浓度对草酸与酸性高锰酸钾溶液褪色反应速率的影响研究

通过比较同体积、不同浓度的草酸溶液与同体积、同浓度的酸性高锰酸钾溶液反应时溶液褪色时间的不同,使学生体会反应物浓度对反应速率的影响。为适应课堂教学,研究了各种反应物浓度对该反应速率的影响,为一线教师配置适合课堂教学的各种反应物的浓度提供了较为准确的数据。     

醇胺溶液吸收二氧化碳的实验研究

CO2的减排和有效利用受到人们的广泛关注.以二乙醇胺(DEA)、三乙醇胺(TEA)、N-甲基二乙醇胺(MDEA)溶液为对象,采用鼓泡吸收装置考察了醇胺的种类及浓度对CO2吸收速率和吸收容量的影响,研究了吸收前后溶液pH的变化,以及醇胺溶液再生后的情况.实验表明,醇胺溶液浓度增大有利于CO2的吸收,相同条件下DEA和TEA的吸收效果好于MDEA,醇胺溶液吸收CO2后pH由接近于11降至7左右,TEA的再生效果好于DEA.     

氢氧化锰共沉淀分离-催化极谱法测定土壤中有效钼

土壤样品中有效钼用草酸铵-草酸混合溶液(pH 3.3)振摇提取,所得悬浮液用干滤纸过滤,分取部分滤液蒸缩体积后加入10 g.L-1酸性高锰酸钾溶液并蒸发至近干,趁热加0.25 mol.L-1氢氧化钠溶液进行共沉淀分离。分取部分上清液,用硫酸(1+1)溶液酸化后加入混合底液(其中含有二苯基乙醇酸、二苯胍及氯酸钠)及少许钛铁试剂溶液作为与钼(Ⅵ)进行催化反应的试剂体系。用JP-303极谱仪进行测定。在-220 mV峰电位处测得的峰电流值与其相应的钼(Ⅵ)的质量浓度在0.8～20μg.L-1范围内呈线性关系。此方法的检出限(3s/k)为0.002 6μg.g-1。用此方法分析了5个土壤标准物质,所测得有效钼的含量与其认定值相符。     

氯化汞鉴别碳酸钠和碳酸氢钠实验的设计与研究

通过实验和理论推导论证了HgCl2鉴别Na2CO3和NaHCO3溶液的可能性.结果表明,用Cl-调变的HgCl2能鉴别常量浓度的Na2CO3和NaHCO3溶液.主要存在以下原因:①即使是稀Na2CO3溶液也比近饱和的NaHCO3溶液所产生的OH-和CO32-的平衡浓度要大.②HgCl2溶液的Hg2+浓度易受Cl-调变.该方法仪器简单操作方便,药品易得耗时短,现象明显易观察,成功率高效果好.     

壳聚糖-盐酸溶液中温度敏感的相分离行为

研究了壳聚糖 盐酸溶液温度敏感的相分离行为.通过对壳聚糖-盐酸溶液浊度变化的考察以确定相分离温度.测定不同盐酸浓度、壳聚糖浓度以及不同脱乙酰度的条件下的相分离温度，并用DLVO理论(Deijaguin-Landau and Verwey-Overbeck Theory)进行了解释. FTIR、X-ray以及SEM分别描绘了壳聚糖经相分离过程后官能团、结晶状态、颗粒形态的特点.     

体积排阻色谱和激光光散射对大豆蛋白热诱导聚集体的研究

采用体积排阻色谱(SEC-HPLC)和激光光散射(LLS)研究了不同浓度和离子强度下大豆蛋白热诱导聚集体的分子量分布和粒径分布。在离子强度为0时,SEC-HPLC的结果表明,热处理后的蛋白溶液主要由3部分组成,即聚集体、中间体和未聚集部分。聚集体部分随着浓度增加而逐渐增加;LLS的结果表明:体系有不均一的粒径分布,且浓度增加时体系的平均粒径增加。上述样品在较高离子强度下加热时,SEC-HPLC和LLS的结果都证明溶液中的中间体部分逐渐消失。因此,控制浓度和离子强度可以制备不同性质的大豆蛋白聚集体。     

