自溶液中的吸附 Ⅶ.硅胶自环己烷中吸附醇、酮和酯

测定了10℃和30℃时硅胶自环己烷中吸附几种单功能团的醇、酮和酯的等温线.吸附次序是:环己醇>正辛醇>环己酮>4-甲基戊酮-2>乙酸正丙酯≈乙酸正戊酯.吸附皆随温度的升高而减少.除了极低浓度外,吸附等温线可以Langmuir公式表示.饱和吸附量(n_m~s)并不符合一个分子吸附在一个表面自由羟基上的假设.除了表面条件和吸附物的功能团以外,看来饱和吸附还与温度、溶剂、吸附物的链长等因素有关.文中还导出了由Langmuir参数计算吸附标准自由能(ΔG°)和热焓(ΔH°)的方法.计算结果表明,ΔH°的绝对值皆大于ΔG°的绝对值,ΔS°皆为负值.不同醇或酯的ΔG°或ΔH°实际上没有差别;据此提出一个简单的吸附模型,即:在稀溶液中只有分子的极性基直接吸附在硅胶上,而分子的碳氢链部分仍处在液相中.4-甲基戊酮-2的ΔG°和ΔH°的绝对值都比环己酮低一些,一个可能的解释是吸附时4-甲基戊酮-2的异丁基可能较接近表面,从而导致吸附的减少和ΔG°ΔH°绝对值的降低.     

自溶液中的吸附——Ⅻ.活性炭自水中吸附芳香化合物的热力学研究

测定了25℃和35℃时活性炭自水中吸附苯甲酸、邻苯二甲酸、邻羟基苯甲酸、间羟基苯甲酸、对羟基苯甲酸、苯酚和邻苯二酚共七种芳香化合物的等温线,计算了吸附过程的ΔG°,ΔH°和ΔS°。七种芳香化合物的-ΔG°都在5.9～7.7kcal·mol~(-1)的范围内,差别不大;-ΔH°都小于-ΔG°的值;ΔS°则都是正的。这些结果表明熵变是这类体系的吸附过程的重要驱动力,而且往往是主要驱动力。在液相吸附中,溶质的吸附必伴随着溶剂的脱附,前者是熵减少的过程,后者是熵增加的过程。因为上述芳香化合物的摩尔体积约是水(溶剂)的5～7倍,也就是说,吸附1摩尔的溶质将伴随5～7摩尔的水由表面脱附。因此,由于水的脱附引起的熵增加远远超过溶质吸附所引起的熵减少。这可以解释为何这类体系的吸附过程的熵变总是相当大的正值。根据这个理论,可以设想倘若溶剂的摩尔体积与溶质的相近或比溶质的更大时,吸附过程的熵变可能出现负值,文献中的一些数据支持了这一推测。     

VOCs在吸附剂上吸附性能的热力学研究

采用色谱法与热重(TG)法,测量了正己烷、甲苯和乙酸乙酯在活性炭、5A、NaY、13X、ZSM-5 (SiO_2/Al_2O_3=27、300)、Hβ以及M CM-41等吸附剂上不同温度下的吸脱附行为,并基于反相气相色谱法测得的数据,计算了其吸附热力学参数ΔH、ΔS和ΔG,分析了上述VOCs分子与吸附剂之间的作用机制,并借助FT-IR验证了吸附质在分子筛表面的吸附机制。结果表明,上述吸附过程存在物理吸附和化学吸附两种方式,其中,物理吸附的作用力大小与吸附剂的孔径分布和分子直径相关,而化学吸附的作用力大小依赖于分子筛硅铝比和Ca~(2+)、Na~+、H~+等阳离子及吸附质分子的偶极矩,且强的化学吸附使得部分吸附质分子的脱附温度高于200℃。     

