Tetrachloroethane Research Articles

Recovery of Chromium and Two Solvents (Dichloromethane-DCM Tetrachloroethane-TCE) Using Nanofiltration and Reverse Osmosis Membranes from Leather Industry Wastewater

In this study, for removal of the leather industry pollutants and to recovery of chromium (Cr), dichloromethane (DCM) and tetrachloroethane (TCE) two sequential nanofiltration (NF) (NF90 and NF270) and two reverse osmosis (RO) (BW30 and SW30) reactor membranes were used. The membrane surface properties were investigated by Fourier Transform Infrared Spectroscopy-Attenuated Total Reflectance (FTIR-ATR) and Scanning Electron Microscopy (SEM). The permeate of the SW30 reverse osmosis exhibited high removals varying between 98% and 99% for sodium ion (Na+ ), potassium ion (K+ ), magnesium ions (Mg2+), calcium ions (Ca2+), total chemical oxygen demand (CODtotal), dissolved chemical oxygen demand (CODdis), dissolved organic carbon (DOC) and inert chemical oxygen demand (inert COD), Chromium (Cr3+ ), Dichloromethane and Tetrachloroethane. In the NF90 nanofiltration process lower removals were detected (96%-97%) for all pollutants mentioned above. The effluent of reverse osmosis with a BW30 membrane match to the Turkish Water Pollution Control Regulation rules for treated water discharged to the receiving environment while SW30 reverse osmosis membrane was perfect for ultimate treatment of the pollutants present in the leather industry discharges. From the concentrate of the SW30 reverse osmosis, 945 mg/l chromium, 460 mg/l dichloromethane and 360 mg/l tetrachloroethane were reused. The performance and recoveries of Cr and two solvents (DCM and TCE) data in NF and RO membrane reactors were evaluated with Artificial Neural Network (ANN) process and Kruskal Wallis test statistic coupled with Mann-Whitney U statistic in this study.

Tetrachloroethane (TeCA) removal through sequential graphite-mixed metal oxide electrodes in a bioelectrochemical reactor

Electro-bioremediation offers a promising approach for eliminating persistent pollutants from groundwater since allows the stimulation of biological dechlorinating activity, utilizing renewable electricity for process operation and avoiding the injection of chemicals into aquifers. In this study, a two-chamber microbial electrolysis cell has been utilized to achieve both reductive and oxidative degradation of tetrachloroethane (TeCA). By polarizing the graphite granules cathodic chamber at −650 mV vs the standard hydrogen electrode and employing a mixed metal oxide (MMO) counter electrode for oxygen production, the reductive and oxidative environment necessary for TeCA removal has been established. Continuous experiments were conducted using two feeding solutions: an optimized mineral medium for dechlorinating microorganisms, and synthetic groundwater containing sulphate and nitrate anions to investigate potential side reactions. The bioelectrochemical process efficiently reduced TeCA to a mixture of trans-dichloroethylene, vinyl chloride, and ethylene, which were subsequently oxidized in the anodic chamber with removal efficiencies of 37 ± 2%, 100 ± 4%, and 100 ± 5%, respectively. The introduction of synthetic groundwater with nitrate and sulphate stimulated reductions in these ions in the cathodic chamber, leading to a 17% decrease in the reductive dechlorination rate and the appearance of other chlorinated by-products, including cis-dichloroethylene and 1,2-dichloroethane (1,2-DCA), in the cathode effluent. Notably, despite the lower reductive dechlorination rate during synthetic groundwater operation, aerobic dechlorinating microorganisms within the anodic chamber completely removed VC and 1,2-DCA. This study represents the first demonstration of a sequential reductive and oxidative bioelectrochemical process for TeCA mineralization in a synthetic solution simulating contaminated groundwater.

