十六烷基三甲基溴化铵在N,N二甲基乙酰胺/长链醇体系中临界胶束浓度和热力学函数的微量量热法研究

用微量量热法测定了阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)在非水溶剂N,N二甲基乙酰胺(DMA)中,分别加入长链醇(正庚醇、正辛醇、正壬醇、正癸醇)体系的热功率一时间曲线,由测得的曲线上的数据得到了临界胶束浓度(CMC)和形成热(ΔHθm).根据热力学理论,计算了热力学函数(ΔGθm,ΔSθm),讨论了温度、醇中的碳原子数、醇的浓度与临界胶束浓度(CMC)和热力学函数之间的关系.结果表明:十六烷基三甲基溴化铵(CTAB)的DMA溶液,在含有相同浓度的各种醇的体系中,CMC,ΔHθm和ΔSθm的值随着温度的升高而增加;而ΔGθm的值随着温度的升高而略有降低.在相同温度及相同浓度的醇体系中,CMC,ΔHθm,ΔGθm和ΔSθm的值都随着醇中碳原子数的增加而降低.在相同温度及相同醇的体系中,CMC和ΔGθm的值随着醇的浓度的增加而增加;而ΔHθm和ΔSθm的值随着醇的浓度的增加而减少.     

丁二酸二异辛酯磺酸钠在长链醇/N,N-二甲基甲酰胺体系中临界胶束浓度和热力学函数的微量量热法研究

用微量量热法研究了丁二酸二异辛酯磺酸钠(AOT)在N,N-二甲基甲酰胺(DMF)/长链醇(正戊醇、正己醇、正庚醇、正辛醇)体系中的临界胶束浓度(CMC)和热力学函数( , 和 ). 并分析讨论了醇的浓度、醇中的碳原子数及温度与CMC及热力学参数之间的关系. 结果表明, 在AOT/长链醇/DMF体系中, 当醇中的碳原子数相同且醇的浓度相同时, CMC, , 随温度的升高而增大, 而 随温度的升高而降低|当温度相同且醇中的碳原子数相同时, CMC, , 和 随醇浓度的增加都降低|而当温度相同且醇的浓度相同时, CMC, , 和 随醇中碳原子数的增加都降低.     

微量量热法研究阴离子表面活性剂在DMA/长链醇体系中CMC和热力学函数

在N,N-二甲基乙酰胺(DMA)/长链醇非水溶液体系中, 利用微量量热仪, 研究阴离子表面活性剂十二烷基羧酸钠(SLA)、十二烷基硫酸钠(SDS)的临界胶束浓度(CMC)和热力学函数. 本文在十二烷基羧酸钠, 十二烷基硫酸钠的N,N-二甲基乙酰胺溶液中, 分别加入长链醇(庚醇、辛醇、壬醇、癸醇), 测定体系的热功率-时间曲线. 借助热力学理论, 由测得曲线, 进一步得到临界胶束浓度和热力学函数(ΔH_m⁰, ΔG_m⁰和ΔS_m⁰). 讨论了温度、醇的碳原子数目、醇的浓度与热力学参数之间的关系. 结果表明, 对十二烷基羧酸钠或十二烷基硫酸钠的DMA溶液, 在含有相同浓度的各种醇的体系中, CMC, ΔH_m⁰和ΔS_m⁰的值随着温度的升高而增加, 而ΔG_m⁰的值随着温度的升高而降低. 在相同温度及相同浓度的醇体系中, CMC, ΔH_m⁰,ΔG_m⁰和ΔS_m⁰的值都随着醇中碳原子数目的增加而降低. 在相同温度及相同醇的体系中, CMC, ΔG_m⁰的值随着醇的浓度的增加而增大, 而ΔH_m⁰, ΔS_m⁰的值随着醇的浓度的增加而减少.     

新型脲基双子表面活性剂的合成及其性能

以N,N-二甲基-1,3-丙二胺、固体光气、溴代烷为原料合成了三种新型含脲基双子表面活性剂(LY-12、LY-14、LY-16),并通过1H NMR、ESI-MS和FT-IR表征了结构。测定了其Krafft点、乳化性能、起泡性能;通过测定表面张力γcmc以及不同温度下的临界胶束浓度(CMC)计算表面活性参数(Γmax、Amin、pc20)与热力学参数(ΔGmθ、ΔHmθ、ΔSmθ)。结果表明,LY-12、LY-14的Krafft点低于0℃,LY-16的Krafft点低于10℃;LY-12、LY-14、LY-16的乳化时间分别为173、275和338 s;LY-12的起泡性显著优于LY-14和LY-16;三种表面活性剂的表面张力γcmc分别为38. 77、37. 42和36. 59 m N/m;298. 15K条件下,其CMC值分别为0. 19、0. 15、0. 13 mmol/L。表面活性参数与热力学参数计算表明,三种表面活性剂均具有高的表面活性且胶束的形成是熵驱动的自发放热过程。     

