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1.
The GHCl values of PVC foils, containing 18% of dioctylphthalate, irradiated with accelerated electrons were studied after addition of various amounts of the stabilizers: (I) ethylene glycol bis-β-aminocrotonate, (II) calcium/zinc laurate + epoxy compounds, (III) calcium/zinc stearate, (IV) dioctyltin bis(octylthioglycolate). The effect of stabilization turned out to be very good, especially when stabilizer I was used. In the case of soft PVC foils in contact with water, elution of hydrogen chloride occurs. This creates difficulties in preparing PVC foils sterilized radiatively for medical purposes, especially if the foils are expected to be in contact with water.  相似文献   

2.
The oxidation-reduction thermodynamics for the manganese(III), -(IV), and -(II) ions, and their various complexes, are reviewed for both aqueous and aprotic media. In aqueous solutions the reduction potential for the manganese(III)/(II) couple has values that range from +1.51 V vs. NHE (hydrate at pH 0) to −0.95 V (glucarate complex at pH 13.5). The Mn(IV)/(III) couple has values that range from +1.0 V (solid MnIVO3 at pH 0) to −0.04 V (tris gluconate complex at pH 13.5). With anhydrous media the propensity for the Mn(III) ion to disproportionate to solid MnIVO2 and Mn(II) ion is avoided. For aprotic systems the range of redox potentials for various manganese complexes is from +2.01 V and +1.30 for the Mn(IV)/(III) and Mn(III)/(II) couples (bis terpyridyl tri-N-oxide complex in MeCN), respectively, to −0.96 V for the Mn(IV)/(III) couple (tris 3,5,-di-tert-butylcatecholate complex in Me2SO). The redox reactions between manganese complexes and dioxygen species (O2, O2, and H2O2) also are reviewed.  相似文献   

3.
Saturated (I, ROSO3Na) and unsaturated (II, R’OSO3Na) tallow alcohol sulfates, the disodium salt ofa-sulfonated saturated tallow fatty acids (III, RCH(SO3Na)CO2Na), the sodium salt of the methyl ester ofa-sulfonated saturated tallow fatty acids (IV, RCH(SO3Na) CO2CH3), and commercial tallow soap flakes (V) were compared, singly and in combinations, as built and unbuilt solutions in soft and hard water, with respect to foam height and detergency, using four different types of standard soiled cotton. Built solutions of combinations of the two most soluble detergents, II and IV, at concentration 0.05% total active ingredient plus 0.20% builder in hard water of 300 ppm, remained perfectly clear on standing for several months. Built solutions containing I or II had the best foaming properties. The presence of soap decreased foam height. Cloths A and B showed the detergency of built solutions to be in the order I=II>IV>III>V, and all combinations containing I or II were superior detergents. With cloth C, detergents ranked in the order I=II=IV>III>V, and many combinations containing I or II with IV were synergistic. Cloth D did not distinguish sharply between detergents in built solutions in hard water. In general, detergent systems containing tallow alcohol sulfates witha-sulfo esters had the most desirable solubility, wetting, foaming, and detergent properties. Presented at the AOCS Meeting, Philadelphia, October 1966. E. Utiliz. Res. Dev. Div., ARS, USDA.  相似文献   

4.
Non-peripherally substituted cobalt 1,(4)-(tetraphenylthiophthalocyaninato) and peripherally substituted cobalt 2,(3)-(tetraphenylthiophthalocyaninato) complexes were synthesized. Redox processes were observed at E1/2 = ?1.44 V (I), ?0.39 V (II), +0.37 V (III), +0.78 V (IV) and 1.15 V (V) for the non-peripherally substituted and at E1/2 = ?1.42 V (I), ?0.57, ?0.39 V (II), +0.27 V (III), +0.79 V (IV) and +1.10 V (V) for the peripherally substituted complexes, respectively. The couples were assigned to CoIPc?2/CoIPc?3 (I), CoIIPc?2/CoIPc?2 (II), CoIIIPc?2/CoIIPc?2 (III), and CoIIIPc?1/CoIIIPc?2 (IV) using spectroelectrochemistry. The last process (V) could not be ascertained by spectroelectrochemistry but is associated with ring oxidation. Upon reduction or oxidation, the Q band of the non-peripherally substituted complex became less red shifted compared to that of its peripherally substituted counterpart.  相似文献   

