首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 78 毫秒
1.
In the present work, kinetics of tartrazine decay by UV irradiation and H2O2 photolysis, and the removal of total organic carbon (TOC) under specific experimental conditions was explored. Irradiation experiments were carried out using a photoreactor of original design with a low-pressure Hg vapour lamp. The photodegradation rate of tartrazine was optimised with respect to the H2O2 concentration and temperature for the constant dye concentration of 1.035 × 10?5 M. Tartrazine degradation and the removal of TOC followed the pseudo-first-order kinetics. The much higher k obs value for tartrazine degradation (7.91 × 10?4 s?1) as compared with the TOC removal (2.3 × 10?4 s?1) confirmed the presence of reaction intermediates in the solution.  相似文献   

2.
An electrochemical method for the simultaneous determination of benzene, toluene and xylenes (BTX) in water was developed using square‐wave voltammetry (SWV). The determination of BTX was carried out using a cathodically pre‐treated boron‐doped diamond electrode (BDD) using 0.1 mol L?1 H2SO4 as supporting electrolyte. In the SWV measurements using the BDD, the oxidation peak potentials of the total xylenes‐toluene and toluene‐benzene couples, present in ternary mixtures, display separations of about 100 and 200 mV, respectively. The attained detection limits for the simultaneous determination of benzene, toluene and total xylenes were 3.0×10?7, 8.0×10?7 and 9.1×10?7 mol L?1, respectively. The recovery values taken in ternary mixtures of benzene, toluene and total xylenes in aqueous solutions are 98.9 %, 99.2 % and 99.4 %, respectively.  相似文献   

3.
The adsorption of several toluene-soluble polymers at the toluene–water interface has been investigated by using the duNouy ring method of measuring interfacial tension γT /W . Polystyrene and poly(ethylene-co-vinyl acetate) (11.1 mole-% vinyl acetate) have little affinity for this interface at 29°C, but poly(methyl methacrylate) (PMMA) (M?n = 420,000) and ethyl cellulose (EC) (M?n = 50,100; 49.1% ethoxyl) adsorb significantly at concentrations as low as 1.0 × 10?4 g/100ml. A plot of interfacial tension lowering versus initial logarithm of initial bulk phase polymer concentration is linear from 1.0 × 10?4 to 1.0 × 10?1 g/100 ml for EC and 1.0 × 10?4 to 1.0 × 10?2 g/100 ml for PMMA. When the PMMA concentration increases to 1.15 × 10?1 g/100 ml, its adsorption behavior changes markedly. Prolonged time effects occur and adsorption becomes dependent upon dissolved water content of the toluene prior to formation of the toluene/water interface. Such effects are not observed with the other solutions studied. Increasing temperatures have variable effects on values of γT /W for the polymer solutions studied. Experiments with various polymer mixtures indicate that the polymer lowering T /W the most is preferentially adsorbed at the toluene–water interface and rapidly displaces less strongly adsorbed polymers.  相似文献   

4.
An electroanalytical study of the oxidation processes of umbelliferone and hymecromone at a glassy carbon electrode in micellar solution and emulsified medium by different voltammetric techniques is described. The non-ionic surfactant Triton X-405 in acetate-buffered medium at pH 4.8 was found to be the most suitable. Different ranges of linearity were obtained in the micellar solutions, depending on the technique used; the limits of determination for differential pulse voltammetry (DPV) at a stationary electrode were 2.9×10?6 mol l?1 and 3.3×10?6 mol l?1 for umbelliferone and hymecromone, respectively. In the emulsified medium formed with a mixture of toluene and ethyl acetate (3:2), the oxidation processes yielded similar results. With DPV, linear calibration plots were obtained in the ranges 1.0×10?5–9.0×10?7 mol l?1 umbelliferone and 1.0×10?5–2.0×10?6 mol l?1 hymecromone. The media used are predominantly aqueous so that special reference electrodes and solvent purification are not needed.  相似文献   