β-/γ-环糊精与Gemini草酸酯季铵盐的相互作用

本文对新合成的双子草酸酯季铵盐表面活性剂以表面张力法测定了25～45℃范围内的临界胶束浓度(0.6698～0.6099mmol·L-1),并计算了胶束形成的相关热力学参数ΔGm0、ΔHm0、ΔSm0.对其与β-,γ-环糊精(β-,γ-CD)的包结作用进行了研究.β-环糊精与双子草酸酯季铵盐表面活性剂的主客体包结物包结比主要为2:1.实验结果表明,环糊精对双子草酸酯季铵盐的胶束化有显著影响.由于双子草酸酯季铵盐的水链被环糊精的空腔包裹,削弱了其胶束生成的能力,使溶液的表面张力随环糊精浓度的增加而大大增加.     

聚氧乙烯-聚氧丙烯嵌段共聚物在水溶液中的胶束化作用

本实验采用表面张力法,苯红紫可见光吸收法测定L64,AE32,AP221等三种不同结构的聚氧乙烯-聚氧丙烯嵌段共聚物的临界胶束形成浓度CMC,发现L64与AE32在低浓度下形成单分子胶束,在高浓度下形成聚集胶束。AP221则只在较低的浓度下形成聚集胶束。不同温度下CMC的测定结果表明温度对L64形成单分子胶束的CMC影响较小,而聚集胶束的浓度则随着温度升高而迅速下降,后者胶束形成热ΔH较高,为140.6kJ/mol。     

两种大孔吸附树脂对麻黄碱和伪麻黄碱的吸附动力学和热力学研究

通过等温静态吸附实验研究大孔树脂AB-8和D101对麻黄碱及伪麻黄碱的等温吸附过程,根据Langmuir平衡吸附速率方程考察两种树脂对两种成分吸附的平衡速率常数,用Van’t Hoff公式计算各热力学参数(ΔHm,ΔGm及ΔSm)。结果表明麻黄碱、伪麻黄碱的吸附平衡数据符合Freundlich吸附等温方程和Langmuir平衡吸附速率方程,相关性良好。吸附的焓变(ΔHm)和熵变(ΔSm)均大于零,吉布斯自由能变(ΔGm)均小于零,表明麻黄碱及伪麻黄碱在树脂上的吸附属于自发的物理吸附过程。     

聚氧乙烯山梨醇酐脂肪酸酯乳化剂对聚氧乙烯(10)油基醚胶束形成的影响

通过平衡表面张力的测定,研究了聚氧乙烯山梨醇酐脂肪酸酯（Tween）系列与聚氧乙烯(10)油基醚（Brij97）混合胶束形成的相互作用参数βm、分子交换能εm及热力学参数（ΔGom、ΔHom、ΔSom）,并探讨了Tween系列分子结构、混合体系的组成及温度对胶束形成的影响。 研究表明,随着Tween碳链的增大,混合胶束中Tween的摩尔分数Xm1增大,协同效应增强;在Tween60/Brij97混合胶束中,ΔGom随着Tween60摩尔分数（α1）的增大而增大;在混合胶束形成中,α1≤0.33时,两组分表现出协同效应;在α1＞0.33时,未表现出协同效应;温度对Tween60/Brij97混合体系的影响表明,温度升高,CMC和ΔGom减小,ΔHom和ΔSom增大,协同效应减弱。     

含酯基Gemini表面活性剂在有机醇-水体系中的胶束热力学及聚集行为

采用电导法研究了不同温度下含酯基Gemini表面活性剂在纯水和在质量分数为10%的甲醇-水(MAWR),乙二醇-水(EG-WR),丙三醇-水(GL-WR)四种体系中的集聚行为和胶束热力学;聚集行为参数包括临界胶束浓度(cmc)和抗衡离子的解离程度(α)以及胶束的热力学参数,包括标准吉布斯自由能(ΔG_m~o)、吉布斯迁移自由能(ΔG_(trans)~o)、吉布斯烷基链胶束化自由能(ΔG_(tail)~o)、标准焓变(ΔH_m~o)和标准熵变(ΔS_m~o),均被计算和讨论。研究表明在所有的研究体系中,cmc值随着疏水链的增加而减小,随着加入的醇结构中羟基数目的增加而增大,随温度的升高先变小,后变大呈U字形;胶束化过程都是自发进行的,并且在293.15 K下,胶束化过程是吸热的,在293.15 K上,胶束化过程是放热的;通过稳态荧光光谱法研究了表面活性剂在纯水、有机醇-水混合溶液中的微极性,结果表明,在相同溶剂中,随着烷基链长度的增加,溶液微环境的疏水性越强;对于相同的Gemini表面活性剂,随着加入含羟基数目越多的醇,其微环境的疏水性越强。并研究了Gemini表面活性剂在混合体系中形成胶束过程的焓-熵补偿曲线。     