Efficient chlorinated alkanes degradation in soil by combining alkali hydrolysis with thermally activated persulfate

Alkali activation is the most commonly used activation method for persulfate (PS) in in-situ remediation. However, the role of alkali in pollutant degradation is still elusive, limiting the optimization of relevant remediation strategies. In this study, we found that chlorinated alkanes (e.g., tetrachloroethane (TeCA)) could be efficiently degraded by thermal-alkali activation of PS. The main role of alkali was not activating PS but hydrolyzing the chlorinated alkanes, which was evidenced by the immediate conversion of TeCA into trichloroethylene (TCE) with NaOH and PS or with sole NaOH solution. Electron paramagnetic resonance analysis also showed that with a high NaOH/PS molar ratio (4:1) the intensity of oxidative radicals decreased, implying that high levels of alkali did not favor the formation of free radicals. Interestingly, better degradation of TeCA and its product TCE was observed by the combination of alkaline hydrolysis and thermal activation of PS (where alkali was added 6 h before PS rather than simultaneously) in comparison to thermal-alkali activation of PS. This study provides new insights into the remediation of chlorinated alkane-contaminated soils by in-situ chemical oxidation.

Analysis of the association of parameters in the formation of ultrafine fibers from PEI and PMMA

Objective: The aim of the study was to fabricate and morphologically characterize ultrafine Polyetherimide fibers (PEI) associated with Polymethylmethacrylate (PMMA) – PP (group formed by the association of PEI with PMMA), produced by the electrospinning process. Material and Methods: A solution of PEI (0.562 g) + PMMA (0.377 g) dissolved in 2.5 mL of chloroform, 0.85 mL of Dimethylformamide (DMF) and 0.85 mL of 1.1.2.2 Tetrachloroethane (TCE) was prepared. For the electrospinning process, different continuous voltages (10 to 18 kV) and two different distances (8 and 12 cm) between the needle tip and the collecting apparatus were used, giving rise to 6 distinct groups of ultrafine fibers (PP 1 to 6) that were observed in Scanning Electron Microscopy to check for defects and calculate the average diameter of the fibers. Results: The best parameter, the parameter that was most effective for the production of fibers, observed was subjected to Energy Dispersion X-ray Spectroscopy (EDS), X-ray Diffraction (XRD) and Contact Angle Analysis tests. The data were analyzed using the ANOVA and Tukey test (p <0.05). From the comparative analysis of the pre-established parameters, the pattern of PP4 ultrafine fibers was shown to be more effective. Conclusion: The PP4 standard (13 kV – 12 cm) had an average diameter of 0.37 µm. An adequate parameter to electrospinning was able to produce ultrafine fibers of PMMA/PEI. Keywords Polymethylmethacrylate; Scanning electron microscopy; Polyetherimide; Electrospinning process.

Reactivity of CuIN4 Flattened Complexes: Interplay between Coordination Geometry and Ligand Flexibility.

The relation between redox activity and coordination geometry in CuIN4 complexes indicates that more flattened structures tend to be more reactive. Such a preorganization of the ligand confers to the complex geometries closer to a transition state, which has been termed the "entatic" state in metalloproteins, more recently extending this concept for copper complexes. However, many aspects of the redox chemistry of CuI complexes cannot be explained only by flattening. For instance, the role of ligand flexibility in this context is an open debate nowadays. To analyze this point, we studied oxidation properties of a series of five monometallic CuI Schiff-base complexes, [CuI(Ln)]+, which span a range of geometries from a distorted square planar (n = 3) to a distorted tetrahedron (n = 6, 7). This stepped control of the structure around the CuI atom allows us to explore the effect of the flattening distortion on both the electronic and redox properties through the series. Experimental studies were complemented by a theoretical analysis based on density functional theory calculations. As expected, oxidation was favored in the flattened structures, spanning a broad potential window of 370 mV for the complete series. This orderly behavior was tested in the reductive dehalogenation reaction of tetrachloroethane (TCE). Kinetic studies show that CuI oxidation by TCE is faster as the flattening distortion is higher and the oxidation potentials of the metal are lower. However, the most reactive complex was not the more planar, contradicting the trend expected from oxidation potentials. The origin of this irregularity is related to ligand flexibility and its connection with the atom/electron transfer reaction path, highlighting the need to consider effects beyond flattening distortion to better understand the reactivity of this important class of complexes.

