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 890 毫秒
1.
The aqueous polymerization of MMA was studied kinetically at 40° C using low concentrations of Py-SO2 complex as initiator. For [Py-SO2] < 2 × 10?2 mol/L, Rp ∞ [PY-SO2]0.5 [M]1.5, and for [Py-SO2] > 2 × 10?2 mol/L, Rp ∞ [Py-SO2]0,0[M]1.08. Polymerization is considered to proceed by a radical mechanism. The radical generation or the initiation step is believed to proceed through equilibrium complexation between the Py-SO2 complex and monomer molecules. For [Py-SO2] < 2 × 10?2 mol/L, the polymerization is characterized by bimolecular termination. Above this [Py-SO2], chain termination by a degradative initiator transfer process assumes prominence.  相似文献   

2.
Benzil (BZL)-dimethylaniline (DMA) exciplex interaction has been utilized to initiate the photopolymerization of methyl methacrylate at 40°C in bulk and in solution. Depending on the nature of the solvent used, the monomer exponent values varied between 0.47 to 2.76. Initiator exponent values were found to be 0.29 and 0.15 with respect to [BZL] and [DMA], respectively. A low value of kp 2/kt and the high initiator transfer constant values indicated significant initiator-dependent termination. The semipinacol radical formed during irradiation is thought to be mainly responsible for primary radical termination while the generated ion radicals are presumed to participate in degradative initiator transfer.  相似文献   

3.
Free radical photopolymerization of methyl methacrylate (MMA) in visible light was studied at 40°C using sulfur dioxide-halogen (Cl2, Br2, and I2) combinations as photoinitiators. Of the three SO2/halogen systems, only the SO2/Br2 combination formed an interesting initiating system due to 1:1 complexation between the two components resulting in pronounced enhancement of the rate of photopolymerization over those produced by each of the initiator components when used as a lone photoinitiator. Photopolymerization of MMA induced by (SO2-Br2) complex (1:1) as the photoinitiator exhibited a low initiator exponent value, 0.26, and a monomer exponent value of 1.5. Kinetic nonidealities were explained on the basis of (a) monomer-dependent chain initiation and (b) significant initiator-dependent chain termination along with the usual bimolecular mode of chain termination.  相似文献   

4.
Two chemosensors 4H‐1‐benzopyran‐3‐carboxaldehyde, 4‐oxo‐, 3‐(2‐phenylhydrazone), [I1] and 4H‐1‐benzopyran‐3‐carboxaldehyde, 4‐oxo‐, 3‐[2‐(2,4‐dinitrophenyl)hydrazone], [I2] with hydrazone‐NH group as binding site have been shown excellent selectivity for arsenite ion. It is confirmed by the UV‐vis titration that I2 is more selective than I1. The performance of the coated graphite electrode (CGE) was found to be better than polymeric membrane electrode (PME) in terms of linear range of 4.89×10?7–1.0×10?1 mol L?1, low detection limit of 8.31×10?8 mol L?1 and short response time. The proposed sensors were also used to determine the arsenite ion in different water samples.  相似文献   

5.
A simple and reliable novel kinetic method for the determination of piroxicam (PX) was proposed and validated. For quantitative determination of PX, the Bray-Liebhafsky (BL) oscillatory reaction was used in a stable non-equilibrium stationary state close to the bifurcation point. Under the optimized reaction conditions (T = 55.0°C, [H2SO4]0 = 7.60×10?2 mol L?1, [KIO3]0 = 5.90×10?2 mol L?1, [H2O2]0 = 1.50×10?1 mol L?1 and j 0 = 2.95×10?2 min?1), the linear relationship between maximal potential shift ΔE m , and PX concentration was obtained in the concentration range 11.2–480.5 μg mL?1 with a detection limit of 9.9 μg mL?1. The method had a rather good sample throughput of 25 samples h?1 with a precision RSD = 4.7% as well as recoveries RCV ≤ 104.4%. Applicability of the proposed method to the direct determination of piroxicam in different pharmaceutical formulations (tablets, ampoules and gel) was demonstrated.   相似文献   