均三嗪芳醚聚氧乙烯非离子表面活性剂

近年适应石油化学工业的需要,聚氧乙烯(POE)型非离子表面活性剂的研究得以发展。桑村常彦等合成了一类均三嗪烷醚POE非离子表面活性剂,测定了它们的浊点和临界胶束浓度(CMC)。等合成了均三嗪胺醚POE非离子表面活性剂,测定了它们的     

Studies on the adsorption of Brij-35 and CTAB at the coal-water interface

The adsorption behavior of polyoxyethylene (23) lauryl ether (Brij-35) and cetyl trimethyl ammonium bromide (CTAB) on coal sample has been studied. The adsorption process is found to be sensitive to pH, temperature, electrolyte concentration, and the amount of surface active agent. An attempt has been made to explain the adsorption behavior of the surfactants using the Langmuir equation. The extent of adsorption of Brij-35 on coal is found to be the highest at pH 2, which decreases with increase in pH and remains constant in the neutral and alkaline pH regions. But, the adsorption of CTAB exhibits the opposite behavior of that of Brij-35. Adsorption of any of the surfactant at the coal/water interface sharply decreases the apparent viscosity of 55 wt% coal-water slurry (CWS) at a shear rate of 100 s(-1). Electrostatic adsorption of the surfactants on the coal surface decreases the surface charge and renders the coal surface hydrophobic which is manifested in the form of high apparent viscosity of the coal-water slurry under the test conditions.     

Microcalorimetric Studies on the CMC and Thermodynamic Functions of a Nonionic Surfactant (Tween80) in DMF/Long-Chain Alcohol Systems from <Emphasis Type="Italic">T</Emphasis>=298.15 to <Emphasis Type="Italic">T</Emphasis>=313.15 K

The power-time curves of the micelle formation process were determined for the nonionic surfactant Tween80/nonaqueous solvent (DMF)/long-chain alcohol (n-heptanol, n-octanol, n-nonanol, and n-decanol) systems by titration microcalorimetry at temperatures of (298.15, 303.15, 308.15, and 313.15) K. From the power-time curves, the CMC and DH_m^\uptheta\Delta H_{\mathrm{m}}^{\uptheta} values were obtained. The corresponding values of DG_m^\uptheta\Delta G_{\mathrm{m}}^{\uptheta} and DS_m^\uptheta\Delta S_{\mathrm{m}}^{\uptheta} were also calculated. The relationships of the CMC with the carbon number of the alcohol, the concentration of alcohol, and the temperature, along with the thermodynamic functions, are discussed.     

Conformation and dynamics of polyoxyethylene lauryl ether (Brij-35) chains in aqueous micellar solution studied by 2D NOESY and 1H NMR relaxation

Spin-lattice relaxation time, spin-spin relaxation time and two-dimensional nuclear Overhauser enhancement spectroscopy (2D NOESY) experiments of polyoxyethylene lauryl ether (Brij-35) micelles in aqueous solutions at a concentration of 100 times the critical micellar concentration (cmc) give direct evidence that the hydrophilic polyoxyethylene chains, staying in the exterior of the micellar core, are coiled, bent and aligned around the micellar core with a certain number of water molecules included. This hydrophilic layer is in contact with the solvent, water, keeping the micellar solution stable. 1H NMR relaxation time measurements show that the first oxyethylene group next to the alkyl chain participates in the formation of the surface area of the micellar core. The motion of the hydrophilic polyoxyethylene chains is less restricted as compared with the hy-drophobic alkyl chains.     