A novel process integrating vacuum distillation with atmospheric chlorination reaction for flexible production of tetrachloroethane and pentachloroethane

Abstract In this paper, we developed a novel process integrating vacuum distillation with atmospheric chlorination reaction (VD-ACR) to realize the flexible production of tetrachloroethane (TeCA) and pentachloroethane (PCA) from 1,2-dichloroethane (DCA). During the simulation, the distillation column and reactors were operated for separation and chlorination respectively under variable pressures and temperatures. It is interesting to note that VD-ACR processes producing pure TeCA or PCA can exhibit the similar configuration parameters after optimization, which enables the flexible production of TeCA and PCA with different molar ratios via changing operating parameters. The molar ratio of TeCA/PCA can be fine-tuned within the range of 0.9:0.1 - 0.1:0.9 through adjusting the amount of chlorine pumped into side reactors, giving rise to the increase of the heat duty of reboiler by five times. A pilot-scale experiment was then operated based-upon this VD-ACR process and the result matched well with the simulation. Therefore, the VD-ACR model presented in this study will be beneficial for the industrial-scale flexible production of TeCA and PCA from DCA.

H2 effect in Chevron–Phillips ethylene trimerization catalytic system: an experimental and theoretical investigation

Effect of H2 amount on the activity and selectivity of Chevron–Phillips trimerization system, i.e., chromium(III) tris(2-ethylhexanoate)/2,5-dimethylpyrrole/triethylaluminum (TEA)/tetrachloroethane (TCE), was examined. In this regard, in addition to catalytic ingredients and ethylene monomer, 2.5 and 5 bar H2 were utilized in the oligomerization reactor and the reaction results were compared with those without H2. Results showed that addition of hydrogen has a remarkable effect on polymer formation and catalyst activity so that 147% decrease in polymer formation and 38% increase in activity were observed upon addition of 5 bar H2. However, its effect on 1-hexene selectivity was not pronounced. Then, molecular modeling with DFT method was employed to simulate oligomerization process in molecular level. Energy results revealed that formation of 1-hexene has less energy barrier than the formation of 1-butene and 1-octene which confirms higher selectivity of Chevron–Phillips system toward 1-hexene formation. Furthermore, interaction of hydrogen with catalytic active center was studied via hydrogenolysis of metalacycles. Energy results revealed that it is energetically a facile process so that the bigger the circle, the easier hydrogenolysis.

Understanding Noncovalent Interactions of Small Molecules with Carbon Nanotubes.

We combine experimental methods, density functional theory (DFT) calculations, and molecular dynamics (MD) simulations in the quantitative analysis of noncovalent interactions between (6,5)-enriched single-walled carbon nanotubes (SWNTs), as hosts, and a set of pyrene derivatives with different electronic properties and surface areas, as guests. The experiments and calculations were carried out in two solvents with markedly different polarities, namely 1,1',2,2'-tetrachloroethane (TCE) and N,N-dimethylformamide (DMF). Our results show that dispersion forces govern the supramolecular association of small molecules with (6,5)-SWNTs, with negligible contributions from ground-state charge-transfer effects. In the nonpolar solvent (TCE), the binding constants are highly correlated with the contact area between the SWNT and the guests. In the polar solvent (DMF), the binding constants show a complex dependence on the chemical nature of the pyrene substituents, as demonstrated by MD simulations with the explicit inclusion of solvent molecules. The solvation of the small molecules is shown to play a leading role in the binding process. Remarkably, the binding constants obtained from the MD simulations for the five guest molecules correlate with those derived from experiment. Furthermore, the MD simulations also reveal the structure of the adsorbed guest from low to high SWNT surface coverage.