5.
Biston robustum Butler, a polyphagous defoliator, multiplied on Hachijo-jima Island in 1997–1998. Based on GC-MS data of authentic standards, an analysis of a pheromone gland extract of the females indicated that it included (Z,Z)-6,9–nonadecadiene (I), (Z,Z,Z)-3,6,9–nonadecatriene (II), cis-(Z)-6,7–epoxy-9–nonadecene (III), and cis-(Z,Z)-6,7–epoxy-3,9–nonadecadiene (IV) in a ratio of 13 : 2 : 70 : 15. The structure of III was confirmed by a GC-MS analysis of another extract treated with dimethyl disulfide (DMDS). This epoxymonoene was successfully converted into the corresponding DMDS adduct that showed diagnostic ions fragmented at an epoxy ring and at thiomethoxy groups reflecting the position of an original double bond. Furthermore, the 6S,7R configuration was assigned for the epoxy ring of III by chiral HPLC analysis. Field examination of synthetic lures revealed that the two epoxy compounds (III and IV) with the 6S,7R configuration were essential components and that the two unsaturated hydrocarbons (I and II) showed a synergistic effect on male attraction.  相似文献   

6.
Abstract

A new unsymmetrical diglycolamide, N,N-di-2-ethylhexyl-N',N'-di-octyl-3-oxapentane-1,5-diamide, trivially known as di-ethylhexyl-di-octyl-diglycolamide (DEHDODGA) has been synthesized, and characterized by 1H, and 13C nmr, mass, and IR spectroscopy. Extraction behavior of 241Am(III), (152+154)Eu(III), 239Pu(III), 239Pu(IV), 233U(VI), 137Cs(I), and (85+89)Sr(II) from nitric acid medium by a solution of DEHDODGA in n-dodecane was studied, at 298–333 K. The effect of concentrations of HNO3 and DEHDODGA and of temperature on the distribution ratio (D M) was studied. Extraction of Eu(III), Am(III), Pu(III), and Pu(IV) increased with increase in nitric acid concentration, and the distribution ratio of Cs(I) was insignificant. However, the distribution ratios of U(VI) and Sr(II), though not insignificant, but was quite less compared to trivalents, and Pu(IV). The D Sr(II) increased with increase in the concentration of nitric acid, reaching a maximum at 4 M followed by decrease. The stoichiometry of Am(III) – DEHDODGA was determined by slope analysis of extraction data, and the enthalpy change accompanied by the extraction of Eu(III), Pu(III), and Am(III) was determined and reported in this article.  相似文献   

7.
In this combined experimental and theoretical study the thermal degradation of 2‐nitroazidobenzene ( I ), 2,4‐dinitroazidobenzene ( II ) and 2,4,6‐trinitroazidobenzene ( III ) to yield benzofuroxan ( IV ), 4‐nitrobenzofuroxan ( V ), and 4,6‐dinitrobenzofuroxan ( VI ) were investigated by thermoanalytical (TG, DSC) and computational methods. In contrast, furoxan formation was not observed for 4‐nitroazidobenzene ( VII ) under heating due to the para position of the nitro group in the benzene ring. All compounds were characterized by elemental analysis, vibrational (IR) spectroscopy and mass spectrometry. The crystal structure of compound III was determined by single‐crystal X‐ray diffraction. DFT‐based structure optimizations and frequency analyses were performed at the B3LYP/cc‐pVDZ level of theory. The structural parameters of the fully optimized compound III showed very good agreement with the single‐crystal X‐ray data. The enthalpies of formation for compounds I , II , III , IV , V , and VI were calculated using the complete basis set (CBS‐4M) method of Petersson and co‐workers in order to obtain accurate energies. The enthalpies of degradation for compounds I , II , and III were obtained from calculated enthalpies of formation according to the Hess Law and were compared with the experimental values, which were available from DSC analysis and were found to be in very good agreement.  相似文献   