表面活性剂对部分水解聚丙烯酰胺溶液抗盐性的影响

通过实验研究了阴离子表面活性剂(SDS)、非离子表面活性剂(OP-10)、两性表面活性剂(C12BE)浓度及KCl浓度对部分水解聚丙烯酰胺(阴离子型,HPAM)水溶液黏度的影响规律,进而分析各因素对聚合物溶液抗盐性的影响。实验结果表明:当表面活性剂浓度低于临界缔合浓度CAC时,聚合物溶液黏度变化不大;高于CAC后,随着表面活性剂浓度增大,聚合物溶液黏度急剧增加;当表面活性剂浓度达到聚合物饱和浓度PSP时,聚合物溶液黏度达到最大值;再加入阴离子和两性表面活性剂,将导致黏度降低,而加入非离子表面活性剂不再改变聚合物溶液的黏度,无机盐KCl对聚合物溶液有双重作用,低浓度KCl促进聚合物溶液黏度升高,高浓度KCl则导致聚合物溶液黏度急剧降低后趋于稳定,在相同KCl浓度下,三种表面活性剂的抗盐能力表现为:SDSOP-10C12BE。     

基于ITO电极的细胞色素c吸附层的直接电化学

采用未经修饰的铟锡氧化物(ITO)工作电极直接探测到了细胞色素c(Cytc)吸附层的氧化还原峰,并得出了Cytc的表面浓度,随着溶液浓度从2μmo·lL-1增大到10μmo·lL-1,Cytc的表面浓度相应地从0.35×10-12mo·lcm-2增大到1.53×10-12mo·lcm-2.实验获得的表面浓度倒数与溶液浓度倒数的准线性关系说明Cytc在ITO表面的吸附基本满足Langmuir等温吸附理论.对Cytc溶液的循环伏安测试结果表明参与电极反应的Cytc包括游离分子和吸附分子,前者的贡献大于后者,电极反应主要受扩散控制并呈准可逆过程.根据Nicholson方法估算得到反应物的标准异相速率常数的平均值为1.65×10-3cm·s-1.实验结果显示在室温下放置1h后Cytc吸附层电化学活性部分丧失,在80℃下放置1h后吸附层完全失活.失活的Cytc吸附层对铁氰化钾溶液在Au电极上的电极反应具有明显的阻碍作用.     

溶液中离子浓度大小比较

溶液中离子浓度大小比较是高中化学的重点和难点,也 是高考命题的热点,但有一部分同学对这部分内容感到非常 棘手、不知所措.现结合教学过程中学生常犯错误讨论一下 如何比较溶液中离子浓度大小.     

溶液中尼龙11的NMR弛豫研究

用 2DNMR(HMQC)技术归属了溶液中尼龙 11分子的主要1H和13 C NMR共振信号 ,并通过变温和变浓度 1H NMR弛豫时间的测定 ,得到了尼龙 11溶液中氢键结构变化的动力学信息 .结果表明 ,溶液中尼龙 11分子的弛豫行为与一般高聚物不同 ,随着温度升高 ,尼龙链间相互作用逐渐减弱 ,尼龙分子与溶剂小分子间相互作用逐渐增强 ,尼龙链间氢键逐渐离解 ,而离解出来的自由NH和CO基团又与溶剂小分子间生成氢键 .尼龙 11链卷曲堆积成无规线团状 ,一部分溶剂被包裹在内部并和α CO质子成为一个整体而一起运动 .变浓度实验弛豫过程呈现双指数特性 ,快弛豫部分随体系浓度增加而增多 ,表明聚合物溶液中凝聚缠结含量的增大 ,这种凝聚缠结是由溶液中氢键引起分子链物理交联成网而形成的 .随着浓度增加 ,溶液逐渐变成局部粘度较大的类似软固体     