Catalytic Ring-Opening (Co)polymerization of Semiaromatic and Aliphatic (Macro)lactones

The ring-opening polymerization (ROP) of cyclic butylene terephthalate oligomers (cBT) using an aluminum salen catalyst was investigated. The kinetic analysis of the ROP of cBT in tetrachloroethane (TCE) revealed a first-order dependence of the rate constant in catalyst as well as monomer concentration. Comparison with the ROP in other solvents showed that TCE significantly retards the reaction by short-term reversible catalyst deactivation and by long-term permanent deactivation. The apparent activation energy for the ROP of cBT and e-caprolactone (CL) were determined independently, and the difference in reactivity was used to investigate the possibility to synthesize blocky copolymers. Sequence distribution analysis of the copolymers obtained over a period of time from a single feed copolymerization revealed that over the full reaction range the degree of randomness was high. A sequential feed approach, in which CL was added after the polymerization of cBT was completed, showed that the propagation reac...

Synthesis and characterization of new soluble polyamides from Acenaphtohydrazinomercaptotriazole diamine

A diamine Acenaphtohydrazinomercaptotriazole (AHTD) was synthesized in one step from acenaphthoqinone and 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole. The diamin was characterized by FTIR, 1HNMR, 13CNMR and melting point. Diamin was used to prepare novel polyamides. The low temperature solution polycondensation of diamin with tow aromatic and tow aliphatic diacid chlorides afforded diamin-containing polyamides with inherent viscosities of 0.38–0.47 dl/g in DMF at 25 °C. The polyamides were generally soluble in a wide range of solvents such as dimethylformamide(DMF), N-Methylpyrolidone(NMP), tetrachloroethane (TCE), dimethylsulfoxide(DMSO) and H2SO4. Thermal analysis showed that these polyamides were practically crustily and with Tg under 100 °C.

Photoconductive and nonlinear optical properties of composites based on metallophthalocyanines

AbstractThe photoconductive, photorefractive and nonlinear optical properties of composites from polyvinylcarbazole or aromatic polyimide containing supramolecular ensembles of (tetra-15-crown-5) - phthalocyaninato gallium, indium, - phthalocyaninateacetato yttrium, - phthalocyaninato ruthenium with axially coordinated pyrazine molecules were investigated at 633, 1030 and 1064nmusing continuous and pulsed lasers. Supramolecular ensembles (SE) were prepared through dissolution of molecular metallophthalocyanines in tetrachloroethane (TCE) and subsequent treatment via three cycles of heating to 90∘C and slow cooling to room temperature. The zscan method in femtosecond and nanosecond regimeswas used for measuring nonlinear optical properties phthalocyaninato indium and yttrium in TCE solutions and polymer films. It was established that effect of heavy metallic atom is basic factor which determines the quantum yield, photorefractive amplification of laser object beam, dielectric susceptibility of third order and nonlinear optical properties of metallophthalocyanines.

Photorefractive and nonlinear optical properties of indium(III) tetra(15-crown-5)phthalocyaninate-based composites