8.
The GHCI values of γ-irradiated PVC mixtures were studied after addition of various amounts of three epoxy stabilizers: diglycidyl ether of 2,2-bis(4-hydroxy-3-methylphenyl)propane (I); diglycidyl ether of 1,1-bis(4-hydroxyphenyl)cyclohexane (II), and butyl-cis-9,10-epoxystearate (III). The results indicated that two processes are essential for the stabilization: HCI capture by the epoxy groups, and an external protective effect, due to the remaining part of the stabilizer molecule. The role of the benzene rings in stabilizers I and II, as compared with the protective effect due to the long chains of stabilizer III, is not as dominant as one would expect.  相似文献   

9.
1-Phenyl-2-acetoxy-2-methyl-propanone-1 (III) and 1-phenyl-2-methoxy-2-methyl-propanone-1 (IV) were irradiated at room temperature with 15 or 25 ns flashes of 265 nm or 347 nm light in Ar-saturated cyclohexane or benzene solution. Transient absorptions and emissions were recorded as a function of time between 300 and 550 nm. Triplet lifetimes of III in cyclohexane and benzene and of IV in p-dioxane were determined as ca. 2 μs. In contrast to the photolysis of 1-phenyl-2-hydroxy-2-methyl-propanone-1 (compound I) and of 1-[4-(2-propyl)-phenyl]-2-hydroxy-2-methyl-propanone-1 (compound II), α-cleavage occurs upon UV irradiation of III and IV to a minor or negligible extent. Triplets of III were found to react effectively with N-methyldiethanol amine, but a reaction with cyclohexane did not become noticeable. They react with O2 with k(T + O2) = 1.6 · 109 l/mol s. Triplets of IV react with cyclohexane with k(T + CH) = 8.6 · 105 l/mol s and with O2 with k(T + O2) = 1.1 · 109 l/mol s. They are inert towards p-dioxane. Photocuring of a transparent acrylate coating system yielded the following results on the basis of pendulum hardness measurements: I and II exhibit excellent initiator effectivity, III and IV are not capable of initiating curing if applied without coinitiator, e.g. N-methyldiethanol amine. In the presence of the latter III and IV exhibit satisfactory curing capability. In conclusion: the high curing effectivity of I and II is due to the high yield and the high rate of α-cleavage. III and IV do not undergo α-cleavage and therefore do not initiate curing. The curing capability of III and IV in the presence of a coinitiator is due to the formation of ketyl radicals by a hydrogen transfer mechanism.  相似文献   

10.
《分离科学与技术》2012,47(5):717-725
Abstract

Distribution coefficients (K) determined by the batch technique in acidic glycine media using Dowex 50W-X8 cation exchanger (H+?form, 100–200 mesh size) revealed that this medium can effectively be employed to separate a number of tetravalent and trivalent metal ions from bivalent metal ions. In fixed glycine (0.40 M) and varying concentration of nitric acid (0.10 to 1.0 M), a number of mixtures containing two or three metal ions were resolved on columns using about 8 g of exchanger. In 0.40 M glycine-1.0 M HNO3 medium, Th(IV)/Ce(IV) were separated from Al(III)/Fe(III)/Bi(III)/Co(II)/Ni(II)/Cu(II)/Zn(II)/Cd(II)/Hg(II)/Pb(II)/Ag(I) and also Al(III)/Bi(III) from a number of divalent metal ions. In 0.40 M glycine-0.50 M HNO3 medium, the resolution of following ternary mixtures were also achieved: Th(IV)/Ce(IV)-Al(III)/Bi(III)-Fe(III)/Co(II)/Ni(II)/Cu(II)/Zn(II)/Cd(II)/Hg(II)/Pb(II)/Ag(I). Th(IV)/Al(III)/Fe(III)/Bi(III) were also separated from other divalent metal ions in 1.60 M glycine-0.50 M HNO3 medium. The values of K, elution characteristics of metal ions, elution curves, and the results of the resolution of a number of mixtures of metal ions along with standard deviations are reported.  相似文献   