5-氨基间苯二甲酸钠和5-羟基间苯二甲酸钠的热力学性质

在水溶液中合成了5-氨基间苯二甲酸钠(1)和5-羟基间苯二甲酸钠(2)固态样品,元素分析和TG-DTG确定其组成符合C8H5O4NNa2·H2O(1)和C8H4O5Na2·H2O(2).用精密自动绝热热量计测定了它们在78～400K温区的低温热容,将实验值用最小二乘法拟合,得到热容随温度变化的多项式方程,用此方程进行数值积分,得到该温区内每隔5K的舒平热容值和各种热力学函数值.用RD496-2000型微热量计测定了样品在298.15K时的标准摩尔溶解焓分别为ΔsolHmθ(1,s)=-44.552±0.164kJmol-1和θΔsolHm(2,s)=-36.055±0.154kJmol-1,计算了其水合阴离子标准摩尔生成焓分别为θΔfHm(C8H5O4N2-,aq)=-684.56±1.67kJmol-1和ΔfHmθ(C8H4O52-,aq)=-1263.43±2.13kJmol-1.用RBC-II型精密转动弹热量计测定了样品的恒容燃烧热分别为ΔcU(1,s)=-13382.14±5.28Jg-1和ΔcU(2,s)=-10339.15±4.15Jg-1,计算了它们的标准摩尔燃烧焓和标准摩尔生成焓分别为ΔcHmθ(1,s)=-3252.90±1.28kJmol-1和θΔcHm(2,s)=-2522.64±1.01kJmol-1,ΔfHmθ(1,s)=-1406.46±1.66kJmol-1,θΔfHm(2,s)=-1993.79±1.46kJmol-1.     

Conformation and dynamics of polyoxyethylene lauryl ether (Brij- 35) chains in aqueous micellar solution studied by 2D NOESY and <Superscript>1</Superscript>H NMR relaxation

Spin-lattice relaxation time, spin-spin relaxation time and two-dimensional nuclear Overhauser enhancement spectroscopy (2D NOESY) experiments of polyoxyethylene lauryl ether (Brij-35) micelles in aqueous solutions at a concentration of 100 times the critical micellar concentration (cmc) give direct evidence that the hydrophilic polyoxyethylene chains, staying in the exterior of the micellar core, are coiled, bent and aligned around the micellar core with a certain number of water molecules included. This hydrophilic layer is in contact with the solvent, water, keeping the micellar solution stable. ¹H NMR relaxation time measurements show that the first oxyethylene group next to the alkyl chain participates in the formation of the surface area of the micellar core. The motion of the hydrophilic polyoxyethylene chains is less restricted as compared with the hydrophobic alkyl chains.     

Valen席夫碱单核铜配合物的合成、热化学性质及其对粟酒裂殖酵母细胞作用的热动力学研究

以甲醇为溶剂,邻香草醛缩乙二胺席夫碱(H2vanen)与一水合醋酸铜[Cu(OAc)2·H2O]反应,合成了一种Valen席夫碱单核铜配合物[Cu(vanen)(H2O)].以盖斯定律为理论基础,设计了一个合理可行的热化学循环.根据该热化学循环,依次测定了各样品的标准摩尔溶解焓,进而求得配位反应的标准摩尔反应焓(θr m?H)为?(16.61±0.54)kJ/mol.再结合其他相关的文献值,求得配合物的标准摩尔生成焓(θf m?H)为?(756.5±2.4)kJ/mol.在32℃条件下,用热导式等温微量热仪测定了不同浓度配合物作用下粟酒裂殖酵母细胞的产热曲线,探讨了不同浓度的配合物对酵母菌生长的影响,分析了配合物的浓度与酵母菌代谢的生长速率常数k、抑制率I、最大发热功率Pmax、半抑制浓度IC50以及达到最大发热功率所需时间tmax等动力学参数之间的关系.分析结果表明,配合物对粟酒裂殖酵母细胞的生长具有低浓度促进、高浓度抑制的Hormesis效应.     

Effect of Alcohols on the CMC and Thermodynamic Functions of Anionic Surfactants in DMF/Long‐Chain Alcohol Using Microcalorimetric Method

The critical micelle concentration (CMC) of two kinds of anionic surfactant (including sodium laurate (SLA) and sodium dodecyl sulfate (SDS)) in mixed alcohol and N, N‐dimethyl formamide solvent (DMF) were investigated through measuring power‐time curves by titration microcalorimetry. From data of the lowest point and the area of the power‐time curves, their CMC and ΔH _m ⁰ can be obtained. According to standard thermodynamic equations, ΔG _m ⁰ and ΔS _m ⁰ also can be calculated. For different surfactant, the influences of the carbon number and the concentration of alcohol on the CMC and standard thermodynamic functions are different in DMF polar medium. These thermodynamic functions for micelle formation can be further interpreted.     

稳态荧光探针法研究二聚壬基酚聚氧乙烯醚硫酸钠的表面行为

介绍了以二聚壬基酚聚氧乙烯醚,氨基磺酸,氢氧化钠为原料,合成二聚壬基酚聚氧乙烯醚硫酸钠(GNPES),同样方法合成壬基酚聚氧乙烯醚硫酸钠(NPES),以芘为荧光探针,用稳态荧光探针法测定了合成的GNPES和NPES的临界胶束浓度。