Effects of additives on the cloud points of selected nonionic linear ethoxylated alcohol surfactants

Effects of various additives including inorganic salts, nonionic and ionic surfactants, water-soluble polymers and alcohols on the cloud points of three linear nonionic surfactants, Tergitol 15-S-7, Tergitol 15-S-9 and Neodol 25-7, were investigated. These surfactants are readily biodegradable and either linear primary or secondary ethoxylated alcohols. Cloud points of these surfactants were functions of their concentrations and concentrations of additives. The cloud points of nonionic surfactant mixtures lay in between the cloud points of individual component surfactants. Presence of two ionic surfactants, sodium dodecyl sulfate (SDS) and cetyl trimethyl ammonium bromide (CTAB), increased the cloud point of 1 wt% Tergitol 15-S-7 micellar solution dramatically when concentrations of ionic surfactants approaching their critical micelle concentration. Addition of water-soluble polymers decreased the cloud point, while addition of inorganic salts can either increase or decrease the cloud points. However, the effect of an alcohol additive on cloud point was dependent on its chain length or its water solubility. Interestingly, synergistic effects between sulfate or phosphate and pentanol on depression of cloud points of Tergitol 15-S-9 were discovered. A linear model predicting cloud points of Tergitol 15-S-X (X = 7, 9 and 12) surfactants and Neodol 25-X (X = 7, 9 and 12) surfactants were proposed with a correlation to logarithm of their ethylene oxide numbers.     

Oleate Ester-Derived Nonionic Surfactants: Synthesis and Cloud Point Behavior Studies

The synthesis and cloud point behavior of high oleate ester-derived nonionic surfactants are now reported. The effect of various polyethoxylate chain lengths (polyethylene glycol with 7, 11, and 16 units of ethylene oxide (EO) monomer) as the surfactant's hydrophilic head on the cloud point was investigated. The effect of varying amounts of sodium chloride and five different ionic surfactants on the cloud points of the synthesized nonionic surfactants were also presented. When the chain length of polyethoxylate increased, the cloud point of the synthesized nonionic surfactant also increased, ranging from 16°C, 43°C, and 64°C for 7, 11, and 16 EO units, respectively. Increments in sodium chloride concentration depressed the cloud point values of the synthesized nonionic surfactants linearly. The addition of ionic surfactants elevated the cloud points of the synthesized nonionic surfactant. However, in the presence of sodium chloride, the cloud point of the mixed ionic-nonionic solution was suppressed and anincrease in ionic surfactant concentration was required to elevate the cloud point. It was also found that the cloud points of synthesized surfactants can be raised up to 95°C in the presence of 4wt% NaCl solution.     

用定量结构性质关系预测表面活性剂的浊点

用结构、电子、空间和热力学等性质为描述符，建立了宏观性质非离子表面活性剂浊点与微观结构之间的定量结构性质关系. 这些描述符包括辛醇/水分配系数lgP、分子表面积A、相对分子质量Mr、偶极矩μ-y和μ-z.通过49个非离子表面活性剂浊点的实验数值与五个性质之间的关系式，成功地预测了其他非离子表面活性剂的浊点.     

Separation of phenols from aqueous micellar solutions by cloud point extraction

The cloud point technique was used to recover phenol, 4-methylphenol, and 4-nitrophenol from aqueous solutions using oxyethylated methyl dodecanoates as nonionic surfactants. Oxyethylated methyl dodecanoates are convenient nonionic surfactants for such separations. Their cloud points can be easily modified by a change in surfactant hydrophilicity or by the addition of a second nonionic surfactant and/or an electrolyte. The use of the hydrophile lipophile balance is preferred to model the cloud point of oxyethylated methyl dodecanoates and their mixtures with other surfactants. The composition of the surfactant-rich phase depends on electrolyte type and the overheating. The phase can contain only 5-15% of water. Recovery of phenols changes in the order 4-nitrophenol >4-methylphenol > phenol and is increased in the presence of sodium chloride. The presence of salting-out electrolytes is preferred both to decrease the cloud point and to increase the efficiency of extraction.     