5.
The gas permeability and n‐butane solubility in glassy poly(1‐trimethylgermyl‐1‐propyne) (PTMGP) are reported. As synthesized, the PTMGP product contains two fractions: (1) one that is insoluble in toluene and soluble only in carbon disulfide (the toluene‐insoluble polymer) and (2) one that is soluble in both toluene and carbon disulfide (the toluene‐soluble polymer). In as‐cast films, the gas permeability and n‐butane solubility are higher in films prepared from the toluene‐soluble polymer (particularly in those films cast from toluene) than in films prepared from the toluene‐insoluble polymer and increase to a maximum in both fractions after methanol conditioning. For example, in as‐cast films prepared from carbon disulfide, the oxygen permeability at 35 °C is 330 × 10?10 cm3 (STP) cm/(cm2 s cmHg) for the toluene‐soluble polymer and 73 × 10?10 cm3 (STP) cm/(cm2 s cmHg) for the toluene‐insoluble polymer. After these films are conditioned in methanol, the oxygen permeability increases to 5200 × 10?10 cm3 (STP) cm/(cm2 s cmHg) for the toluene‐soluble polymer and 6200 × 10?10 cm3 (STP) cm/(cm2 s cmHg) for the toluene‐insoluble polymer. The rankings of the fractional free volume and nonequilibrium excess free volume in the various PTMGP films are consistent with the measured gas permeability and n‐butane solubility values. Methanol conditioning increases gas permeability and n‐butane solubility of as‐cast PTMGP films, regardless of the polymer fraction type and casting solvent used, and minimizes the permeability and solubility differences between the various films (i.e., the permeability and solubility values of all conditioned PTMGP films are similar). © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2228–2236, 2002  相似文献   

6.
Iodide is determined after oxidation with nitrous acid in 5 M hydrochloric acid to ICl?2. The ion-pair formed with rhodamine B is extracted into toluene and measured spectrophotometrically (0.5–5 × 10?5 M) or spectrofluorimetrically (1–10 × 10?6 M). The relative standard deviations were 1.8% for the determination of 5 × 10?6 M iodide (n = 5) by spectrofluorimetry and 2.3% (n = 50) for 1 × 10?5 M iodide by spectrophotometry. Periodate, iodate and iodine responded exactly as iodide.  相似文献   

7.
The kinetics of the atmospherically important gas-phase reactions of acenaphthene and acenaphthylene with OH and NO3 radicals, O3 and N2O5 have been investigated at 296 ± 2 K. In addition, rate constants have been determined for the reactions of OH and NO3 radicals with tetralin and styrene, and for the reactions of NO3 radicals and/or N2O5 with naphthalene, 1- and 2-methylnaphthalene, 2,3-dimethylnaphthalene, toluene, toluene-α,α,α-d3 and toluene-d8. The rate constants obtained (in cm3 molecule?1 s?1 units) at 296 ± 2 K were: for the reactions of O3; acenaphthene, <5 × 10?19 and acenaphthylene, ca. 5.5 × 10?16; for the OH radical reactions (determined using a relative rate method); acenaphthene, (1.03 ± 0.13) × 10?10; acenaphthylene, (1.10 ± 0.11) × 10?10; tetralin, (3.43 ± 0.06) × 10?11 and styrene, (5.87 ± 0.15) × 10?11; for the reactions of NO3 (also determined using a relative rate method); acenaphthene, (4.6 ± 2.6) × 10?13; acenaphthylene, (5.4 ± 0.8) × 10?12; tetralin, (8.6 ± 1.3) × 10?15; styrene, (1.51 ± 0.20) × 10?13; toluene, (7.8 ± 1.5) × 10?17; toluene-α,α,α-d3, (3.8 ± 0.9) × 10?17 and toluene-d8, (3.4 ± 1.9) × 10?17. The aromatic compounds which were observed to react with N2O5 and the rate constants derived were (in cm3 molecule?1 s?1 units): acenaphthene, 5.5 × 10?17; naphthalene, 1.1 × 10?17; 1-methylnaphthalene, 2.3 × 10?17; 2-methylnaphthalene, 3.6 × 10?17 and 2,3-dimethylnaphthalene, 5.3 × 10?17. These data for naphthylene and the alkylnaphthalenes are in good agreement with our previous absolute and relative N2O5 reaction rate constants, and show that the NO3 radical reactions with aromatic compounds proceed by overall H-atom abstraction from substituent-XH bonds (where X = C or O), or by NO3 radical addition to unsaturated substituent groups while the N2O5 reactions only occur for aromatic compounds containing two or more fused six-membered aromatic rings.  相似文献   