Photoelectric, nonlinear optical, and photorefractive properties of hybrid composite materials based on polyvinylcarbazole (PVK) and indium(III) 2,3,9,10,16,17,23,24-tetra(15-crown-5)phthalocyaninate [(15C5)4Pc]In(OH) are studied in detail. Field dependence of the quantum efficiency in a 7.8 μm-thick layer containing 5 at % [(15C5)4Pc]In(OH) is measured. The best approximation of the quantum efficiency with Onsager’s equation corresponds to a quantum yield of thermalized electron-hole pairs φ0 = 0.01 at initial separation r 0 = 9.8 A. Z-scan measurements in a nanosecond range showed that the electric susceptibility of [(15C5)4Pc]In(OH) solution in tetrachloroethane (TCE) with a concentration of 7 × 10−4 mol/L is χ(3) = 1.34 × 10−9 esu. The maximum coupling gain coefficient found for the material composed of PVK and 5 wt % [(15C5)4Pc]In(OH) at an electric-field intensity of 200 V/μm is Γ = 80 cm−1, and the difference between the coupling gain and absorption coefficients is Γ − α = 70 cm−1. The dependence of the coupling gain coefficient on the intensity ratio of interfering beams 1 and 2 (β = I 1(0)/I 2(0)) in a composite containing 3 wt % [(15C5)4Pc]In(OH) is measured. An increase in β was attained by decreasing intensity of the signal beam I 2(0) at constant intensity of the pump beam I 1(0) = 0.15 W/cm2 and E 0 = 214 V/μm. Within the initial segment of the curve, the coupling gain coefficient increases from 30 to 60 cm−1; then, the coefficient drops almost to the initial value. The data obtained show that the composite materials studied can be used in practice for correcting faded images. The combined analysis of the results obtained and similar data for gallium and ruthenium tetra-15-crown-5-phthalocyaninate complexes revealed the regularities in the change of the quantum yield of thermalized electron-hole pairs and the photorefractive coupling gain coefficient in a series of complexing metals: gallium(III), ruthenium(II), and indium(III). An increase in the molecular weight of the central metal atom is found to result in a substantial decrease in Γ and φ0 due to the increase in the spin-orbit coupling constant.

Synthesis and characterization of soluble polyester based on calixarene dicarboxylic acid with tertiary butyl pendant groups

A series of new polycalixesters (PCES) were synthesized by polyesterification of calixarene dicarboxylic acid derivatives having tertiary butyl pendant groups at the upper rim using five different diols. All polyesters were readily soluble in polar solvents such as NMP (N-methylpyrrolidone), DMF (dimethylformamide), DMSO (dimethylsulfoxide), pyridine, THF (tetrahydrofurane), HMPA (hexamethylenephosphoramide) and DMAC (dimethylacetamide). The PCES were also partially soluble in TCE (tetrachloroethane) and ethanol and they were unsoluble in aceton. The glass transition temperatures of polyesters were between 80–184 °C, the crystallinity temperatures of polyesters were between 130–212 °C and the melting temperatures of polyesters were between 185–234 °C, as determined by differential scanning calorimeter (DSC). The inherent viscosities of polyesters were obtained from 0.55 dL/mg to 0.61 dL/mg. The temperatures at 10% weight loss of polyesters ranged from 182 °C to 237 °C. The temperatures at 25% weight loss of polyesters ranged from 258 °C to 331 °C. The half weight loss (50%) temperatures of polyesters were among 315 °C to 371 °C and the char yields at 600 °C were determined within 13% to 22.3% in N2 atmosphere, as determined by thermo gravimetric analysis (TGA). The polyester, PES3, has the higher melting point (234 °C) and higher inherent viscosity (molecular weight) than the other polyesters.

Nonlinear optical properties of systems based on (tetra-15-crown-5-phthalocyaninato)indium(III)

The nonlinear optical properties of solutions of (2,3,9,10,16,17,23,24-tetra-15-crown-5-phthalocyaninato)indium(III) [(15C5)4Pc]In(OH) in tetrachloroethane (TCE) have been studied by the z-scan method. It has been found that a nonlinear optical response is due to supramolecular associates formed in a tetrachloroethane solution by heating to 90°C/slow cooling to room temperature cycling. The formation of the supramolecular associates has been studied by atomic force microscopy (AFM) and electronic absorption spectroscopy (EAS). It has been shown that a single thermal treatment of [(15C5)4Pc]In(OH) solutions in TCE results in the predominant formation of dimers, as evidenced by both a short-wavelength shift of the Q-absorption band of the monomeric complex (λmax = 692 nm) to the band of λmax = 653 nm and height doubling of molecular entities as measured by AFM. The dimers are responsible for the two-photon absorption measured in the femtosecond range, which has a relatively high cross section of σ2 = 1.38 × 10−46 cm4 s/(molecule, photon) or 1.38 × 104 GM. According to the AFM data, three cycles of heat treatment of the solution leads to the formation of supramolecular assemblies of about 200 nm length. The optical spectrum exhibits long-wavelength absorption at λmax = 841 nm and the long-wavelength edge near 1300 nm. In the case of nanosecond 1064-nm laser irradiation, the linear absorption S 0 → S 1 is primary, having the cross section of σ0 = α0/N = 2.3 × 10−20 cm2. The known high quantum yield (close to unity) of triplet states of indium phthalocyanines suggests that the main nonlinear optical effect is determined by intersystem crossing S 1 → T 1 and triplet-triplet absorption T 1 → T 2. The absorption cross section is σ T-T = 1.14 × 10−19 cm2.