非离子表面活性剂和β-环状糊精包结作用的微量热法研究

用Model-4200型恒温滴定量热系统,研究了非离子表面活性剂(TritonX-114,TritonX-100,TritonX-102,TritonX-405)和β-环状糊精的包结的热力学性质,结果表明:对所有体系,均形成1:1的包结物,ΔHⅲ和ΔSⅲ值均为负值,形成包结物的过程是焓有利而熵不利的过程,而且-ΔHⅲ和ΔSⅲ值随非离子表面活性剂环氧乙烷(EO)链长的增加而减少。另外,非离子表面活性剂环氧乙烷(EO)链越长,包结物稳定常数越小。     

阳离子膨润土对分散染料的吸附动力学研究

研究了阳离子膨润土(EPI-DMA/Bt, PD/Bt, CTMAB/Bt)对分散染料(分散黄棕S-2RFL, 分散大红S-R, 分散蓝SBL, 分散黄SE-6GFL)的吸附动力学行为. 结果表明, 阳离子膨润土对分散染料的吸附过程符合二阶段吸附速率方程, 各阶段具有不同的吸附动力学常数(k1, k2)以及吸附活化能(Ea1, Ea2)、活化焓(ΔH*1, ΔH*2)和活化熵(ΔS*1, ΔS*2); 在阳离子膨润土对分散染料的吸附过程中, k1随着阳离子插层剂烷烃链的增加而增大, 表明较大的晶片层间距, 疏水的层间域和表面正电荷增加均有利于吸附速率增大; 对于两个吸附动力学阶段, ΔH★1<-TavΔS★1, △H★2<-TavΔS★2和ΔG★>0表明整个吸附过程活化熵的影响大于活化焓.     

外墙保温板残料基活性炭吸附苯酚的研究

活性炭是我们生活中常用的吸附剂,此次研究以外墙保温板残料为碳源制备了活性炭,并考察了所制备的活性炭对苯酚的吸附性能;针对吸附时间、吸附温度、p H、浓度等因素对苯酚吸附的影响,确定了吸附工艺参数:吸附苯酚最优条件为吸附时间90min,温度40℃,p H为4,浓度为0.78mg·m L~(-1),吸附量606.88 mg·g~(-1)。动力学分析:苯酚在外墙保温板残料基活性炭上的吸附符合内分子扩散模型,活化能为Ea=24.5kJ·mol~(-1),苯酚在外墙保温板残料基活性炭上的吸附符合Temkin模型;热力学分析得:在温度低于40℃时,ΔG(0,ΔH=15.761kJ·mol~(-1)(0,ΔS=141.7J·mol~(-1)/K(0,活性炭对苯酚的吸附是自发的吸热过程;混乱度增加,即活性炭更容易吸附苯酚。由此可见以外墙保温板残料为碳源制备的活性炭可以处理应急被苯酚污染的水。     

聚乙二醇、聚丙二醇和环氧乙烷-环氧丙烷嵌段共聚物在固-液界面上的吸附 III:硅烷化活性炭/水和甲基化硅胶/水界面

测定了25℃时硅烷化不同时间(1至30天)的活性炭及甲基化硅胶自水溶液中吸附四种聚乙二醇(PEG)、三种聚丙二醇(PPG)和环氧乙烷(EO)-环氧丙烷(PO)嵌段共聚物pluronic-L64的等温线。结果表明, 在各活性炭样品上的等温线均为Langmuir型的; 同一炭样对不同PEG的极限吸附量(g·g^-^1)与分子量无关; 极限吸附时每个PEG分子所占面积(A)与分子中所含EO数(nEO)间有直线关系, 直线的斜率与硅烷化时间有关, 这一结果可用硅烷化时间延长时吸附分子的EO基可能以其氧原子向水, 碳氢链节靠近固体表面取向的模型解释。根据PPG的极限吸附量与分子量有关和极限吸附时的分子面积推断PPG分子不是以平躺方式吸附。甲基化硅胶对PEG的吸附量极小, 对PPG的吸附量随分子量减小急剧降低, 而对L64的吸附量明显大于在亲水硅胶上的。文中对所得结果给出了初步的解释。     

硅烷化活性炭的表面性质

测定了活性炭经三甲基氯硅烷蒸气处理后比表面、比孔容、平均孔径等的变化;研究了硅烷化炭表面的润湿性质和吸附性质.结果表明,随活性炭与三甲基氯硅烷反应时间的延长,其比表面和比孔容急剧减小,而孔径分布和平均孔径无明显变化;硅烷化后炭表面的疏水性明显增强;硅烷化炭自水中对正丁醇的吸附量增大.     