8.
Rate constants have been determined at 296 ± 2 K for the gas phase reaction of NO3 radicals with a series of aromatics using a relative rate technique. The rate constants obtained (in cm3 molecule?1 s?1 units) were: benzene, <2.3 × 10?17; toluene, (1.8 ± 1.0) × 10?17; o? xylene, (1.1 ± 0.5) × 10?16; m? xylene, (7.1 ± 3.4) × 10?17; p? xylene, (1.4 ± 0.6) × 10?16; 1,2,3-trimethylbenzene, (5,6 ± 2.6) × 10?16; 1,2,4-trimethylbenzene (5.4 - 2.5) × 10?16; 1,3,5-trimethylbenzene, (2.4 ± 1.1) × 10?16; phenol, (2.1 ± 0.5) × 10?12; methoxybenzene, (5.0 ± 2.8) × 10?17; o-cresol, (1.20 ± 0.34) × 10?11; m-cresol, (9.2 ± 2.4) × 10?12; p-cresol, (1.27 ± 0.36) × 10?11; and benzaldehyde, (1.13 ± 0.25) × 10?15. These kinetic data, together with, in the case of phenol, product data, suggest that these reactions proceed via H-atom abstraction from the substituent groups. The magnitude of the rate constants for the hydroxy-substituted aromatics indicates that the nighttime reaction of NO3 radicals with these aromatics can be an important loss process for both NO3 radicals and these organics, as well as being a possible source of nitric acid, a key component of acid deposition.  相似文献   

9.
Charge transport properties in thin films of Poly(2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylenevinylene) (MDMO PPV) cast using either chloroform (CF), toluene (TOL), or chlorobenzene (CB) as solvent were investigated. Hole mobility (μ) in these thin films measured using time‐of‐flight transient photoconductivity showed an increasing trend with respect to the solvent used in the same order, that is, μCF (2.4 × 10?7 cm2/Vs) < μTOL (6.9 × 10?7 cm2/Vs) < μCB (2.3 × 10?6 cm2/Vs). Observed variations in mobilities were attributed to different morphologies of MDMO PPV chains in thin films cast using the aforesaid solvents. Nature of the interchain interactions and aggregate formation were obtained using photoluminescence (PL), Raman spectroscopy, and AFM studies. Ratio of PL peak intensities of 0–0 and 0–1 transitions, which is a direct measure of interchain interaction, was the highest in CB and lowest in CF. Variation in the relative intensities of out‐of‐plane wagging of vinylene group (~963 cm?1 mode) in Raman spectra suggested different extent of coiling of polymer chains in these thin films. From these observations, it was elicited that aggregate size and interchain interactions are highest in CB and least in CF. AFM‐based topographic images of thin films further supported these variations in the size of aggregates. Variation in the aggregate sizes and interchain interactions explained the corresponding variation in the mobility. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1431–1439  相似文献   

10.
The rate constant for the bimolecular combination of benzyl radicals in cyclohexane and toluene is determined as a function of temperature. Further, it is studied in cyclohexane–toluene mixtures of different compositions. In the entire range covered, 9.8 × 108 ? 2kt ? 9.0 × 109M?1·sec?1, the data are very well described by the Smoluchowski equation for a diffusion-controlled reaction to ground-state products using a spin statistical factor of 1/4, a temperature- and solvent-independent reaction distance, and the known diffusion coefficient of toluene.  相似文献   

