made with gradient techniques. This article describes a novel setup to measure speciated aerosol fluxes by the more direct eddy covariance technique. The system is based on the Aerodyne quadrupole-based Aerosol Mass Spectrometer (Q-AMS), providing a quantitative measurement of aerosol constituents of environmental concern at a time resolution sufficient for eddy-covariance. The Q-AMS control software was modified to maximize duty cycle and statistics and enable fast data acquisition, synchronized with that of an ultrasonic anemometer. The detection limit of the Q-AMS based system for flux measurements ranges from 0.2 for NO₃ ^? to 15 ng m^?2 s^?1 for hydrocarbon-like organic aerosol (HOA), with an estimated precision of around 6 ng m^?2 s^?1, depending on aerosol loading. At common ambient concentrations the system is capable of resolving deposition velocity values < 1 mm s^?1, sufficient for measurements of dry deposition to vegetation. First tests of the system in the urban environment (6 to 20 June 2003) in Boulder, CO, USA, reveal clear diurnal, presumably traffic related, patterns in the emission of HOA and NO₃ ^?, with indication of fast production of moderately oxygenated organic aerosol below the measurement height, averaging about 15% of the HOA emission. The average emission factor for HOA was 0.5 g (kg fuel)^?1, similar to those found in previous studies. For NO₃ ^? an emission factor of 0.09 g (kg fuel)^?1 was estimated, implying oxidation of 0.5% of the traffic derived NO_x below the measurement height of 45 m. By contrast, SO₄ ^2? fluxes were on average downward, with deposition velocities that increase with friction velocity from 0.4 to 4 mm s^?1.     

Darstellung,Konfigurationen und NMR-Daten der Säuren CH3(SR)  CHCOOH (R  C6H5, CH2C6H5, CH2COOH)

Preparation, Configurations and N.M.R. Dates of the Acids CH₃(SR)CHCOOH (R  C₆H₅, CH₂C₆H₅, CH₂COOH) The cis and trans isomers of the acids CH₃(SR)CHCOOH (R  C₆H₅, CH₂C₆H₅, CH₂COOH) were prepared by addition of HSR to CH₃CCCOOH in alkaline water solution and by alkaline hydrolysis of CH₃C(SR)₂CH₂COOC₂H₅ (R  C₆H₅, CH₂C₆H₅, CH₂COOC₂H₅). The oxidation products CH₃C(SO₂R)  CHCOOH (R  C₆H₅, CH₂COOH) were also prepared. The n.m.r. dates of the acids were obtained and some relations between them were discussed.     

Equilibrium Distribution Coefficients of Some Nitrate Impurities in Sodium Nitrate from Zone Refining

Abstract

The equilibrium distribution coefficients of 10 impurities (Li, K, Rb, Cs, Ag, TI, Mg, Ca, Sr, and Ba) in sodium nitrate were determined from the measured values of the effective distribution coefficients obtained by zone refining. The equilibrium distribution coefficients obtained are as follows: LiNO₃, 9.2 × 10^?2; KNO₃, 3.0 × 10^?1; RbNO₃, 2.2 × 10^?2; CsNO₃, 1.3 × 10^?3; AgNO₃, 7.8 × 10^?1; TlNO₃, 5.2 × 10^?1; Mg(NO₃)₂, 7.4 × 10^?2; Ca(NO₃)₂, 1.5 × 10^?2; Sr(NO₃)₂, 3.0 × 10^?2; and Ba(NO₃)₂, 2.1 × 10^?2. These values are in favorable agreement with those estimated from the phase diagrams and/or those calculated from the heat of solid solution.     

Gasification of aqueous biomass in supercritical water: A thermodynamic equilibrium analysis

The aim of this work is to give insights into the gasification of aqueous biomass in supercritical water. More precisely, a mathematical model based on the thermodynamical equilibrium assumption is derived in this study. This model allows the computation of the solid, liquid and gas phases produced in a process composed of a gasification reactor and a separator. The composition of these three phases is computed in terms of fractions of CH₄, H₂, H₂O, CO, CO₂, H₂S, NH₃, C₆H₅OH, CH₃COOH, CH₃CHO, C_(s) and minerals. In the reactor, this composition is computed according to the derivation of balance equations on atoms and to the derivation of equations translating chemical equilibrium between species. Because of the specific conditions prevailing in this device (above the critical point of pure water), the computation of the activity of chemical species in the reacting media is performed using Peng-Robinson equation of state. The modelling of the separator is performed using mass balances as well as equations translating physical equilibrium of species between liquid and gaseous phases. The numerical predictions of this mathematical model are compared to experimental results obtained in the case of gasification of methanol and glucose in supercritical water. The gasification of sewage sludge is also investigated in this study.     