Tubular or Subsurface Morphology of Octabutoxyphthalocyanine upon Self‐Assembly in Polymer Matrices: Effect of the Casting Solvent

Spontaneous phase-separated, controlled aggregate structures of photo- and electroactive molecules in polymer matrices are of interest for device fabrication. We show that the self-assembly of octabutoxyphthalocyanine (Pc) in polymer matrices leads to tubular morphology of Pc when the film is prepared with tetrachloroethane (TCE) and subsurface droplet morphology with chloroform. The same morphology is seen with both bisphenol A polycarbonate (BPAPC) and poly(methyl methacrylate) (PMMA) as the matrix. The subsurface morphology results from the rapid association of Pc in the polymer matrix, as the film forms. With the tubular morphology in the films prepared with TCE, percolation threshold is reached with a concentration of Pc as low as 3% (wt) in the polymer. Such phase-separated self-assembly occurs, without any annealing of the films. Even in the absence of the polymer, Pc crystallized from TCE also shows tubular morphology, whereas it exhibits a columnar morphology with chloroform. X-ray diffraction of Pc crystallized from either solvent shows the columnar stacking of the Pc molecules. However, the morphology is tubular when TCE is used. We attribute the difference in the morphology to the higher viscosity of TCE and the diffusion-limited growth, which causes the tubular morphology, whereas the instantaneous self-assembly in less-viscous chloroform leads to droplets. The solvent effect observed here could be used to tailor the morphology of such photoconductive molecules in polymer matrices.

Synthesis and characterization of Schiff-base-containing polyamides

A series of new Schiff base polyamides (PAs) were synthesized by polycondensation of benzilbisthiosemicarbazone diamine (LH6) with different commercially available aliphatic and aromatic diacid chlorides. The monomer and all the PAs were characterized by FTIR, 1H-NMR, and elemental analysis. The prepared polyamides showed inherent viscosities in the range of 0.30–0.36 dL/g in DMF at 25°C, indicating their moderate molecular weight. The PAs were completely soluble in aprotic polar solvents such as dimethylformamide (DMF), N-methylpyrolidone (NMP), tetrachloroethane (TCE), dimthylsulfoxide (DMSO) and also in H2SO4 and partially soluble in THF, acetone and chloroform at room temperature. Thermal analysis showed that these PAs were practically amorphous and exhibited 10% weight loss above 220°C.

Synthesis and characterization of Schiff-base-containing polyimides

A series of new Schiff base polyamides (PAs) were synthesized by polycondensation of benzilbisthiosemicarbazone diamine (LH6) with different commercially available aliphatic and aromatic diacid chlorides. The monomer and all the PAs were characterized by FTIR, 1H-NMR, and elemental analysis. The prepared polyamides showed inherent viscosities in the range of 0.30–0.36 dL/g in DMF at 25°C, indicating their moderate molecular weight. The PAs were completely soluble in aprotic polar solvents such as dimethylformamide (DMF), N-methylpyrolidone (NMP), tetrachloroethane (TCE), dimthylsulfoxide (DMSO) and also in H2SO4 and partially soluble in THF, acetone and chloroform at room temperature. Thermal analysis showed that these PAs were practically amorphous and exhibited 10% weight loss above 220°C.

