Hydrotropic properties of a novel alkylnaphthalene sulfonate

Alkylbenzenesulfonates based on toluene, xylene, as well as cumene, and alkylnaphthalenesulfonates, act as hydrotropes in surfactant systems. A novel sodium diisopropyl-naphthalene sulfonate (SDIPNS) has been devepoped that contains about 92% diisopropylnaphthalene sulfonate, compared to other diisopropylnaphthalene sulfonate preparations that contain less than 50% diisopropylnaphthalene sulfonate. This material is both a hydrotrope and a surfactant. The color of a 35% solution is light yellow, Gardner 3, significantly lighter than comparable materials. Draves wetting time for a 0.5% solution is about 30 s. The Ross-Miles foam test (1% solution) indicates a significant level of initial foam, but the foam is unstable. The solubilites of toluene and limonene in SDIPNS are much higher than in other hydrotropes tested. Hydrotropes raise the cloud point of nonionic surfactants; SDIPNS is the most efficient hydrotrope found for this application. Another measure of hydrotropicity is the amount of hydrotrope required to clear a cloudy detergent formulation; this hydrotrope is quite effective. Another measure is the modification of surfactant formulation viscosity; SDIPNS is quite effective. Additionally, SDIPNS changes the solubility of nonionic surfactants in water. SDIPNS is a surfactant as well as a hydrotrope, demonstrating a critical micelle concentration at about 1%. Presented as a poster session at the American Oil Chemists' Society Annual Meeting & Expo, May 11–13, 1998, Chicago, IL.     

Hydrotropic properties of some short-chain alkylbenzene- and alkylnaphthalene sulfonates

Alkylbenzene sulfonates based on toluene, xylene and cumene, and alkylnaphthalene sulfonates act as hydrotropes in surfactant systems. One measure of hydrotropicity is the amount of hydrotrope required to clear a cloudy detergent formulation; some hydrotropes are more effective than others, depending on the surfactant formulation. Another measure is the modification of the viscosity of surfactant formulations; the change in the viscosity depends on the amount and type of hydrotrope used and on the specific formulation involved. Additionally, alkylnaphthalene sulfonate hydrotropes change the solubility of nonionic surfactants in water, and both types of hydrotrope raise the cloud point of nonionic surfactant solutions; however, the naphthalene-based hydrotropes are more efficient. Ross-Miles foam test data are used to compare the foam characteristics of different alkylnaphthalene sulfonates. A critical micelle concentration (CMC) was determined for the alkylnaphthalene sulfonates, but although alkylbenzene sulfonates do show some surface activity, a CMC could not be found for these materials. Presented as a poster session at the AOCS Annual Meeting & Expo, May 1997, Seattle, Washington, and at Soaps, Detergents, and Oleochemicals: An AOCS International Conference, October 1997, Fort Lauderdale, Florida.     

Hydrotropic and surfactant properties of novel diisopropyl naphthalene sulfonates

A novel surfactant and hydrotrope, sodium diisopropylnaphthalene sulfonate (SDIPNS) has been developed. It contains about 92% diisopropylnaphthalene sulfonate, compared to other materials which are less than 50% diisopropylnaphthalene sulfonate. Aqueous solutions of 34–36% active SDIPNS have dual functionality. They have excellent surface properties and are compatible with conventional anionic, nonionic, and amphoteric surfactants. They demonstrate good laundering detergency in combination with sodium lauryl ethoxy sulfate, with or without builder. They maintain surface activity in 150 ppm hard water (Ca²⁺/Mg²⁺=2∶1), 5% NaCl, pH 2, and pH 12. They are effective hydrotropes. They enhance surfactant solubility, raise the cloud point of nonionic surfactants, and modify the viscosity of surfactant formulations. They are light in color and are low-foaming. Presented as a Poster Session at the American Oil Chemists' Society Annual Meeting, May 9–12, 1999, Orlando, Florida.     