11.
《Analytical letters》2012,45(7):531-534
Abstract

The sulfate ion is extracted into toluene with nonionic surfactant span 20 and crystal violet. A linear calibration curve was obtained between the absorbance due to crystal violet in the extract and sulfate concentrations over the range 2.5 × 10?5 to 2.5 × 10?4 mol 1?1 (2.4 to 24 ppm) in the aqueous phase.  相似文献   

12.
The host–guest interaction of tolmetin (TOL) with β-cyclodextrin (β-CD) and the influence of human serum albumin (HSA) on the formation of the inclusion complex were studied by 1D and 2D NMR spectroscopy. The TOL/β-CD inclusion complex formed at a molar ratio of 1:1 with a binding constant value of 2164.5 L·mol?1. Data analysis showed that the addition of 10 μmol·L?1 of HSA weakened the strength of TOL binding to β-CD (K a = 1493 L·mol?1). The interaction of TOL with HSA in the absence and presence of β-CD was studied by analyzing the fluorescence quenching data. The Stern–Volmer quenching constants and the binding constants are found to be smaller in the presence of β-CD, suggesting that β-CD hinders the strong interaction of TOL with HSA by complex formation. Additionally, the presence of β-CD does not induce conformational and microenvironmental changes on HSA.  相似文献   

13.
Ultrasonic (70 W, 20 kHz) solution (2%) degradations of poly(alkyl methacrylates) have been carried out in toluene at 27°C and in tetrahydrofuran (THF) at -20°C. Mw and Mn of all polymers (before and after sonification) were computed from GPC. Irrespective of the alkyl substituent, Mw decreased rapidly at first and then slowly approached limiting values. All Mw/Mn ratios were in the vicinity of 1.5 at the limiting chain lengths. For identical Mn, the rate constants k were (4.2 ± 2.0) × 10?6 min?1 in toluene at 27°C and (5.4 ± 2.0) × 10?6 min?1 in THF at -20°C. For poly(isopropyl methacrylate) and poly(octadecyl methacrylate) with higher, but identical, Mn,0, k values were higher ((9.0 ± 1.0) × 10?6 min?1 at 27°C and (18.0 ± 1.5) × 10?6 min?1 at -20°C). This suggests that Mn,0 and not the bulk size of the alkyl substituents is the factor that determines the rate of degradation. Lowering of the temperature accelerates degradation due primarily to lower chain mobility of poly-(alkyl methacrylates) and enhanced cavitation. The average number of chain scissions ([(Mn)0/(Mn)t] - 1) calculated from component degradation data are much higher than those obtained with overall Mn,t values.  相似文献   

14.
The molecular dimensions of polydipropylsiloxamer were studied by intrinsic viscosity measurements in toluene and in 2-pentanone. The relationships between the molecualr weight and the intrinsic viscosity were found to be: [η]25°C., toluene = 4.35 × 10?4 M0.58; [η]θ(10°C.), toluene = 1.09 × 10?3 M0.5; [η]θ(76°C.), 2-pentanone = 8.71 × 10?4 M0.5. This held reasonably well for molecular weights from 25,000 to 3000,000. The root-mean-square end-to-end length ratio, (r02 /M)1/2 as calculated from the constant K, exceeds the free rotation value by approximately 100%. The disparity is greater than that found with polydimethylsiloxamer, indicating a lower degree of flexibility for the polydipropylsiloxamer. This is largely due to the short range steric interaction between near neighboring units of the chain. Gel permeation chromatography was also employed to demonstrate the lower degree of flexibility for polydipropylsiloxamer as compared with polydimethylsiloxamer.  相似文献   