Effects of Various Additives on the Cloud Point of Dodecyl Polyoxyethylene Polyoxypropylene Ether

Effects of various additives, including electrolytes, alcohols and organic acids, polymers, and ionic and nonionic surfactants, on the cloud point of dodecyl polyoxyethylene (5) polyoxypropylene (4) ether nonionic surfactant aqueous solutions are investigated. The salting-out electrolytes decrease the cloud point while salting-in electrolytes increase it. Most alcohols and organic acids can lower the cloud point except for methanol and ethanol. The polymers form complexes with the surfactant and decrease the cloud point. The added surfactants can be inserted into the micelles of the nonionic surfactant and form mixed micelles, thus raising the cloud point.     

Use of surfactant-mediated phase separation (cloud point extraction) with affinity ligands for the extraction of hydrophilic proteins

The feasibility of utilizing a zwitterionic surfactant, 3-(nonyldimethylammonio)propylsulfate, or nonionic surfactant, Triton X-114, mediated phase separation in conjunction with affinity ligands was studied for hydrophilic protein extractions. Below (or above) its critical temperature (so-called cloud point), aqueous solutions of zwitterionic (or nonionic) surfactants separate into two immiscible phases, a surfactant-rich phase and an aqueous phase. Avidin was successfully extracted into the zwitterionic surfactant-rich phase when a small amount of the affinity ligand, N- biotinoyl)dipalmitoyl- l -alpha- phosphatidyl ethanolamine, was added to the system. It was not possible to extract hexokinase into the surfactant-rich phase of the nonionic surfactant, Triton X-114, even if a considerable amount of octyl-beta-d-glucoside was added to the solution as an affinity ligand. In contrast, the use of the zwitterionic surfactant and octyl-beta-d-glucoside as an affinity ligand proved to be effective for the extraction of hexokinase. The hexokinase extraction efficiency was found to depend upon the solution pH and the concentration of the affinity ligand in the system. The results clearly indicate that hydrophilic proteins can be successfully extracted with surfactant mediated phase separations (cloud point extractions) via use of the zwitterionic surfactant, 3-(nonyldimethylammonio)propylsulfate, and appropriate affinity ligands. Some advantages of zwitterionic surfactants in such extractive processes relative to that of nonionic surfactants are delineated.     

THE INTERACTION BETWEEN DODECYL POLYOXYETH YLENE POLYOXYPROPYLENE ETHER NON1ONIC SURFACTANT AND POLYV1NYLPYRROLIDONE IN AQUEOUS SOLUTIONS

The changes of cloud points and surface tensions of a nonionic surfactant dodecyl polyoxycthylene(5) polyoxypropylene(4) ether (LS54) in aqueous solutions with added polyvinylpyrrolide (PVP-K90) were determined in order to evaluate polymer-surfactant interactions in the bulk solutions. A new model, corona-shaped intra-chain micelles, was applied lo these phenomena and the thermodynamic parameters of micellization were determined.     

Morphology transitions in nonionic surfactant adsorbed layers near their cloud points

The structure of adsorbed layers of several polyoxyethylene alkyl ether (C(n)E(m)) nonionic surfactants on silica and graphite surfaces has been imaged using atomic force microscopy as a function of temperature up to their cloud points. For all surfactants with a cloud point within the experimentally accessible range, the adsorbed layer morphology on silica evolved from globules at low temperatures first into rods and then a mesh with increasing temperature. This mesh structure was retained even when the solutions were heated above their cloud points into the two-phase coexistence region. Only C(12)E(3) was observed to form a laterally unstructured bilayer. On graphite, all surfactants formed straight, parallel hemicylinders at all temperatures examined.     

添加剂对双子表面活性剂DYNOL－604浊点的影响

对双子表面活性剂DYNOL－604的浊点开展研究,考察了添加剂对其浊点的影响 。离子表面活性剂的加入,使其浊点升高,而加入醇时出现了一种双浊点的现象, 我们称之为“下限浊点”和“上限浊点”。即温度低于“下限浊点”和高于“上限 浊点”,体系由浑浊变为澄清。采用NMR手段测定“上限浊点”以上温度体系的自 扩散系数,证明为双连续微乳液结构,并从R比值理论进行分析。     

Clouding and phase behavior of nonionic surfactants in hydrophobically modified hydroxyethyl cellulose solutions

Clouding phenomena and phase behaviors of two nonionic surfactants, Triton X-114 and Triton X-100, in the presence of either hydroxyethyl cellulose (HEC) or its hydrophobically modified counterpart (HMHEC) were experimentally studied. Compared with HEC, HMHEC was found to have a stronger effect on lowering the cloud point temperature of a nonionic surfactant at low concentrations. The difference in clouding behavior can be attributed to different kinds of molecular interactions. Depletion flocculation is the underlying mechanism in the case of HEC, while the chain-bridging effect is responsible for the large decrease of cloud point for HMHEC. Composition analyses for the formed macroscopic phases were carried out to provide support for associative phase separation for the case of HMHEC, in contrast to segregative phase separation for HEC. An interesting three-phase-separation phenomenon was reported in some HMHEC/Triton X-100 mixtures at high surfactant concentrations.     