Surface and aqueous properties of anionic gemini surfactants having dialkyl amide,carboxyl, and carboxylate groups

A systematic study of the equilibrium surface properties (in water and in the presence of 10⁻² M NaCl) of a novel series of anionic gemini surfactants, (CH₂)₂[N(COC_nH_2n+1)CH(COOH)CH₂COOH]·2NaOH (GA), where (n+1)=8, 10, 12, 14, and 16, was investigated. The responses of humans to closed patch tests with (CH₂)₂[N(COC₁₁H₂₃)CH(COOH)−CH₂COOH]₂·2NaOH (GA-12) were also investigated. Premicellar self-aggregation (both in water and 10⁻² M NaCl) occurred when the N-acyl group contained more than 14 carbon atoms, since the critical micelle concentration (CMC) values decreased and the pC₂₀ values increased as (n+1) increased for (n+1) ≤14; the CMC values increased and the pC ₂₀ values decreased as (n+1) increased for (n+1)>14, both in water and in 10⁻² M NaCl. The absence of a break in the specific conductance-surfactant molar concentration plots for the GA homologs indicates protonation of the carboxylate group and strong Na⁺ release during micellization. This is a structural characteristic of the anionic geminis having N-dialkylamide and carboxylate groups in a molecule. The skin irritation potential of GA-12 is lower than that of the corresponding “monomer”, C₁₁H₂₃CON(CH₃)CH(COOH)CH₂(COOH)·NaOH, and the analog, C₁₁H₂₃CON(CH₃)CH₂COONa·H₂O.     

A Chemical Ionization High-Resolution Time-of-Flight Mass Spectrometer Coupled to a Micro Orifice Volatilization Impactor (MOVI-HRToF-CIMS) for Analysis of Gas and Particle-Phase Organic Species

We describe a new instrument, chemical ionization (CI) high-resolution time-of-flight mass spectrometer (ToFMS) coupled to a micro-orifice volatilization impactor (MOVI-HRToF-CIMS). The MOVI-HRToF-CIMS instrument is unique in that, within a compact field-deployable package, it provides (1) quantifiable molecular-level information for both gas and particle-phase organic species on timescales ranging from ≤1 s for gases to 10–60 min for particle-phase compounds that can be used to efficiently probe oxidation and secondary organic aerosol (SOA) formation mechanisms, and (2) relative volatility information of the detected compounds simultaneously estimated using the programmed thermal desorption information obtained from the MOVI. We demonstrate the capabilities of a prototype instrument using known test compounds and complex mixtures generated from the oxidation of biogenic and anthropogenic hydrocarbons. We present spectra obtained using both negative and positive ion CI with acetate (CH₃C(O)O^?) and protonated water clusters (H₃O⁺·(H₂O) _n ), respectively, as reagent ions. The instrument has high mass resolving power (R = 5000 above m/Q 250 Th) and mass accuracy (±20 ppm) enabling estimation of compound elemental composition. Instrument sensitivity in negative ion mode was tested using formic acid as a representative gas-phase compound, and that for particle-phase compounds was tested using palmitic, azelaic, and tricarballylic acids. With a heated MOVI inlet, an ion count rate of ～15 Hz is achieved when sampling 1 pptv (= 1 pmol/mol) of formic acid (or other monocarboxylic acids) under typical operating conditions. This sensitivity translates to detection limits less than 1 ng/m³ for carboxylic acids in the particle-phase. We also discuss the remaining challenges with this instrument to broadly characterizing gaseous and particulate oxygenated organic compounds in situ.

Copyright 2012 American Association for Aerosol Research     

Synthesis and Surface Activities of Novel Succinic Acid Monofluoroalkyl Sulfonate Surfactants

Two environmentally friendly succinic acid monofluoroalkyl sulfonate surfactants were synthesized from maleic anhydride and polyethylene glycol mono (1H,1H,7H‐dodecafluoroheptyl) ether, i.e. H(CF₂)₆CH₂OCH₂CH₂OCOCH(SO₃Na)CH₂COOH (FEOS‐1) and H(CF₂)₆CH₂(OCH₂CH₂)₃OCOCH(SO₃Na)CH₂COOH (FEOS‐3). The obtained surfactants were characterized by FT‐IR, ¹H NMR, ¹³C NMR and ¹⁹F NMR in detail. The synthesized fluorinated surfactants have a high thermal stability on the basis of thermogravimetric analysis. Their surface properties were examined and the results show that FEOS‐1 and FEOS‐3 surfactants can reduce the surface tension of water to 25.55 mN m^?1 at 10.25 mmol L^?1 and 21.63 mN m^?1 at 8.33 mmol L^?1, respectively; meanwhile, the introduction of oxyethylene groups enhances the hydrophilicity and micellar forming ability and the longer oxyethylene chains the better surface properties. The Krafft points (K_p) of FEOS‐1 and FEOS‐3 were both below 0 °C, which was lower than perfluoro‐n‐heptanesulfonic acid sodium salt (n‐C₇F₁₅SO₃Na, K_p = 56.5 °C) at a similar length of fluorocarbon chains. Comparison studies on two surfactants above and the conventional fluorocarbon surfactants, perfluorooctanoate of ammonium (PFOA) show that the surfactants have comparable properties to PFOA, thus offering an environmentally friendly synthesizing alternatives to PFOA.