二甲亚砜热稳定性的实验研究

采用先进的绝热加速量热仪为手段,对二甲亚砜的热稳定性进行了系统研究,其内容涉及纯二甲亚砜的热稳定性、加酸碱和硫化物等杂质后二甲亚砜的热稳定性,包括初始放热温度、温升速率、温度-压力等;通过修正试验数据,消除了热惰性因子的影响;得到了二甲亚砜的热稳定性特性。研究表明,在酸、碱存在时,二甲亚砜在室温下即可发生强烈的放热反应,导致二甲亚砜的分解温度提前。该实验研究结果,对二甲亚砜的安全生产工艺过程控制具有重要参考价值。     

硝酸甲胺反应过程的安全性研究

用反应量热仪(RC1e)对硝酸溶液与一甲胺溶液在反应过程中的热安定性进行初步研究,分别测试不同反应温度、加料速度和初始硝酸浓度下反应的放热情况。实验结果表明:该中和过程反应迅速,在室温就能进行;与反应温度、加料速度相比,起始硝酸浓度对反应安全性影响最大,且硝酸浓度越高,反应的速度和反应的完全程度也越高。实验还表明:RC1e是研究反应过程中热安定性情况的有效工具,能通过反应过程的热量变化体现反应速率,所得结果对硝酸甲胺的工业化生产具有重要的参考价值。     

典型装饰织物在不同氧浓度下热分析研究

人民生活水平的提高使人民对室内环境的舒适程度提出了更高要求 ,室内装饰织物的用量迅速增加 ,室内装饰织物在燃烧时会释放出大量有毒物质和热量 ,对人及环境构成了巨大危害。因此 ,研究装饰织物的燃烧特性非常重要。笔者利用热重 -差热 (TG -DTA)分析仪对纯棉、棉麻和腈纶这几种典型的装饰织物在不同的氧气浓度 (10 % ,15 % ,2 1% )和升温速率 (10K/min ,30K/min)条件下进行了热重分析 (TG)和差热分析 (DTA)实验 ,研究了它们的燃烧特性 ,并着重进行了不同氧浓度下的对比研究 ,发现试样的燃烧分为两个阶段。建立了以一级反应模型为主的动力学方程 ,并得出了各阶段的动力学参数、表观活化能和频率因子。     

用差示分光光度法测定高浓度皮革废水中铬的方法探讨

介绍了应用差示分光光度法直接测定高浓度皮革废水中Cr的方法，通过与原实验方法分析结果的对比，获得了满意的结果，能基本满足环境监测的要求。     

Hazard evaluation for chlorination and amination reactions of fluorocytosine production process

Reaction thermal runaway is one of the most important reasons leading to chemical accidents. With the rapid development of the chemical industry in the world, especially the fine chemical industry, various safety accidents also occur frequently. Therefore, it is necessary to study the exothermic behavior of the reaction process. In this study, reaction calorimeter was used to study the exothermic phenomena during the chlorination reaction and amination reaction. Differential scanning calorimetry was performed on the reactants, and thermogravimetric experiments were performed on the products. In addition, adiabatic experiment was performed to study the thermal runaway behavior of amination products under adiabatic conditions. The results showed that the target reactions generated a large amount of heat in the initial stage. The maximum temperature of amination reaction is higher than the initial decomposition temperature of the amination product under adiabatic condition. The pyrolysis of amination product was divided into three stages. The product had a high apparent activation energy at the beginning of decomposition, and the apparent activation energy decreased as the decomposition progressed.     

汽车用聚合物材料火灾燃烧特性研究

为研究车用聚合物材料的燃烧特性,并对材料的火灾危险性进行全方位的评估,采用锥形量热仪,对汽车上常用的ABS,PP-PVC,PVC革-无纺毡以及无纺布-PVC聚合物材料进行分析表征,测得点燃时间、热释放速率、总热释放量、质量损失速率、烟气生成速率等参数。结果表明:ABS材料的点燃危险性相对最低,PVC革-无纺毡材料相对最高;随热辐射强度的增加,各样品的热释放速率和烟气生成速率明显加快;结合热释放速率峰值、均值和总热释放量可知,无纺布-PVC材料的热危险性相对最低;结合烟气生成速率和总烟释放量可知,ABS材料的发烟危害性相对最高,无纺布-PVC的相对最低;综合比较各样品的FGI和FPI值,安全等级由高到低依次为ABS,PP-PVC,PVC革-无纺毡,无纺布-PVC。     

Electrochemical Monitoring of Methylparathion Degradation in an Acid Aqueous Medium in Presence of Cu(II)

Abstract

A study was undertaken to determine the effect of Cu(II) in degradation of methylparathion (o,o-dimethyl o, 4-nitrophenyl phosphoriotioate) in acid medium. Initial electrochemical characterization of Cu(II) and methylparathion was done in an aqueous medium at a pH range of 2–7. Cu(II) was studied in the presence of different anions and it was observed that its electroactivity depends on pH and is independent of the anion used. Methylparathion had two reduction signals at pH ≤ 6 and only one at pH > 6. The pesticide's transformation kinetic was then studied in the presence of Cu(II) in acid buffered aqueous medium at pH values of 2, 4, and 7. Paranitrophenol appeared as the only electroactive product at all three pH values. The reaction was first order and had k values of 5.2 × 10^?3 s^?1 at pH 2, 5.5 × 10^?3 s^?1 at pH 4 and 9.0 × 10^?3 s^?1 at pH 7. It is concluded that the principal degradation pathway of methylparathion in acid medium is a Cu(II) catalyzed hydrolysis reaction.     