Effect of hydrotropes on solubility and mass transfer coefficient of lauric acid

A comprehensive investigation on the solubility and mass transfer coefficient enhancement of lauric acid through hydrotropy has been undertaken. The solubility and mass transfer studies were carried out using hydrotropes such as sodium cumene sulfonate, sodium p-xylene sulfonate and sodium p-toluene sulfonate under a wide range of hydrotrope concentrations (0 to 3.0 mol/L) and different system temperatures (303 to 333 K). The effectiveness of hydrotropes was measured in terms of Setschnew constant K _s and reported for all hydrotropes used in this study. The solubility data are also fitted in a polynomial equation as the function of hydrotrope concentration.     

Partitioning of o/p-Nitrophenols in the Presence of Hydrotropes in Aqueous Solutions

Abstract

Partitioning of o/p-nitrophenols between organic solvents and water in the presence of hydrotropes such as sodium toluene sulfonate, sodium xylene sulfonate, and sodium cumene sulfonate, has been experimentally investigated and modelled in terms of co-aggregation of the hydrotrope and nitrophenols in aqueous solutions. The phenol-hydrotrope and hydrotrope-hydrotrope interactions are characterized by an aggregation model. The experimental data for a series of hydrotropes are further used to predict the partitioning behavior of p-nitrophenol in the presence of sodium butyl benzene sulfonate (Na-NBBS). The aggregation number of NaNBBS, (～30) obtained from the partitioning data, matches well with that obtained by small angle neutron scattering.     

Aqueous Hydrotropic Solution as an Efficient Solubilizing Agent for Andrographolide from Andrographis paniculata Leaves

Abstract

An aqueous solution based extraction process for andrographolide from Andrographis paniculata leaves has been developed using alkyl benzene sulfonates and carboxylates as hydrotropes. The plant cells are permeabilized by the hydrotrope solutions followed by solubilization of andrographolide into the solutions. The extraction and solubilization of andrographolide is affected by structure and concentration of hydrotrope, temperature and particle size. Sodium cumene sulfonate (Na‐CS) shows the most efficient solubilization of andrographolide amongst the hydrotropes studied. The solubility of andrographolide increased by two orders of magnitude in Na‐CS aqueous solutions and ～96% andrographolide extraction was achieved in just 20 min.     

Hydrotropic Extraction of Reserpine from Rauwolfia vomitoria Roots

Aqueous solutions of sodium cumene sulfonate give quantitative and faster extraction of reserpine from Rauwolfia vomitoria as compared to the extraction using methanol. The extraction rate is influenced by intraparticle diffusion and increases with increasing temperature and hydrotrope concentration. The dynamic extraction data were fitted in a mass transfer model to evaluate diffusion coefficient of reserpine in the solid plant matrix. Amongst all hydrotropes, sodium cumene sulfonate, gave the best extraction and extraction rates of reserpine. The reserpine crystals recovered from aqueous hydrotrope solutions were much smaller in size and showed different morphology than those from methanol.     

ENHANCEMENT OF SOLUBILITY AND MASS-TRANSFER COEFFICIENT OF 1,2-DIHYDROXY-9,10-ANTHRAQUINONE (ALIZARIN) THROUGH HYDROTROPY

The effect of hydrotropes potassium p-toluene sulfonate (KPTS), citric acid, and nicotinamide on the solubility and mass-transfer coefficient of 1,2-dihydroxy-9,10-anthraquinone (alizarin) was studied. Solubility studies were carried out under a wide range of hydrotrope concentrations (0 to 3.0 mol·L^?1) and different system temperatures (303 to 333 K). It was observed that the solubility and mass-transfer coefficient of alizarin increases with an increase in hydrotrope concentration and system temperature. The maximum enhancement factor, the ratio of the value of solubility in the presence and absence of a hydrotrope, was determined for all experiments under study. The effectivity of hydrotropes was measured by the determination of the Setschenow constant, K_s. The order of effectiveness of various hydrotropes based on K_s values is potassium p-toluene sulfonate > citric acid > nicotinamide.     