Elastic properties of crosslinked poly(vinyl alcohol) gels: Network topology

Current network theory exhibits inconsistencies which show up particularly clearly in deformation of networks prepared by crosslinking a polymer in solution. A check of theory can be obtained if one knows precisely the number of crosslinks in the network and if a range of deformations is applied to the network. In an effort to explore this problem we have examined the relation of shear modulus to crosslink density, primary molecular weight, and polymer concentration for a series of poly(vinyl alcohol) gels at low to intermediate concentrations. Aqueous poly(vinyl alcohol) solutions were crosslinked to form infinite networks using terephthalaldehyde. We find a large discrepancy with these poly(vinyl alcohol) gels between measured shear modulus and that calculated from classical elasticity theory assuming quantitative reaction of crosslinking. The ratio of measured to calculated modulus is independent of crosslink density for a given primary molecular weight and concentration. It shows linear dependence on polymer concentration prior to crosslinking and extrapolates to a critical concentration which is consistent with the effective sizes of the polymer molecules.     

A theory of polymer solutions without the mean-field approximation in Flory-Huggins theory

The concept of the volume fraction at chain end is proposed, which is the conditional probability for a site having been occupied, knowing that an adjacent site is occupied by polymer end. The overall entropy of polymer/solvent system is separated into two fundamentally different parts, i.e., the translational entropy and the conformational entropy. Based on these a theory of polymer solutions is established. When a mean-field approximation is introduced, Flory-Huggins (FH) theory is recovered. The FH interaction parameters and spinodal curves of the polystyrene/cyclohexane system are calculated and compared with the experimental data. The good prediction of them two is achieved.     

树状高分子溶液在粘度计毛细管表面的吸附现象

本文测定了树状高分子DAB(PA) n 水溶液和脂肪族超支化聚酯及其硅烷化衍生物溶液性质 .通过粘度测量 ,得到了吸附常数k ,半数吸附浓度ca,分子间缔合常数Km ,特性粘度 [η]等参数 ,解释了特性粘度的反常行为 ,重点研究了吸附现象 .发现树状高分子和超支化高分子溶液在粘度计毛细管表面形成了多层吸附 ,高分子之间的相互作用及高分子与溶剂分子间的氢键作用是形成多层吸附的重要原因     

Effects of added surfactants on thermoreversible gelation of associating polymer solutions

The influence of added surfactants on physical properties of associating polymer solutions was examined by a new statistical‐mechanical theory of associating polymer solutions with multiple junctions and by computer simulation. The sol–gel transition line, the spinodal line, and the number of elastically effective chains in the mixed networks were calculated as functions of the concentration of added surfactants. All of them exhibited nonmonotonic behavior as a result of the following two competing mechanisms. One was the formation of new mixed micelles by binding surfactants onto the polymer associative groups. These micelles serve as crosslink junctions and promote gelation. The other was the replacement of polymer associative groups in the already formed network junctions by added surfactants. Such replacement lowers connectivity of junctions and destroys networks. The critical micelle concentration was also calculated. The results are compared with the reported experimental data on poly(ethylene oxide)‐based associating polymers and hydrophobically modified cellulose derivatives. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 733–751, 2004     

Characterization of thermo-reversible gels by means of sedimentation equilibria

This paper describes the deformation of gels in a centrifugal field leading to a continuous equilibrium. A gel is considered to be a binary mixture of cross-linked polymer and solvent and is assumed to remain isotropic during the deformation. From the equation for the osmotically effective pressure, called swelling pressure, the thermodynamic properties of a gel can be calculated. For highly swollen gels the expression of Svedberg and Pedersen is obtained. It is shown that the complete concentration dependence of the swelling pressure in the concentration range of the maximally swollen gel up to that at the cell bottom can be measured in a single equilibrium experiment. The homogeneity of weakly cross-linked gels can be examined by means of the method described. Soluble parts which are not incorporated into the polymer network can also be detected if they are present. From the swelling pressure-concentration curves it is possible to derive the thermodynamic properties of the physically crosslinked gelatin/water gels that were investigated. These gels can be described by means of a slightly modified Flory-Huggins equation with an interaction parameter χw in the weight fraction scale, which depends linearly on concentration. The interaction parameters show a dependence on concentration which is explained by an increased branching and crosslinking of the polymer with increasing initial polymer concentration of the gels. At low initial polymer concentration, the primary chains have to aggregate to build up relatively long chains between the network junctions. The static shear modulus G which can be calculated from the network term has the same order of magnitude as the real part of the complex shear modulus which is measured at low frequency.     