11.
Molten bisulphates form an interesting class of low-temperature fused salts which quench to form glasses; some technical and theoretical applications of these systems are discussed. The NaHSO4KHSO-4 eutectic (46.5% KHSO4, m.p. 125°C,T g 25°C) is easy to study since at lower temperatures decomposition of the melt is retarded and supercooling readily occurs. The solvent properties of this eutectic towards both inorganic and organic solutes have been investigated. The oxidation states available to transition and post-transition metals were studied spectrophotometrically and voltametrically; the results show a very restricted pattern of redox chemistry. The (abbreviated) electrochemical series is V(V)/V(IV)>Mn(III)/Mn(II)>H(I)/H2(O)>Ag(I)/Ag(O)>Mo(VI)/Mo(V)> Hg(I)/Hg(O)>Cu(II)/Cu(O)>Zn(II)/Zn(O). The Hammett acidity function,H 0, was measured as in the range –1 to –2. Various factors influencing redox reactions in the melt are discussed.  相似文献   

12.
The solvent extraction behaviour of vanadium(V) from hydrochloric acid solutions has been investigated using 2‐ethylhexyl phosphonic acid mono‐2‐ethylhexyl ester (EHEHPA ≡ HX) in kerosene as an extractant. For comparison, extraction studies have also been carried out with vanadium(IV). The results demonstrate that the extraction of vanadium(V) follows the cation exchange mechanism: where (HX)2 refers to the dimeric form of EHEHPA. On the other hand, two dimeric molecules of EHEHPA were found to be involved in the extracted complex of vanadium(IV): The equilibrium constants of the above extracted complexes have been calculated and found to be Kex,V(V) = 3.14 and Kex,V(IV) = 0.32. The effect of the nature of the diluent on the extraction of vanadium(V) with EHEHPA has been studied and correlated with the dielectric constants. IR spectral studies of the extracted complex were used to further clarify the nature of the extracted complex. The separation and recovery possibilities of vanadium(V) from other associated metal ions, viz magnesium(II), aluminium(III), titanium(IV), chromium(III), manganese(II) and iron(III), which are present in the waste chloride liquors from the processing of titanium minerals, are also discussed. © 2002 Society of Chemical Industry  相似文献   

13.
Four different forms of invertase and inulinase named as Invertase, I, II, III, IV and inulinase I, II, III, IV were purified from a culture filtrate of Fusarium oxysporum, grown on a fructan containing medium, by ammonium sulphate fractionation, gel permeation and ion exchange chromatography. Invertases had a higher optimum temperature (55–60°C) as compared to that of inulinases (35–45°C). Of sucrose, raffinose, stachyose and inulin, sucrose was the best substrate for all the four invertases and none of the invertases showed activity with inulin. Inulinases showed maximum activity with inulin. The optimum pH of invertase I and II was 5.5 whereas invertase III and IV showed a maximum activity at pH 4.0. Inulinases I, II, III and IV had an optimum pH of 5.5, 5.5, 6.0 and 6.5, respectively. The thermal stability of invertases was in the order of invertase III > IV > II > I. Inulinase II was more stable than inulinase I whereas inulinase III and IV were the least stable. Inulinases showed a low Km in the range of 10–95 μmol dm?3 of inulin, thereby showing their high affinity for inulin. Km for invertases varied from 2 mmol dm?3 to 4 mmol dm?3 of sucrose. HgCl2 and CuSO4 were found to be strong inhibitors for both invertases and inulinases.  相似文献   