6.
The presence of ceric and bromide ions catalyzes the isomerization of maleic acid (MA) to fumaric acid (FA) in aqueous sulfuric acid. A kinetic study of this bromine-catalyzed reaction was carried out. The reaction between ceric ion and maleic acid is first order with respect to Ce(IV). For [Ce(IV)]0=5.0×10?4 M, [H2SO4]0=1.2 M, μ=2.0 M (adjusted by NaClO4), and [MA]0=(0.5–1.0)M, the observed pseudo-first-order rate constant (k03) at 25° is k03=7.622×10?5 [MA]0/(1+0.205[MA]0). The reaction between ceric and bromide ions is first order with respect to Ce(IV). For [Ce(IV)]0=5.0×10?4 M, [H2SO4]0=1.2 M, μ=2.0 M, and [Br?]0=(0.025–0.150)M, the pseudo-first-order rate constant (k02) at 25° is k02= (4.313±0.095)x10?2[Br?]2+(2.060±0.119)x10?3[Br?]. The reaction of Ce(IV) with maleic acid and bromide ion is also first order with respect to Ce(IV). For [Ce(IV)]0=5.0×10?4 M, [MA]0=0.75 M, [H2SO4]0=1.2 M, μ=2.0 M, and [Br?]0= (0.025–0.150)M, the pseudo-first-order rate constant (k03) at 25° is k03= (5.286±0.045)x10?2[Br?]2+(3.568±0.056)x10?3[Br?]. For [Ce(IV)]0=5.0 × 10?4 M, [Br?]0=0.050 M, [H2SO4]0=1.2 M, μ=2.0 M, and [MA]0=(0.15–1.0)M at 25°, k03=(2.108×10?4+2.127×10?4[MA]0)/(1+0.205[MA]0). A mechanism is proposed to rationalize the results. The effect of temperature on the reaction rate was also studied. The energy barrier of Ce(IV)—Br? reaction is much less than that of Ce(IV)—MA reaction. Maleic and fumaric acids have very different mass spectra. The mass spectrum of fumaric acid exhibits a strong metastable peak at m/e 66.5.  相似文献   

7.
《Electroanalysis》2005,17(23):2129-2136
The investigation of the dissolved iron(III)–nitrilotriacetate–hydroxide system in the water solution (I=0.1 mol L?1 in NaClO4; pH 8.0±0.1) using differential pulse cathodic voltammetry, cyclic voltammetry, and sampled direct current (DC) polarography, was carried out on a static mercury drop electrode (SMDE). The dissolved iron(III) ion concentrations varied from 2.68×10?6 to 6×10?4 mol L?1 and nitrilotriacetate concentrations were 1×10?4 and 5×10?4 mol L?1. By deconvoluting of the overlapped reduction voltammetric peaks using Fourier transformation, four relatively stable, dissolved iron(III) complex species were characterized, as follows: [Fe(NTA)2]3?, mixed ligand complexes [FeOHNTA]? and [Fe(OH)2NTA]2?, showing a one‐electron quasireversible reduction, and binuclear diiron(III) complex [NTAFeOFeNTA]2?, detected above 4×10?4 mol L?1 of the added iron(III) ions, showing a one‐electron irreversible reduction character. The calculations with the constants from the literature were done and compared with the potential shifts of the voltammetric peaks. Fitting was obtained by changing the following literature constants: log β2([Fe(NTA)2]3?) from 24 to 27.2, log β1([FeNTA]?) from 8.9 to 9.2, log β2([Fe(NTA)2]4?) from 11.89 to 15.7 and log β2([Fe(OH)2NTA]3?) from 15.63 to 19. The determination of the electrochemical parameters of the mixed ligand complex [FeOHNTA]?, such as: transfer coefficient (α), rate constant (ks) and formal potential (E°') was done using a sampled DC polarography, and found to be 0.46±0.05, 1.0±0.3×10?3 cm s?1, and ?0.154±0.010 V, respectively. Although known previously in the literature, these four species have now for the first time been recorded simultaneously, i.e. proved to exist simultaneously under the given conditions.  相似文献   