15.
The temperature dependence of the rate coefficients for the OH radical reactions with toluene, benzene, o-cresol, m-cresol, p-cresol, phenol, and benzaldehyde were measured by the competitive technique under simulated atmospheric conditions over the temperature range 258–373 K. The relative rate coefficients obtained were placed on an absolute basis using evaluated rate coefficients for the corresponding reference compounds. Based on the rate coefficient k(OH + 2,3-dimethylbutane) = 6.2 × 10?12 cm3 molecule?1s?1, independent of temperature, the rate coefficient for toluene kOH = 0.79 × 10?12 exp[(614 ± 114)/T] cm3 molecule?1 s?1 over the temperature range 284–363 K was determined. The following rate coefficients in units of cm3 molecule?1 s?1 were determined relative to the rate coefficient k(OH + 1,3-butadiene) = 1.48 × 10?11 exp(448/T) cm3 molecule?1 s?1: o-cresol; kOH = 9.8 × 10?13 exp[(1166 ± 248)/T]; 301–373 K; p-cresol; kOH = 2.21 × 10?12 exp[(943 ± 449)/T]; 301–373 K; and phenol, kOH = 3.7 × 10?13 exp[(1267 ± 233)/T]; 301–373 K. The rate coefficient for benzaldehyde kOH = 5.32 × 10?12 exp[(243 ± 85)/T], 294–343 K was determined relative to the rate coefficient k(OH + diethyl ether) = 7.3 × 10?12 exp(158/T) cm3 molecule?1 s?1. The data have been compared to the available literature data and where possible evaluated rate coefficients have been deduced or updated. Using the evaluated rate coefficient k(OH + toluene) = 1.59 × 10?12 exp[(396 ± 105)/T] cm3 molecule?1 s?1, 213–363 K, the following rate coefficient for benzene has been determined kOH = 2.58 × 10?12 exp[(?231 ± 84)/T] cm3 molecule?1 s?1 over the temperature range 274–363 K and the rate coefficent for m-cresol, kOH = 5.17 × 10?12 exp[(686 ± 231)/T] cm3 molecule?1 s?1, 299–373 K was determined relative to the evaluated rate coefficient k(OH + o-cresol) = 2.1 × 10?12 exp[(881 ± 356)/T] cm3 molecule?1 s?1. The tropospheric lifetimes of the aromatic compounds studied were calculated relative to that for 1,1,1-triclorethane = 6.3 years at 277 K. The lifetimes range from 6 h for m-cresol to 15.5 days for benzene. © 1995 John Wiley & Sons, Inc.  相似文献   

16.
The electrochemical degradation of tetracycline hydrochloride (TeC) was comparatively investigated in artificial urine and chloride-containing media using a one-compartment filter-press flow cell composed of a Ti/Ru0.3Ti0.7O2 dimensionally stable anode. The effect of the current density (10–40 mA cm?2) on the removal levels attained for TeC and total organic carbon (TOC) (in both media), as well as for urea and creatinine in artificial urine medium, was assessed. The TeC removal rate in the artificial urine medium was much lower than in chloride-containing medium, probably due to the higher consumption of the electrogenerated active chlorine species by the urea and creatinine in the artificial urine medium. Moreover, the obtained removal levels for the urea and creatinine were negligible at current densities lower than 30 mA cm?2. As TOC abatement was also very small, it is possible that TeC oxidation leads to intermediate compounds. Thus, if current densities less than 20 mA cm?2 are applied, TeC can be selectively removed.  相似文献   

17.
The effect of a range of 10 organic nitriles on the radiation-induced polymerization of styrene was studied. A dose rate of 4.4 rad s?1 was used. A rate of polymerization of styrene (1.744 mol L?1 of toluene solution) of 5.0 × 10?7 mol L?1 s?1 was found. With organic nitriles present (styrene:nitrile ratio of 1:0.28) the rate of polymerization increased. Rates in the range of 5.5 × 10?7 ?5.2 × 10?6 mol L?1 s?1, depending on the nitrile present, were obtained. The polymers were partially characterized and evidence of involvement of each of the nitriles in the polymer chains was revealed. The increase in rate of polymerization has been attributed to the part played by nitrile radicals in the initiation of styrene polymerization. Radical yield values [as G(nitrile radical)] were derived from the relevant rate expressions. Values ranged from 2.7 to 49.5, depending on the particular nitrile. Corresponding values of G(nitrile radical) in the range of 5.1–129.4 were obtained by the manipulation of number-average molar mass data. Values of kpkt of approximately 2 × 10?5 L mol?1 s?1 were found. Trommsdorff types of effect are absent from these systems.  相似文献   