14.
《Electrochimica acta》1986,31(10):1335-1339
The voltammograms recorded for the oxides V2O5, NaVO3, VOSO4, NaVO2 and V2O3, when incorporated in carbon paste electrodes with conducting binder, show that the electronic transfer occurs between the electrode and the soluble species. The V(V)/V(IV) and V(III)/V(II) systems are reversible and the electrochemical reactions give anodic and cathodic peaks with quite identical potentials, close to that of the standard potential of these systems. The V(IV)/V(III) couple is irreversible and the reduction, shifted towards negative potentials, coalesces with the V(III) to V(II) reduction process. For the oxides containing V(V), the reduction to V(IV) leads to two peaks: the first one is reversible and due to the reduction of the species coming from the instantaneous dissolution of the finest particles, the second one is irreversible and due to the progressive dissolution of the largest particles occuring during the cathodic sweep.  相似文献   

15.
Photocatalytic Systems. XLVIII. Unusual Light-Induced Redox Reactions of Cobalt(III), Iron(III) and Copper(II) Complexes in Presence of Chromic Acid Esters The coordination compounds[Co(NH3)5H2O]3+,[Co(NH3)4(H2O)2]3+,[Co(en)2(H2O)Cl]2+ (en = ethylendiamine), [L2(H2O)Fe-O-Fe(H2O)L2]4+ (L = 1,10-phenanthroline; 2,2′-bipyridine) and [CuL2]2+ (L = 2,9-dimethyl-1,10-phenanthroline) show no or neglegible photo redox reactions upon irradiation wave-length above 350 nm. However, in the presence of chromate(VI), water, and different alcohols like methanol, ethanol, i-propanol and n-propanol a very efficient light-induced formation of cobalt(II), iron(II) and copper(I) (ϕ = 0,7; Λirr = 375 nm) can be observed together with reduced generation of chromium(III). The participation of chromium(V) in the primary step of the photolysis of chromic acid esters was shown to be the reason for these unusual light-induced redox reactions. The coordination compounds under discussion behave as very efficient scavengers for chromium(V) connected with simultaneous reoxidation to chromate(VI) and reduction to the appropriate cobalt(II), iron(II) and copper(I) compounds. The general importance of the participation of chromium(V) in the primary step of the photolysis of chromate(VI) in non-aqueous solvents is also shown by investigations of the photochemical behaviour of the system metal complex/CrO4—, Cr2O7—/dimethylsulfoxide. Possible mechanisms of the light-induced reductions of the metal complexes are discussed.  相似文献   

16.
The concentration of conjugated polyene sequences was studied in γ-irradiated PVC with 4% admixture of four epoxy stabilizers: diglycidyl ether of 2,2-bis(4-hydroxy-3-methylphenyl)propane (I), styrene oxide (1,2-epoxy ethyl benzene) (IV), epoxidized ricinus oil (VI), and epoxidized soybean oil (Drapex 6.8) (VII). As in the former investigations (Papers I and II), the process of the formation of the polyenes occurs in two stages. The concentration of polyene sequences with n double bonds, Hn the total amount of polyene sequences, ∑Hn, the average length of the polyene sequence, n , and the two extents of reaction x and p, were computed. The stabilizing effect of all compounds used agrees with the increasing content of epoxy groups. The addition of stabilizers diminishes the value of n . The decrease of the fraction of long sequences and the increase of short ones occurs. Apart from the binding of evolved HCl, the protective effect towards the macromolecules of PVC consists mainly in the inhibition of growth of chain dehydrochlorination by the epoxy groups.  相似文献   