8.
The structure and complex formation of concentrated aqueous gallium(III) bromide (GaBr3) solutions have been investigated over a temperature range 80–333 K by Raman spectroscopy, X-ray absorption fine structure (XAFS), and X-ray diffraction. The Raman spectra obtained at various [Br?]/[Ga3+] molar ratios and temperatures have shown that complex formation between Ga3+ and Br? occurs as a predominant species, with [GaBr4]? at [Ga3+] as high as 1~2 M (M = mol?dm ?3) and [Br?]/[Ga3+] ratios > ~2, and that cooling of the solutions favors the formation of the aqua Ga3+. The intermediate species were not seen in the Raman spectra. The XAFS data have revealed that the aqua complex has a sixfold coordination as [Ga(H2O)6]3+ with a Ga3+–H2O distance of (1.96 ± 0.02) Å, whereas the [GaBr4]? complex has a Ga3+–Br? distance of (2.33± 0.02) Å, and that vitrification of the aqueous GaBr3 solution at liquid nitrogen temperature shifts the equilibrium toward the aqua complex. The X-ray diffraction data at different subzero temperatures have shown a tendency of decreasing Ga3+–Br? and increasing Ga3+–H2O interactions with lowering temperature, confirming the preference of aqua Ga3+ in the supercooled liquid state as well as in the glassy state. The Ga3+–H2O distance of ~1.8 Å for the tetrahedral coordination was found in a 2.01 M gallium(III) bromide solution with a [Br?]/[Ga3+] ratio of 3.7 and gradually increased to a value of 1.92 Å for octahedral geometry with decreasing temperature, suggesting that equilibrium shifts from [GaBr4]? to [Ga(H2O)6]3+ through intermediate species, [GaBr n ](3?n)+ (n = 2 and 3). The Ga3+–Br? and Br?–Br? distances within [GaBr4]? with an almost tetrahedral symmetry are (2.35± 0.02) and (3.82± 0.03) Å, respectively. The Ga3+ has the second hydration shell at (4.03± 0.03) Å and the hydration of Br? is characterized with a Br?–H2O distance of (3.35± 0.02) Å at all temperatures investigated.  相似文献   

9.
以[Mn(H_2P_2O_7)_3]~(3-)为引发剂,研究了丙烯腈与玉米淀粉的接枝共聚反应。由实验结果求出了反应速率与引发剂浓度、单体浓度、淀粉浓度和反应温度的关系,推导并验证了接枝反应动力学模型,探讨了反应机理,求得了接枝反应活化能。  相似文献   

10.
Kinetics of Bz2O2-initiated polymerization of VAC in pyridine at 60° were investigated. The polymerization was significantly retarded by pyridine. The monomer exponent decreased from 2.5 at a relatively low [Bz2O2] (1.0 × 10?2 M) to 2.0 at [Bz2O2] ? 4.0 × 10?2 M. The observed kinetic features were explained on the basis of degradative chain transfer and copolymerization with pyridine.  相似文献   

11.
Phenyliododichloride, C6H5IC12, can induce photopolymerization of methyl methacrylate almost instantaneously at 40°C under visible light. The initiator order and monomer order were 0.3 and close to 1.5, respectively, for [C6H5IC12] < 5.0 × lo?4 mol/L while the corresponding values were 0 and 1.0, respectively, for [C6H5IC12] > 5.0 × 10?4 mol/L. Kinetic and other data indicate a radical polymerization mechanism that involves complexation of a monomer molecule with C6H5IC12 prior to the radical generation step. Termination appears to take place both by a bimolecular mechanism and by a degrada-tive initiator transfer mechanism at low [C6H5IC12], but it appears to take place almost exclusively by the latter mechanism when [CeH5ICl2] is high.  相似文献   

12.
Photopolymerization of methyl methacrylate in bulk and in solution at 40° using triethylamine nitrobenzene (TEA-NB) complex as photoinitiator was studied kinetically. Initiator order x, given by the relation Rpα([TEA][NB])x, was 0.28 for [TEA][NB] < 25 × 10 ?8 mol2 · l?2; for higher values of [TEA][NB], x was practically zero. Monomer order was 1.1 in benzene and pyridine but much less than unity (0.65–0.70) in carbon tetrachloride and chloroform. Kinetic analysis indicated that the initiation process was monomer and solvent dependent. The halomethane solvents enhanced the polymerization rate through their active participation in the initiation or radical-generation steps. End-group analysis indicated incorporation of basic (amino) end-groups in the polymers. The kinetic non-ideality was explained on the basis of significant initiator-dependent termination through primary radicals or via degradative transfer to initiator.  相似文献   

13.
The construction and general performance characteristics of two poly(vinyl chloride) matrix chemical sensors for lead were described. These sensors were based on the use of ion association complexes of trihydroxoplumbate, [Pb(OH)3]? and tetraiodoplumbate, [PbI4]2?with cetylpyridinium chloride (CP) and iron(II)‐4,7‐bathophenanthroline [Fe(bphen)3]2+ as novel electroactive materials dispersed in o‐nitrophenyloctyl ether (o‐NPOE) plasticizer for ionometric sensor controls, respectively. The sensing membrane (3×5 mm) is immobilized on a wafer polyimide chip (size 13.5×3.5 mm) to offer a planar miniaturized design that could be easily used flow injection system. Under static modes of operation, the sensors revealed a near Nernstian response over a wide Pb2+ ion concentration range 7.9×10?7 to 10?4 and 3.2×10?7 to 10?4 mol L?1 with detection limit of 100 and 45.5 ng mL?1, respectively . In flow injection potentiometry, excellent reproducibility (RSD%=0.5%), fast response, high sensitivity, high sampling rate (50 sample h?1) and stable baseline was observed in the presence of 5×10?2 mol L?1 NaOH and 10?1 mol L?1 KI as a carrier for [CP][Pb(OH)3] and [Fe(bphen)3][PbI4] membrane based sensors, respectively. Validation of the assay method according to the quality assurance standards (range, within‐day repeatability, between‐day variability, standard deviation, accuracy, lower detection limit) reveals good performance characteristics and suggests application for routine determination of lead in industrial wastewaters and stack emissions of lead smelters. The results agree fairly well with data obtained by the standard atomic absorption methods.  相似文献   

