Equilibrium,kinetics and thermodynamics studies of Cd sorption onto a dithizone-impregnated Amberchrom CG-300m polymer resin

Amberchrom CG-300m, a styrene acrylic ester polymer resin, was studied for the first time as sorbent for metal ion sorption in a solid-phase extraction system. The polymer sorbent was modified via impregnation with dithizone to improve its efficiency. Efficiency of the modified sorbent improved by more than 47%. The loading capacity of the resin is 3.2 mg dithizone per gram of sorbent. The mechanisms of Cd(II) sorption from aqueous solutions are presented. Capacity of the modified resin for Cd(II) was investigated in batch experiments as a function of pH, initial metal ion concentration, temperature and time. Maximum capacity of 0.551 mg Cd(II) per gram of sorbent was achieved. The dimensionless separation factor, 0 < R_L < 1, associated with the Langmuir isotherm (at T = 294 K) signifies sorption of Cd(II) was favorable, as do negative values of free energy of sorption (ΔG) at temperatures exceeding 293 K. Sorption was endothermic (ΔH > 0) while ΔS > 0 reflects the affinity of the sorbent towards Cd(II). The pseudo-second order model proved to be the best fit model for Cd(II) sorption kinetics data. Particle-diffusion models suggest sorption follows film as well as pore diffusion mechanisms.     

Preconcentration of trace nickel lons from aqueous solutions by using a new and low cost chelating polystyrene adsorbent

A simple and reliable method has been developed using chelating polymeric adsorbent (PSAHSB) to preconcentration of trace amount of Ni(II) ions from aqueous solutions under static loading conditions, and their determination by Ultraviolet and visible (UV–Vis) absorption spectroscopy. The influences of some analytical adsorption parameters, such as pH, temperature and contact time, the ionization constants of chelating groups in the adsorbent and desorption process were investigated. Maximum adsorption ≥98% was achieved at pH 3–7 after 20 min of contact time and the relative standard-deviation values were ≤5%. Adsorbed metal ions have been desorbed with 10 mL of 2 M HCl acid with the detection limit of 0.0157 μg m⁻¹. The Langmuir and Freundlich isotherm equations were used to describe adsorption behavior of the system at different temperatures. Kinetic and thermodynamic behavior of the adsorbent for Ni(II) ion preconcentration was also studied. The possible adsorption mechanism of Ni (II) ions onto modified adsorbent is also discussed. This method was applied efficiently to remove Ni (II) ions from environmental water samples.     

部分水解聚丙烯酰胺弱凝胶交联动力学的流变学分析

用流变学方法对部分水解聚丙烯酰胺(HPAM)苯酚甲醛间苯二酚交联体系的弱凝胶化过程进行了研究,通过对基团转化率和高分子交联转化率的分析,发现凝胶化过程在接近凝胶点时,处于反应动力学的初期,这使得交联点增加的动力学是比较简单的.通过在不同聚合物浓度和交联剂浓度并在地层温度和矿化度条件下线性粘弹性行为的研究,得到了交联体系凝胶化动力学过程的完整数据,发现聚合物浓度与交联剂浓度对凝胶点与凝胶强度的影响比较类似,反映出交联点增加的共同动力学特征.复数粘度在一个诱导期后,是以指数上升的,类似一个一级反应的特征.产生交联的临界聚合物浓度约为250mg L左右.并提出了剪切粘度数学模型,可以描述凝胶化过程中流变性质的变化.     

原位ATR-FTIR法研究异丁烯正离子聚合反应

应用原位ATR-FTIR法可在线检测异丁烯可控,活性碳正离子聚合反应过程,文章综述了原位ATR-FTIR法的特点,并进一步介绍其在异丁烯碳正离子聚合机理和动力学研究中的应用。     

Intensified dissolution of uranium from graphite substrate using ultrasound

Decontamination of graphite structural elements and recovery of uranium is crucial for waste minimization and recycle of nuclear fuel elements. Feasibility of intensified dissolution of uranium-impregnated graphite substrate using ultrasound has been studied with objective of establishing the effect of operating parameters and the kinetics of sonocatalytic dissolution of uranium in nitric acid. The effect of operating frequency and acoustic intensity as well as the acid concentration and temperature on the dissolution of metal has been elucidated. It was observed that at lower acid concentrations (6 M–8 M), the dissolution ratio increases by 15% on increasing the bath temperature from 45 to 70 °C. At higher acid concentration (>10 M), the increase was only around 5–7% for a similar change in temperature. With 12 M HNO₃, pitting was also observed on the graphite surface along with erosion due to high local reaction rates in the presence of ultrasound. For higher frequency of applied ultrasound, lower dissolution rate of uranium was observed though it also leads to high rates of erosion of the substrate. It was thus established that suitable optimization of frequency is required based on the nature of the substrate and the choice of recycling it. The dissolution rate was also demonstrated to increase with acoustic intensity till it reaches to the maximum at the observed optimum (1.2 W/cm² at 33 kHz). Comparison with silent conditions revealed that enhanced rate was obtained due to the use of ultrasound under optimum conditions. The work has demonstrated the effective application of ultrasound for intensifying the extent of dissolution of metal.     