非离子表面活性剂的雾点研究-电解质的影响

研究了１－１型钠盐对五种非 离子表面活性剂水溶液雾点的影响，有九种钠盐使雾点下降，下降的依次是ＩＯ＾－３＞ＯＨ＾－＞Ｆ＾－＞ＣＨ３ＣＯＯ＾－＞ＢｒＯ＾－３＜＞Ｃｌ＾－＞Ｂｒ＾＿＞ＣｌＯ３＾－≥ＮＯ＾－３；有三种钠盐使雾点升高，升高的效率依次是ＣＮＳ＾－＞ＣｌＯ＾－＞Ｉ＾－。     

Micellar-enhanced ultrafiltration of cadmium ions with anionic–nonionic surfactants

Micellar-enhanced ultrafiltration (MEUF), a surfactant-based separation process, is promising in removing multivalent metal ions from aqueous solutions. The micellar-enhanced ultrafiltration of cadmium from aqueous solution was studied in systems of anionic surfactant and mixed anionic/nonionic surfactants. The micelle sizes and zeta potentials were investigated by dynamic light scattering measurements. The effects of feed surfactant concentration, cadmium concentration and the molar ratio of nonionic surfactants to sodium dodecyl sulfate (SDS) on the cadmium removal efficiency, the rejection of SDS and nonionic surfactants and the permeate flux were investigated. The rejection efficiencies of cadmium in the MEUF operation were enhanced with higher SDS concentration and moderate Cd concentration. When SDS concentration was fixed at 3 mM, the optimal ranges of the molar ratios of nonionic surfactants to SDS for the removal of cadmium were 0.4–0.7 for Brij 35 and 0.5–0.7 for Triton X-100, respectively. With the addition of nonionic surfactants, the SDS dosage and the SDS concentration in the permeate were reduced efficiently.     

Clouding Behavior and Thermodynamic Study of Nonionic Surfactants in Presence of Additives

The present study investigates the effect of different additives on the cloud point (CP) of nonionic surfactants Triton X-100 (TX-100) and Triton X-114 (TX-114) in aqueous solutions. The thermodynamic parameters of these mixtures were calculated at different additive concentrations. The cloud point of nonionic surfactants TX-100 and TX-114 decreased with the increment of electrolyte concentrations and increased with alcohol concentrations. The standard Gibbs free energy was found to be positive for both the surfactants, whereas the enthalpy and the entropy of the clouding phenomenon were found to be positive with alcohols and negative with electrolytes. The overall clouding process was endothermic for alcohols and exothermic for electrolytes.     

双月桂酸三乙醇胺酯水溶液的囊泡性质研究

研究了具有非离子和阳离子双重特性的表面活性剂──双（月桂酸）三乙醇胺酯在稀盐酸溶液中未成囊泡的性质．发现只有当溶液pH值小于4．2时，囊泡才能形成，而在溶液pH值2~3范围内，囊泡稳定性和“耐盐”能力最佳．这些特性被归之于此化合物酸性水解作用的结果．     

某些氰基甲(月无无日)类试剂与表面活性剂的作用机理

本文研究了表面活性剂对1,5-二(2-羟基-5-氯苯基)-3-氰基甲(月朁)(HCPCF)及1,5-二(2-羟基-5-磺基苯基)-3-氰基甲(月朁)(HSPCF)以及其金属络合物吸收光谱的影响;通过对电泳、析相等现象的分析,探讨了HCPCF、HSPCF及其相应络合物反应行为的差别;讨论了胶束对络合反应速度的影响。     

Physicochemical properties of mixed surfacant systems: sodium dodecyl benzene sulfonate with triton X 100