14.
The kinetics of the bromate oxidation of tris(1,10-phenanthroline)iron(II) (Fe(phen)32+) and aquoiron(II) (Fe2+ (aq)) have been studied in aqueous sulfuric acid solutions at μ = 1.0M and with Fe(II) complexes in great excess. The rate laws for both reactions generally can be described as -d [Fe(II)]/6dt = d[Br?]/dt = k[Fe(II)] [BrO?3] for [H+]0 = 0.428–1.00M. For [BrO?3]0 = 1.00 × 10?4M. [Fe2+]0 = (0.724–1.45)x 10?2 M, and [H+]0 = 1.00M, k = 3.34 ± 0.37 M?1s?1 at 25°. For [BrO?3]0 = (1.00–1.50) × 10?4M, [Fe2+]0 = 7.24 × 10?3M ([phen]0 = 0.0353M), and [H+]0 = 1.00M, k = (4.40 ± 0.16) × 10?2 M?1s?1 at 25°. Kinetic results suggest that the BrO?3-Fe2+ reaction proceeds by an inner-sphere mechanism while the BrO?3-Fe(phen)32+ reaction by a dissociative mechanism. The implication of these results for the bromate-gallic acid and other bromate oscillators is also presented.  相似文献   

15.
Abstract

Self-assembly of ZnX2 (X?=?Cl, Br, and I) with 2,7-bis(isonicotinoyloxy)naphthalene (L) in a mixture of ethanol and dichloromethane yields 1-D zigzag chains of [ZnX2L·2CH2Cl2]n composition. The 1-D chains form an ensemble constituting hydrophobic suprachannels of 4.0–4.4?×?4.4–5.0 Å2 with repeat units of ZnL for [ZnCl2L] and [ZnBr2L], and those of 5.2?×?12.0 Å2 with repeat units of Zn2L2 for [ZnI2L] in the appropriate arrays via C–H···π and π···π interactions. The most interesting feature is that alcohol molecules are not incorporated into the haloalkane-philic channels. That is, the channels discriminate haloalkanes from alcohols. Furthermore, the exchange of solvate molecules in a crystalline state indicates that the unique channels show different absorptions of haloalkanes such as CH2Cl2, CH2Br2, CH2I2, CHCl3, 1,2-dichloroethane, and 1,2-dibromoethane.  相似文献   

16.
《Electroanalysis》2005,17(11):1003-1007
A novel PVC membrane ion‐selective electrode based on tribenzyltin(IV) dithiocarbamate [Sn(IV)–TBDTB] as neutral carrier was developed for thiocyanate (SCN?) determination. The electrode exhibits a near‐Nernstian response for SCN? with a slope of 62.8±2.0 mV per decade over a wide concentration range 1.0×10?1–2.0×10?6 mol L?1 and a detection limit of 1.0×10?6 mol L?1 in MES–NaOH buffer, pH 6.0, at 25 °C. The electrode prepared with 1.5 wt.% Sn(IV)–TBDTB, 32.5 wt.% PVC and 66.0 wt.% 2‐nitrophenyloctyl ether (o‐NPOE) shows optimal response characteristics. Anti‐Hofmeister selectivity sequence for a series of anions shown by the electrode was as follows: SCN?>Sal?>I?>ClO >phCOO?>CH3COO?>Br?>Cl?>NO >NO >Citrate>SO42?. The useful pH range for the electrode was found to be 3–7 with a response time 30–40 s. The electrode has been used for direct determination of thiocyanate in wastewater with satisfactory results.  相似文献   