聚乙二醇、聚丙二醇和环氧乙烷-环氧丙烷嵌段共聚物在固-液界面上的吸附 III:硅烷化活性炭/水和甲基化硅胶/水界面

测定了25℃时硅烷化不同时间(1至30天)的活性炭及甲基化硅胶自水溶液中吸附四种聚乙二醇(PEG)、三种聚丙二醇(PPG)和环氧乙烷(EO)-环氧丙烷(PO)嵌段共聚物pluronic-L64的等温线。结果表明, 在各活性炭样品上的等温线均为Langmuir型的; 同一炭样对不同PEG的极限吸附量(g·g^-^1)与分子量无关; 极限吸附时每个PEG分子所占面积(A)与分子中所含EO数(nEO)间有直线关系, 直线的斜率与硅烷化时间有关, 这一结果可用硅烷化时间延长时吸附分子的EO基可能以其氧原子向水, 碳氢链节靠近固体表面取向的模型解释。根据PPG的极限吸附量与分子量有关和极限吸附时的分子面积推断PPG分子不是以平躺方式吸附。甲基化硅胶对PEG的吸附量极小, 对PPG的吸附量随分子量减小急剧降低, 而对L64的吸附量明显大于在亲水硅胶上的。文中对所得结果给出了初步的解释。     

硫化钠改性活性炭对Pb(Ⅱ)的吸附性能研究

采用质量分数为3%的Na_2S溶液对活性炭浸渍,在600℃以N_2作为保护气对其进行高温处理,研究Na_2S改性活性炭(SAC)吸附Pb(Ⅱ)的动力学和热力学机理,并对吸附Pb(Ⅱ)前后的改性活性炭进行了表征和分析。结果表明,与改性前活性炭相比,SAC的比表面积和总孔容减小,S元素含量显著提高。SAC对Pb(Ⅱ)的吸附效果显著提高,在Pb(Ⅱ)初始浓度为300mg/L时,SAC对Pb(Ⅱ)最大吸附量为122.56mg/g,并且在吸附过程的前80min内可达到总吸附量的95%以上。SAC对Pb(Ⅱ)的吸附过程可用Langmuir模型描述,动力学特性符合拟二级动力学模型。SAC对Pb(Ⅱ)的吸附的热力学参数ΔG在-80~-20k J/mol之间,ΔH0,ΔS0,表明吸附是自发进行的物理吸附与化学吸附共同作用的放热过程。对吸附前后改性活性炭的傅里叶变换红外谱图分析表明,经过Na_2S改性后,活性炭表面引入了砜基,并且砜基强化了改性活性炭对Pb(Ⅱ)的吸附性能。     