The physicochemical properties of a mixed surfactant system were studied under various conditions. The surfactants were anionic sodium dodecyl benzene sulfonate and nonionic Triton X 100. Variation of specific conductivity with concentration was used to determine the critical micelle concentration of anionic as well as the mixed surfactants. Iodine solubilization method was used to determine the CMC of the nonionic surfactant. The interaction parameter between the surfactant molecules were calculated. The wetting, foaming and detergent properties of mixed surfactant systems were studied. The variation of contact angle of the solution with teflon surface as a function of surfactant concentration was found to be a reasonably good method to determine the critical micelle concentration. Viscosity and cloud points were also determined. All these quantities are discussed. Received: 14 January 1998 Accepted: 11 June 1998     

Quantifying the hydrophobic effect. 2. A computer simulation-molecular-thermodynamic model for the micellization of nonionic surfactants in aqueous solution

In this article, the validity and accuracy of the CS-MT model is evaluated by using it to model the micellization behavior of seven nonionic surfactants in aqueous solution. Detailed information about the changes in hydration that occur upon the self-assembly of the surfactants into micelles was obtained through molecular dynamics simulation and subsequently used to compute the hydrophobic driving force for micelle formation. This information has also been used to test, for the first time, approximations made in traditional molecular-thermodynamic modeling. In the CS-MT model, two separate free-energy contributions to the hydrophobic driving force are computed. The first contribution, gdehydr, is the free-energy change associated with the dehydration of each surfactant group upon micelle formation. The second contribution, ghydr, is the change in the hydration free energy of each surfactant group upon micelle formation. To enable the straightforward estimation of gdehydr and ghydr in the case of nonionic surfactants, a number of simplifying approximations were made. Although the CS-MT model can be used to predict a variety of micellar solution properties including the micelle shape, size, and composition, the critical micelle concentration (CMC) was selected for prediction and comparison with experimental CMC data because it depends exponentially on the free energy of micelle formation, and as such, it provides a stringent quantitative test with which to evaluate the predictive accuracy of the CS-MT model. Reasonable agreement between the CMCs predicted by the CS-MT model and the experimental CMCs was obtained for octyl glucoside (OG), dodecyl maltoside (DM), octyl sulfinyl ethanol (OSE), decyl methyl sulfoxide (C10SO), decyl dimethyl phosphine oxide (C10PO), and decanoyl-n-methylglucamide (MEGA-10). For five of these surfactants, the CMCs predicted using the CS-MT model were closer to the experimental CMCs than the CMCs predicted using the traditional molecular-thermodynamic (MT) model. In addition, CMCs predicted for mixtures of C10PO and C10SO using the CS-MT model were significantly closer to the experimental CMCs than those predicted using the traditional MT model. For dodecyl octa(ethylene oxide) (C12E8), the CMC predicted by the CS-MT model was not in good agreement with the experimental CMC and with the CMC predicted by the traditional MT model, because the simplifying approximations made to estimate gdehydr and ghydr in this case were not sufficiently accurate. Consequently, we recommend that these simplifying approximations only be used for nonionic surfactants possessing relatively small, non-polymeric heads. For MEGA-10, which is the most structurally complex of the seven nonionic surfactants modeled, the CMC predicted by the CS-MT model (6.55 mM) was found to be in much closer agreement with the experimental CMC (5 mM) than the CMC predicted by the traditional MT model (43.3 mM). Our results suggest that, for complex, small-head nonionic surfactants where it is difficult to accurately quantify the hydrophobic driving force for micelle formation using the traditional MT modeling approach, the CS-MT model is capable of making reasonable predictions of aqueous micellization behavior.     

SOLUBILIZATION IN MIXED REVERSE MICELLAR SYSTEMS OF AOT/NONIONIC SURFACTANTS/n-HEPTANE

Solubilization of water and aqueous NaCl solutions in mixed reverse micellar systems of anionic surfactant AOT and nonionic surfactants in n-heptane was studied. It was found that the maximum solubilization capacity of water was higher in the presence of certain concentrations of NaCl electrolyte, and these concentrations increased with the increase of nonionic surfactant content and their EO chain length. Soluibilization capacity was enhanced by mixing AOT with nonionic surfactants. The observed phenomena were interpreted in terms of the stability of the interfacial film of reverse micellar microdroplet and the packing parameter of the surfactant that formed mixed reverse micelles.