17.
The reaction of H2[OsBr6] with DMSO in ethanol solution resulted in DMSO complex [H(dmso-O)2][OsIII(dmso-S)2Br4] (1) described previously as an intermediate product in the reaction of K2[OsBr6] with DMSO and characterized by EAS and ESR spectra. The coordination of DMSO molecules was established by IR and 1H and 13C NMR spectroscopy. The oxidation state of osmium and trans arrangement of DMSO molecules in the anion were established by ESR. The behavior of complex 1 in solutions was studied by EAS, ESR, and mass-spectrometry: a displacement of Br? ions accompanied by the reduction of osmium to oxidation state +2 occurs in DMSO, a solvation with displacement of DMSO molecules is observed at the first stage in water and methanol (rate constants 2.3 × 10?4 and 1.7 × 10?3 s?1, respectively), the sequential substitution of DMSO molecules and osmium oxidation to form [OsIVBr6]2? ions takes place in 4 mol/L HBr.  相似文献   

18.
A novel [Ru(bpy)2(dcbpy)NHS] labeling/aptamer‐based biosensor combined with gold nanoparticle amplification for the determination of lysozyme with an electrochemiluminescence (ECL) method is presented. In this work, an aptamer, an ECL probe, gold nanoparticle amplification, and competition assay are the main protocols employed in ECL detection. With all the protocols used, an original biosensor coupled with an aptamer and [Ru(bpy)2(dcbpy)NHS] has been prepared. Its high selectivity and sensitivity are the main advantages over other traditional [Ru(bpy)3]2+ biosensors. The electrochemical impedance spectroscopy (EIS) and atomic force microscopy (AFM) characterization illustrate that this biosensor is fabricated successfully. Finally, the biosensor was applied to a displacement assay in different concentrations of lysozyme solution, and an ultrasensitive ECL signal was obtained. The ECL intensity decreased proportionally to the lysozyme concentration over the range 1.0×10?13–1.0×10?8 mol L?1 with a detection limit of 1.0×10?13 mol L?1. This strategy for the aptasensor opens a rapid, selective, and sensitive route for the detection of lysozyme and potentially other proteins.  相似文献   

19.
Two novel potentiometric azide membrane sensors based on the use of manganese(III)porphyrin [Mn(III)P] and cobalt(II)phthalocyanine [Co(II)Pc] ionophores dispersed in plasticized poly(vinyl chloride) PVC matrix membranes are described. Under batch mode of operation, [Mn(III)P] and [Co(II)Pc] based membrane sensors display near‐ and sub‐Nernstian responses of ?56.3 and ?48.5 mV decade?1 over the concentration ranges 1.0×10?2?2.2×10?5 and 1.0×10?2?5.1×10?5 mol L?1 azide and detection limits of 1.5×10?5 and 2.5×10?5 mol L?1, respectively. Incorporation of both membrane sensors in flow‐through tubular cell offers sensitive detectors for flow injection (FIA) determination of azide. The intrinsic characteristics of the [Mn(III)P] and [Co(II)Pc] based detectors in a low dispersion manifold show calibration slopes of ?51.2 and ?33.5 mV decade?1 for the concentration ranges of 1.0×10?5?1.0×10?2 and 1.0×10?4?1.0×10?2 mol L?1 azide and the detection limits are1.0×10?5 and 3.1×10?5 mol L?1, respectively. The detectors are used for determining azide at an input rate of 40–60 samples per hour. The responses of the sensors are stable within ±0.9 mV for at least 8 weeks and are pH independent in the range of 3.9?6.5. No interferences are caused by most common anions normally associated with azide ion.  相似文献   

20.
《Electroanalysis》2006,18(21):2070-2078
A highly selective potentiometric sensor for thiocyanate ion based on the use of a newly synthesized organo‐palladium ion exchanger complex dispersed in a plasticized poly(vinyl chloride) membrane is described. The sensor displays a Nernstian response (?57.8±0.2 mV decade?1) over a wide linear concentration range of thiocyanate (1.0×10?6–1.0×10?1 mol L?1 ), low detection limit (6.3×10?7 mol L?1), fast response (20 s), stable potential readings (±0.4 mV), good reproducibility (±0.9%), long term stability (8 weeks), high precision (±0.7%) and applicability over a wide pH range (4–10). Negligible interferences are caused by F?, Cl?, I?, Br?, NO3?, NO2?, CN?, SO42?, S2O32?, PO43?, citrate, acetate and oxalate ions. Under hydrodynamic mode of operation (FIA), the calibration slope is ?51.1±0.1 mV decade?1, the linear response range is 1.0×10?5–1.0×10?1 mol L?1 SCN? and the sample throughput is 40–45 per hour. The sensor is satisfactory used for manual and flow injection potentiometric determination of SCN? in the saliva and urine of cigarette smokers and non smokers. The data agree fairly well with results obtained by the standard spectrophotometric technique. Direct potentiometry and potentiometric titration of SCN? with Ag+ are also monitored with the sensor.  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