自溶液中的吸附 VII: 硅胶自环己烷中吸附醇,酮和酯

The adsorption isotherms of some monofunctional alcohols, ketones and esters from cyclohexane onto silica gel have been determined at 30`C and 10`C. The silica gel used bad a BET area of 417 m2/g and an average pore radius of 45A. The concentrations of free and associated hydroxyls on the silica gel were 1.4 and 4.1/100A^2 respectively. The adsorption order is cyclohexanol>n-octyl alcohol>cyclohexanone>methyl isobutyl ketone>n-propyl acetate=n-amyl acetate. The adsorption decreases with increasing temperature as normal. Except at very low concentrations, the isotherms can be represented by the Langmuir equation. The limiting adsorption, nms, on the silica gel does not accord with the stoichiometric ratio (1:1) between the free surface hydroxyl groups of the adsorbent and the adsorbate. In addition to surface conditions and the functional group of the adsorbate, it seems that the limiting adsorption is also controlled by the other factors, including temperature, solvent, and, sometimes the chain length of the adsorbate. The standard free energy (ΔG0) and standard enthalpy (ΔH0) of the adsorbates in adsorptien processes have been determined from the Langmuir parameters. The results indicate that the absolute value of ΔH0 is higher than that of ΔG0 (in other words, standard entropy ΔS0 is negative), as in the case of the adsorption of gases. Since there is practically no difference in ΔG0 or ΔH0 of adsorption between alcohols or esters, it is suggested that in dilute solution only the polar groups take part in adsorption, and the hydrocarben chains remain in solution during the adsorption process. For ketones, the absolute values of ΔG0 and ΔH0 are somewhat lower for methyl isobutyl ketone than that for cyclohexanone. A possible explanation is that in the adsorbed state the isobutyl chain of the methyl isobutyl ketone may somewhat close to the surface and thus decreases the adsorption and changes the ΔG0 and ΔH0.     

药物曲美布汀对映体在涂敷三(4-甲基苯甲酸)纤维素酯手性固定 相上的HPLC分 离

涂敷15%(wt)三(4-甲基苯甲酸)纤维素酯于大孔硅胶担体上,制备手性固定相,以此手性固定相作填料,湿法装填液相色谱柱,直接分离(±)-曲美布汀对映体。确定对映体在固定相与洗脱液之间分配的自由能变之差值、焓变之差值和熵变之差值,考察洗脱液正己烷-异丙醇(v/v)中异丙醇含量在色谱分离对映体性能方面的影响。当洗脱液中异丙醇含量增加时,对映体的容量因子逐渐降低,分离因子变化不大,分离度逐渐降低。     

Kinetics and thermodynamic study of aniline adsorption by multi-walled carbon nanotubes from aqueous solution

Multi-walled carbon nanotubes (MWCNTs) were used in the adsorptive removal of aniline, an organic pollutant, from an aqueous solution. It was found that carbon nanotubes with a higher specific surface area adsorbed and removed more aniline from an aqueous solution. The adsorption was dependent on factors, such as MWCNTs dosage, contact time, aniline concentration, solution pH and temperature. The adsorption study was analyzed kinetically, and the results revealed that the adsorption followed pseudo-second order kinetics with good correlation coefficients. In addition, it was found that the adsorption of aniline occurred in two consecutive steps, including the slow intra-particle diffusion of aniline molecules through the nanotubes. Various thermodynamic parameters, including the Gibbs free energy change (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°), were calculated. The results indicated that the spontaneity of the adsorption, exothermic nature of the adsorption and the decrease in the randomness reported as ΔG°, ΔH° and ΔS°, respectively, were all negative.     

1-苯基-3-甲基-4-苯甲酰吡唑啉酮-5萃取镓的研究

首次报道了1-苯基-3-甲基-4-苯甲酰吡唑啉酮-5(HPMBP)萃取镓的热力学和动力学, 指出在体系中形成Ga(PMBP)3(H2O)2萃合物, 配体PMBP既有一次溶剂化作用, 又有二次溶剂化作用, 并得到红外光谱和核磁共振谱的证实。镓的萃取过程为水相化学反应控制, 决速步骤为一次溶剂化过程: Ga^3^++HPMBP→Ga(PMBP)^2^++H^+。添加剂三辛基氧化膦(TOPO)不影响HPMBP萃取镓的分配比, 但降低了HPMBP萃取镓的正向速率, 表明动力学抑萃作用与热力学抑萃作用无对应关系。     

固-液界面上的吸附膜

利用Gibbs吸附公式处理了硅胶自四氯化碳和环己烷中吸附脂肪醇、环己醇、苯甲醛、苯甲醚、乙酸丙酯的实验结果,得到吸附膜的表面压(π)和分子面积(A)的关系曲线,这些曲线均可用描述不溶物液态扩张膜的Smith方程描述。文中对所得结果给出了初步的解释。     