Simultaneous determination of three herbicides by differential pulse voltammetry and chemometrics

A novel differential pulse voltammetry method (DPV) was researched and developed for the simultaneous determination of Pendimethalin, Dinoseb and sodium 5-nitroguaiacolate (5NG) with the aid of chemometrics. The voltammograms of these three compounds overlapped significantly, and to facilitate the simultaneous determination of the three analytes, chemometrics methods were applied. These included classical least squares (CLS), principal component regression (PCR), partial least squares (PLS) and radial basis function-artificial neural networks (RBF-ANN). A separately prepared verification data set was used to confirm the calibrations, which were built from the original and first derivative data matrices of the voltammograms. On the basis relative prediction errors and recoveries of the analytes, the RBF-ANN and the DPLS (D – first derivative spectra) models performed best and are particularly recommended for application. The DPLS calibration model was applied satisfactorily for the prediction of the three analytes from market vegetables and lake water samples.     

Maternal investment in Antarctic fur seals: evidence for equality in the sexes?

Studies of the otariids (fur seals and sea lions), a highly sexually dimorphic group, have provided conflicting evidence of differential maternal expenditure in male and female offspring and, thus, suggestions that they conform to predictions of investment theory are equivocal. Since the mid-1970s, a diversity of research on Antarctic fur seals (Arctocephalus gazella) including studies of their reproductive ecology, lactation energetics, and foraging behaviour have been conducted at Bird Island, South Georgia that have resulted in one of the more complete and diverse data sets for any species of otariid. These long-term data were reviewed to determine whether there was any evidence to support that differential maternal expenditure occurred in Antarctic fur seals. Most of the data examined were collected during five consecutive austral summers from 1988 through 1992 and included years in which local food resources were abundant and scarce. We were unable to detect differences in the sex ratios of pups at birth or sex-biased differences in growth rates estimated from serial data, the number of foraging trips made, the duration of attendance ashore, diving behaviour, suckling behaviour, or milk consumption in any year and in the duration of foraging trips or age at weaning in 2 of 3 years. In addition, we found no evidence of greater reproductive costs between mothers with sons or daughters relative to their reproductive performance the following year. In contrast, sex-biased differences were only found in the duration of foraging trips in 1990, the age at weaning in 1988, and consistently in growth rates estimated from cross-sectional data. We suggest that differential maternal expenditure does not occur in Antarctic fur seals because male pups probably do not gain greater benefit from additional maternal expenditure than female pups. After weaning, males experience a period of rapid juvenile growth over 3–4 years during which time body mass nearly trebles. This growth will almost certainly be dependent upon available food resources then rather than on any maternal expenditure received over the first 4 months of life and, thus, the assumptions of the Trivers and Willard hypothesis are probably invalid for Antarctic fur seals. Received: 10 July 1996 / Accepted after revision: 3 March 1997     

Evidence for sexy sons in European starlings (Sturnus vulgaris)

The sexy son hypothesis suggests that females obtain future fitness benefits from mating with polygynous males through the inheritance by their sons of traits contributing to mating success. We tested this hypothesis in the facultatively polygynous European starling (Sturnus vulgaris) in two ways. We first compared sons of monogynous and polygynous free-living males for their abilities in nest site acquisition and female-directed behaviors in controlled aviary tests. We then investigated eggs laid in monogynous and polygynous matings for concentrations of maternal steroid hormones that could affect behavioral differentiation of sons. Sons of polygynous fathers defended more nest boxes and produced more courtship song than sons of monogynous fathers. Mean concentrations of maternal androstenedione (A4), 5-dihydrotestosterone (DHT), testosterone (T), and 17-estradiol (E) in yolks were not affected by mating status. However, the within-clutch pattern of A₄ depended on mating status, with higher concentrations in last than in first eggs of clutches of monogynous but not polygynous matings. These results suggest that (1) sons may inherit from their fathers behavioral qualities for the successful acquisition of nest sites and attraction of mates; (2) differential exposure to maternal steroid hormones during development in the egg is unlikely the cause of the behavioral differences between adult sons of monogynous and polygynous fathers; and (3) females adjust the within-clutch pattern of androgen to mating status, possibly in response to the expected contribution of their mate to nestling care.