Energy Storage by Poly(<Emphasis Type="Italic">o</Emphasis>-anisidine) Matrix During Oxidative Hydrolysis

The chromaticity of poly(o-anisidine) (POAN) doped with different acids (HA), HA-doped POAN, has been studied by the spectrophotometric technique and the results were substantiated by molecular mechanics (MM+) calculations. The observed absorbance decrease (λ around 720 nm, dark green coloration) with increasing concentration of the inorganic oxidizing agent (KMnO₄) can be attributed to the oxidative hydrolysis mechanism. The oxidative hydrolysis constant (K _h) is highly dependent on the strength of the acid used. The HClO₄-doped POAN matrix has the ability to store about 128.878 kJ⋅g⁻¹ chromogenic energy (CE) at the wavelength 720 nm in a condensed lightweight form. MM+ calculations suggest that the potential energy (PE) in kJ⋅mol⁻¹ of the optimum molecular geometric (OMG) structure of the HClO₄-doped POAN matrix is at least two (2.052) times more stable than the OMG of the base form (POAN-EB) of the POAN matrix. Kinetic parameters of the oxidative hydrolysis reaction of the HA-doped POAN matrix were deduced from absorbance variations with time. The results of computer-oriented kinetic analysis indicate that the rate-controlling step for HA-doped POAN oxidative hydrolysis is governed by the Ginstling-Bronshein equation that represents three-dimensional diffusion (D4). Activation parameters for the oxidative hydrolysis of the HClO₄-doped POAN matrix were computed and discussed.     

溶剂诱导聚合物结晶的研究进展

溶剂诱导结晶(SINC)又称为液体诱导结晶,它是结晶性高聚物在溶剂(或包括其蒸汽)作用下,在低于通常Tg下诱导结晶,而在高于通常Tg时能加速结晶的现象。本文主要对溶剂诱导结晶的机理、动力学和形态学进行了讨论。     

Sm_(0.5)Sr_(0.5)CoO_3阴极氧还原动力学

利用极化、交流阻抗技术考察了担载于La0.9Sr0.1Ga0.8Mg0.2O3(LSGM)电解质上的Sm0.5Sr0.5CoO3-La0.8Sr0.2Ga0.8Mg0.15Co0.05O3(SSC-LSGMC5)复合阴极的氧还原反应动力学.在SSC-LSGMC5阴极氧还原反应的阻抗谱中可以观察到明显的两个半圆.高频环的电导与氧分压无关,低频环的电导正比于氧分压的0.5次方.并且低频环的氧分压级数随着反应温度的降低而减小,可能对应于吸附氧原子的扩散过程.SSC-LSGMC5极化曲线与经典的Butler-Volmer方程吻合.阴、阳极的电荷转移系数均为1左右,交换电流密度的氧分压级数为1/4,对应于电荷转移过程.实验结果显示SSC-LSGMC5上的氧还原反应机制随反应条件的不同而发生变化.     

调节剂存在下双金属氰化络合催化剂催化环氧丙烷聚合的动力学

研究了双金属氰化络合催化剂DMC催化环氧丙烷调节聚合的动力学 .通过测定反应过程体系压力的变化来决定聚合的起始速率 ,发现聚合反应速率与分子量调节剂浓度Tr的线性函数的 - 1次方成正比 .考察了DMC催化剂在反应不同阶段的远红外吸收变化 ,提出了聚合反应可能的反应历程 ,并推导出调节聚合的动力学方程 .研究结果表明调节聚合的动力学特点在于链引发是发生在催化剂与单体之间 ,而不是催化剂与调节剂之间     

Physico-chemical aspects of polyethylene processing in an open mixer. Part 24: Experimental kinetics of aldehyde and carboxylic acid formation

The experimental kinetics for carboxylic acids shows more complexity than that for ketones. The fitting of the experimental results for the initial stages to the equation consisting of a linear and a quadratic term in processing time accounts well for the ketone data but not for the acid data. Instead of that, the data for the acids show fair fit to an equation containing a linear term and another term that is cubic in processing time. In the temperature range of the experiments the linear term is practically constant. The cubic term increases strongly with temperature. The combination of a linear and a quadratic term can account for the advanced stages of processing. The corresponding quadratic term shows strong increase if the processing temperature passes from 150 to 160 °C. However, for higher processing temperatures it remains constant within experimental error. The difference carbonyl absorbance measured after treatment of the polyethylene films with ammonia corresponds to the sum of the acids and aldehydes. It shows similarly complex kinetics. Some of the difficulties encountered with the experimental kinetics cannot be resolved with the data available. It is only the comparison with the formal kinetics based on potential mechanisms of product formation that allows for better understanding of the experimental results.