硅沸石完美骨架上的吸附Ⅱ.乙胺、正戊烷、乙醇在 FAU型沸石上的吸附热

用测定吸附等温线法研究乙胺、正戊烷和乙醇在疏水高硅FAU沸石上的吸附热效应。根据Clapeyron-Clausius方程,处理吸附等温线,得到不同覆盖度C(C=被吸附分子数/晶胞)的等量吸附热Qst(C)(一定覆盖度C时由Clapeyron-Clausius方程计算的吸附热)及平均等量吸附热Qst^*(一定温度区间里等量吸附热Qst的平均值),以及Qst^*与沸点蒸发热△Hv的差值△H1(定义为相互作用强度△H1=Qst^*-△Hv)。所研究的三种有机分子的△H1的次序为△H1(乙胺)>△H1(正戊烷)>>△H1(乙醇)。这与AT值(定义为脱附温度Td与吸附质的沸点温度Tb的差值,无需单位)有正相关关系。由AT值观察到的高硅FAU沸石Si-O骨架与被吸附乙胺之间可能存在的强相互作用、为本研究测定的热力学定量数据△H1值所证明。     

盐酸在氨基酸水溶液中热力学性质的研究 I. 甘氨酸+盐酸+水体系

Standard potentials (E°_m) of the Ag-AgCl electrode in Glycine+H_2O mixture at 25 ℃, 30 ℃, 35 ℃, 40 ℃, and 45 ℃ have been determined from the EMF measurements of cells of the type: Pt, H (g, 101.325 kPa)|HCl(m)+Glycine+H_2O|AgCl-AgThese values have been utilized to evaluate the transfer energetics (ΔG°_t, ΔH°_t, ΔS°_t) accompanying the transfer of 1 mol HCl from the standard state in water to the standard state in Glycine+H_2O mixtures. Attempts have been made to explain the transfer energetics varying with different compositions of Glycine+H_2O mixtures in the light of ion-solvent interactions and the structureal effects of the solvents.     

煤制活性焦性质对其脱除烟道气中二氧化硫性能的影响

讨论了四种煤制活性焦的性质对其脱除烟道气中SO2性能的影响,活性焦的表面碱性与微孔面积决定了其对烟道气中SO2的吸附与氧化。生成的硫酸主要贮存在活性焦的微孔内。活性焦内的硫酸在脱附温度为300℃时达到最大脱附速率。     

Analysis of interfacial and micellar behavior of sodium dioctyl sulphosuccinate salt (AOT) with zwitterionic surfactants in aqueous media

The interfacial and bulk properties of mixtures of the anionic surfactant (dioctyl sulphosuccinate sodium salt, AOT) with zwitterionic surfactants 3-(N,N-dimethyldodecylammonio) propane sulfonate (DPS), 3-(N,N-dimethyltetradecylammonio) propane sulfonate (TPS), 3-(N,N-dimethylhexadecylammonio) propane sulfonate (HPS) have been studied employing surface tension, fluorescence, and viscometric techniques in aqueous media at 25 °C. It is observed that these mixtures exhibit synergism and these synergistic interactions increase with the enhancement of the hydrocarbon chain of the zwitterionic surfactant. The various physicochemical properties such as critical micelle concentration (cmc), surface excess concentration (Г(max)), minimum area per molecule (A(min)), aggregation number (N(agg)), interaction parameters (β(σ), β(m)), and thermodynamic parameters such as standard Gibbs free energy of adsorption (ΔG(ads)(o)), excess free energy of micellization (ΔG(ex)), and standard Gibbs free energy of micellization (ΔG(m)(o)) have been evaluated. The negative values of ΔG(m)(o) and ΔG(ads)(o) show that the micelle formation and adsorption of surfactant at the air/solution interface is energetically favorable, while a negative value of ΔG(ex) ensures stability of the mixed micelles formed. The Regular Solution Approximation, Motomura and Rosen's approaches have been used to explain and compare the results. The packing parameter (p) ensures the formation of vesicles or bilayers for AOT+DPS/TPS mixtures, which can potentially be used as delivery agents for industrial applications.