17.
Summary The polymerization of butadiene(Bd), isoprene(Ip) and styrene(St) has been examined using the six catalyst systems composed of lanthanocene, (C5H9Cp)2NdCl(I), (C5H9Cp)2SmCl(II), (MeCp)2Sm OAr'(III), (Ind)2NdCl(IV), Me2Si(Ind)2NdCl(V) and (Flu)2NdCl(VI), and methylaluminoxane(MAO) respectively. All of them can be used to form the polyisoprene with molecular weights of 1 to 10 thousand and cis-1,4-unit contents of 41 to 47%. (I), (II) and (III) of them can be also used to form the polybutadiene with molecular weights of 10 to 20 thousand and cis-1,4-unit contents of 62 to 78%. In addition, the catalysts from (II) to (V) are still active for St polymerization and (II) of them gives a syndio -rich random polystyrene. It is noteworthy that (II) and (III) are active for homopolymerization of Bd, Ip and St in the same polymerization condition. Received: 16 December 1997/Revised version: 17 March 1998/Accepted: 24 March 1998  相似文献   

18.
An ICP‐AES method using a new spherical macroporous epoxy–polyamide chelating resin to enrich and separate trace Ga(III), In(III), Bi(III), V(V), Cr(III), and Ti(IV) ions from solution samples is established. The results show that the analyzed ions can be enriched quantitatively by 0.1 g of the resin at pH 4, with recoveries > 98%. The ions can be desorbed quantitatively with 10 mL of 2M HCl from the resin column with recoveries > 96%, and 100–1000‐fold excesses of Ca(II), Mg(II), Fe(III), Cu(II), Zn(II), Al(III), Ni(II), and Mn(II) cause little interference in the determination of these ions by ICP‐AES. The chelating resin is reused for ten times; the recoveries of these ions are still over 95%. The relative standard deviations for enrichment and determination of 100 ng ml?1 Ga(III), In(III), and Bi(III), 10 ng ml?1 V(V), Cr(III), and Ti(IV) are in the range 0.6–2.3%. The concentration of each ion found in the real wastewater sample and alloy sample is in good agreement with the values provided by the plant. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2330–2334, 2005  相似文献   

19.
The conversion of methane and the selectivities to the various products have been measured at 700 and 775 °C on a variety of phosphates of La(III), Zr(IV), V(V), Cr(III), Mn(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Al(III), B(III), Pb(II), Bi(III) and Sm(III) in the presence and absence of carbon tetrachloride. The conversions reach as high as 30 and 49% at 700 and 775 °C, respectively, with methane and oxygen at partial pressures of 200 and 25 Torr, respectively. The highest C2+ selectivities (61 and 82%, respectively) were obtained for lead(II) phosphate at 700 and 775 °C, respectively. In general the conversions and C2+ selectivities are enhanced on addition of carbon tetrachloride (1.1 Torr) to the feedstream, although there are notable exceptions. Significantly high selectivities to formaldehyde are observed with a number of the catalysts, in particular 32% with boron(III)phosphate.  相似文献   

20.
The solvent extraction of magnesium(II), aluminium(III), titanium(IV), vanadium(V), chromium(III), manganese(II) and iron(III) from hydrochloric acid solutions has been investigated using the trialkylphosphine oxide Cyanex 923 (TRPO) in kerosene as extractant. The results demonstrate that titanium(IV), vanadium(V) and iron(III) are extracted into kerosene as TiOCl2·2TRPO, VO2Cl·TRPO and HFeCl4·2TRPO, respectively. On the other hand magnesium(II), aluminium(III), chromium(III) and manganese(II) are not extracted with TRPO from hydrochloric acid solutions (1.0–4.0 mol dm?3) under the experimental conditions. IR spectral studies of the extracted complexes were further used to clarify the nature of the extracted complexes. The effect of the diluent on the extraction of titanium(IV), vanadium(V) and iron(III) has been studied and correlated with the dielectric constant. The loading capacity of the TRPO system has been evaluated and the potential for the separation and recovery of titanium(IV), vanadium(V) and iron(III) from simulated waste chloride liquors of the titanium minerals processing industry has been assessed. Copyright © 2004 Society of Chemical Industry  相似文献   

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