18.
The photocatalytic oxidation of diclofenac, metoprolol, estrone and chloramphenicol was tested in the tube reactor using different commercially available TiO2. The photocatalysts were characterized using BET, XRD and SEM. The studied photocatalysts differed in SBET, pore volume and rutile presence. It was observed that generally anatase TiO2 possessed the highest activity in the photocatalytic oxidation of diclofenac, chloramphenicol and estrone. The presence of rutile enhanced the photooxidation of metoprolol. In case of the other pollutants, however, rutile diminished the photooxidation efficiency. The most effective in the reduction of the COD parameter of treated water was anatase with 21 nm crystals. The photooxidation of all studied pollutants can be described by the pseudo-first order kinetics with the values ranging from 0.46 × 10?2 min?1 in case of estrone removal over Tytanpol (Z.A. Police, Poland) to 1.87 × 10?2 min?1 for the removal of chloramphenicol over TiO2 21 nm (Sigma-Aldrich). The highest initial reaction rates were obtained for metoprolol removal over TiO2 21 nm (Sigma-Aldrich) 1.9 × 10?6 mol dm3 min?1 being three times higher than that determined for estrone photocatalytic oxidation over TiO2 (Sigma-Aldrich).  相似文献   

19.
The rate constants of self-reactions of ketyl radicals of acetophenone in n-heptane [2k = (3.2 ± 0.5) × 109 M?1 s?1] and diphenylaminyl radicals in toluene [2k = (3.3 ± 0.5) × 107 M?1 s?1] have been determined at 298 K using the flash photolysis technique. The rate constant of ketyl radicals is equal to the calculated diffusion constant and, therefore, this reaction is diffusion-controlled. The aminyl radical recombination rate is independent of the viscosity of the toluene/vaseline oil binary mixture (0.55 ? η ? 12 cP) and this reaction is activation-controlled. Reactivity anisotropy averaging due to the cage effect has been considered for ketyl and some other radicals. On the basis of the analysis it has been proposed that ketyl recombination involves formation of not only pinacol, but also iso-pinacols.  相似文献   

20.
Abstract

Chromatographic methods for the determination of toluene diisocyanates (TDI) in air, at concentrations of 20–40μg/m3, were evaluated. Test atmospheres were generated by a gas-phase permeation principle. The GC method was based on sampling in impingers containing an acidic aqueous solution (0.4 M HC1), where the isocyanates are hydrolysed into the corresponding amines. The pentafiuoropropionic acid derivatives of the amines were analysed using glass capillary GC with thermionic detection. The HPLC methods were based on reaction with the amine reagents 9-(N-methylaminomethyl)-anthracene (1 × 10?4M in toluene) and 1-(2-methoxyphenyl)-piperazine (2 × 10?4M in toluene). The urea derivatives were determined using UV detection. The sampling efficiency for gaseous TDI with toluene as absorbing solution was 97%. Sampling efficiencies in various acidic aqueous solutions were 83–88%. The relative standard deviation for the various methods was ca. 6%. No sampling losses for TDI, due to influences of interfering substances (diethylamine, dimethylethylamine, N-methylmorpholine, DABCO, aniline, ethanol, phenol) using acidic aqueous 0.4 M HC1 were obtained. Diethylamine, N-methylmorpholine and DABCO affected the analytical results when toluene solutions of the amine reagents MAMA and MPP were used.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号