Mechanistic Insight into the Initiation Step of the Coupling Reaction of Oxetane or Epoxides and CO2 Catalyzed by (salen)CrX Complexes

The most active and robust current catalysts for the copolymerization of carbon dioxide and epoxides or oxetanes, (salen)CrX in conjunction with PPNX (PPN(+) = (Ph3P)2N(+)) or n-Bu4NX (X = Cl, N3, CN, NCO), are characterized both in solution by infrared spectroscopy and in the solid-state by X-ray crystallography. All anions (X) afford six-coordinate chromium(III) PPN(+) or n-Bu4N(+) salts composed of trans-(salen)CrX2(-) species. Of the X groups investigated in (salen)CrX, chloride is easily displaced by the others, that is, the reaction of (salen)CrCl with 2 equiv of N3(-), CN(-), or NCO(-) quantitatively provide (salen)Cr(N3)2(-), (salen)Cr(CN)2(-), and (salen)Cr(NCO)2(-), respectively. On the other hand, addition of less than 2 equiv of azide to (salen)CrCl leads to a Schlenk (ligand redistribution) equilibrium of the three possible anions both in solution and in the solid-state as shown by X-ray crystallography and electrospray ionization mass spectrometry. It was further demonstrated that all trans-(salen)CrX2(-) anions react with the epoxide or oxetane monomers in TCE (tetrachloroethane) solution to afford an equilibrium mixture containing (salen)CrX x monomer, with the oxetane adduct being thermodynamically more favored. The ring-opening steps of the bound cyclic ether monomers by X(-) were examined, revealing the rate of ring-opening of the epoxides (cyclohexene oxide and propylene oxide) to be much faster than of oxetane, with propylene oxide faster than cyclohexene oxide. Furthermore, both X anions in (salen)CrX2(-) were shown to be directly involved in monomer ring-opening.

Spectroscopic and lasing characterisation of a luminescent phenylene/bipyridine polymer

The luminescent polymer, poly[2,2′-bipyridine-5,5′-diyl-(2,5-dihexyl-1,4-phenylene)] (abbreviated PPBpy) dissolved in tetrachloroethane (TCE) and as neat film is characterised by optical absorption and emission spectroscopy. The absorption and stimulated emission cross-section spectra, the fluorescence quantum distributions, fluorescence quantum yields, degrees of fluorescence polarisation, and fluorescence lifetimes are determined. A lasing characterisation is carried out by pumping with single second harmonic pulses of a mode-locked ruby laser (wavelength 347.15 nm, duration 35 ps). The excited-state absorption at the pump-laser wavelength is determined by saturable absorption measurements. Laser oscillation of the polymer in TCE in an uncoated rectangular cell was achieved by transverse pumping using the cell windows for light feedback. From the laser threshold pump pulse energy density the effective stimulated emission cross-section at the lasing wavelength is extracted. The travelling-wave lasing behaviour of the polymer as neat film is studied by analysis of the amplification of the transverse pumped spontaneous emission. Surface emitting distributed-feedback lasing was achieved with a neat film on corrugated second-order periodic gratings.

Effect of tetrachloroethane on the equilibrium between ionic and molecular complexes in the methylsulfonic acid-butyl acetate system

In concentrated solutions of methylsulfonic acid in butyl acetate (BA), molecular and ionic complexes were found to be in equilibrium: $$ AH \cdots B \cdots HA + HA \leftrightarrow AH \cdots BH^ + + (AHA)^ - . $$ The base is fully protonated only at a more than 10-fold excess of the acid. In the presence of tetrachloroethane (TCE), a neutral solvent, the IR spectra of the system are indicative of an increase in the concentration of undissociated acid molecules (HA) and a decrease in the concentration of proton solvates (AHA)−. This means that the equilibrium shifts to the formation of molecular structures. At C TCE 0 :C BA 0 > 2, TCE molecules attenuate the promoting effect of undissociated acid molecules, which are known to facilitate the transfer of a proton to a base molecule with the formation of an (AHA)− ion with a strong symmetrical H-bond.