基于链端体积分数的聚合物溶液理论

提出“链端体积分数”的概念以克服Flory-Huggins(FH)理论中的平均场假设.将聚合物多链体系看成一条“间隔连续链”,使一些热力学量写成路径积分的形式.在聚合物/溶剂体系中,保留了FH理论的无热熵假设,把总熵分为两部分,建立了一个新的聚合物溶液理论.计算了聚苯乙烯/环己烷体系的FH相互作用参数和相分离曲线,并与实验数据和FH理论作了比较,结果表明,我们的理论结果比FH的理论结果有了很大的改进.     

聚偏氟乙烯凝胶电解质组成间相互作用及其凝胶化研究

通过冷却聚偏氟乙烯 (PVDF) 丙烯碳酸酯 (PC)或PVDF PC LiClO4的溶液 ,制备了数个聚合物凝胶 .实验表明 ,聚合物凝胶的凝胶化时间 (tgel)与凝胶温度、聚合物浓度有关 ,且强烈地依赖于体系中盐的浓度 ,因为盐会缩短体系的tgel.凝胶体系中LiClO4的存在提高了其凝胶熔融温度 (Tgm) ,LiClO4的含量越大 ,相应凝胶的Tgm 越高 .用DSC和落球法所测凝胶的Tgm 有较大的差别 .这说明凝胶中可能存在热稳定性好和热稳定性相对较差的两种不同结构部分 .FT IR的研究结果表明 ,凝胶电解质的各组成 (LiClO4,PC和PVDF)间存在较强的相互作用 .对含盐和不含盐的两类凝胶体系的对比研究表明 ,两者不同的凝胶化现象和Tgm 归因于盐与聚合物或溶剂间的络合作用     

梯度折射率聚合物细棒的制备和数学模拟

在聚甲基丙烯酸甲酯 (Poly(methylmethacrylate) ,PMMA)管中 ,加入单体甲基丙烯酸甲酯 (Methylmethacrylate ,MMA)和另一种高折射率的掺杂剂溴苯 (Bromobenzene ,BB) ,用界面凝胶均聚合方法制备了梯度折射率聚合物光纤预制棒 .这种光纤预制棒的梯度折射率是通过具有不同折射率的分子扩散而形成的 .通过对界面凝胶聚合过程的描述 ,该工作讨论了预制棒中聚合物的浓度分布及边界条件的假设 .并根据自由体积理论对其折射率分布进行理论模拟 .将得到的折射率抛物线分布与实验结果进行对比 ,结果表明聚合浓度的分布为ω =a(r/R) 2 +b时 ,理论预计的光纤预制棒的折射率分布与实验结果有着较好的符合 .同时 ,对聚合体系中BB对聚合物浓度分布的影响进行了讨论     

Enthalpy of mixing for polymer solutions based on Gibbs excess function limit of hard spheres mixtures

Enthalpy of mixing of polymer with solvent has been evaluated by the new polymer/solvent theory proposed by the authors in a previous article. The new theory was based on the excess Gibbs function limit of hard sphere mixtures with infinite size difference. The calculated enthalpy of mixing for polymer/solvent mixtures by the new theory, agreed with experimental data with good accuracy and indicated that the theory is capable to produce the enthalpy of mixing in the whole concentration range of polymer compared with Flory–Huggins theory. Also the calculations provided information on the studied polymer chains and the molecular interaction effects which were consistent with the properties of polymers and solvents used in the mixtures.     

Energy storage in drag-reducing polymer solutions

A new theory, which relates viscous drag reduction to the energy stored by polymer molecules subjected to a fluctuating wall shear rate, is proposed for the origin of the Toms effect. The strain energy densities of several polymer solutions were estimated from bead-spring theory. The requisite molecular polymers were optimized by a least-squares fit of calculated to observed intrinsic viscosities. Friction reduction was found to be a monotonic function of the strain energy density for a given polymer–solvent combination. The correlation was independent of molecular weight and concentration for pipes of 0.5–2.0 in. diameter. Differences between the points of onset of drag reduction for different polymer–solvent combinations may be due to the unequal effect of internal viscosity.