EXTRACTIVE DISTILLATION WITH AQUEOUS SOLUTIONS OF HYDROTROPES

The effect of hydrotropes on vapor-liquid equilibrium of a mixture provides a potential technique of extractive distillation for systems which are difficult or impossible to separate by normal rectification. Various hydrotropes, such as sodium toluate, sodium toluence sulfonate, sodium cymcnc sulfonate, sodium mesitylene sulfonate and sodium salicylate, in aqueous solutions have been tested for the separation of close-boiling point mixtures, such as p-cresol/2,6-xylenol, isopropanol/ fm-butanol, and wc-butanol/rert-butanol. The changes in the relative volatility increase with the concentration of hydrotrope and with the hydrotrope to solute ratio.     

Amphiphilic antidepressant drug amitriptyline hydrochloride under the influence of ionic and nonionic hydrotropes; micellization and phase separation

Herein we report the micellization and cloud point of an amitriptyline hydrochloride (AMT) under the influence of cationic, anionic and nonionic hydrotropes. Anionic hydrotropes were employed to know the micellar and surface behaviors, besides studying the clouding behavior of AMT drug with cationic, anionic and nonionic hydrotropes. Tensiometric study has been performed and the properties studied include the critical micelle concentration (cmc), maximum surface excess at the air/water interface (Γ_max), the minimum area per of amphiphilic molecule at air/water interface (A_min), and the different thermodynamic parameters, besides clouding phenomenon. Interaction parameters of micelles (β^m) and monolayer (β^σ) indicate that drug-hydrotrope systems show better interaction at the interface than in micelles.     

Effective Separation of Petro Products through Hydrotropy

This paper presents a comprehensive study on the effect of hydrotropes such as sodium salicylate, sodium benzoate, and nicotinamide on the separation of a near boiling mixture, o‐/p‐xylene. The influence of a wide range of hydrotrope concentrations (0 to 3.0 mol/L) and different system temperatures (303 to 333 K) on the separation of o‐/p‐xylene were studied. All hydrotropes used in this work showed an enhancement in the percentage extraction of p‐xylene to different degrees. The percentage extraction of p‐xylene from the o‐/p‐xylene mixture increases with an increase in hydrotrope concentration and also with system temperature. A minimum hydrotrope concentration (MHC) was found essential to initiate significant extraction of p‐xylene from the o‐/p‐xylene mixture. The maximum enhancement factor, which is the ratio of the value in the presence and absence of a hydrotrope, was determined for both cases. The Setschenow constant, k_s, a measure of the effectiveness of a hydrotrope, was determined for each case.     

Aggregation and Phase Separation Phenomenon of Amitriptyline Hydrochloride Under the Influence of Pharmaceutical Excipients

The interaction between the amphiphilic drug amitriptyline hydrochloride (AMT) and the nonionic surfactants used in drug delivery has been investigated. Herein, we report the micellization behavior of AMT in presence of ethoxylated alkyl phenols in aqueous medium and the clouding phenomenon in the absence and presence of different nonionic surfactants in buffer solution. The values of critical micelle concentration (CMC) of AMT obtained using the conductivity method, decrease as nonionic surfactant concentration increases. With an increase in temperature, the CMC first increases and then decreases. At 303.15 K, the maximum CMC values were obtained with or without nonionic surfactant. The results obtained indicate attractive interactions (synergism) between the two mixing amphiphiles in solution. The experimentally obtained critical micelle concentration (CMC) values are always lower than ideal CMC values. Micellar mole fraction (X₁) values, calculated by different proposed models, show the contribution of nonionic surfactant concentration. At a fixed drug concentration (50 mmol kg^?1) and pH (=6.7) nonionic surfactants show continuous increase in cloud point (CP). Increase in drug concentration and pH, in the presence of fixed amounts of nonionic surfactant, increases and decreases the CP, respectively.     

Effect of organized anionic surfactant system on kinetics of polymerization of acrylonitrile initiated by Ce(IV): Citric acid and other organic substrates

The polymerization of acrylonitrile (AN) using the Ce(IV)–citric acid (CA) redox system as an initiator in aqueous nitric acid solution, in the presence of an anionic surfactant, sodium dodecyl sulfate (SDS), has been kinetically studied at a temperature range of 25–45°C. The rate of polymerization (R_p) and disappearance of Ce(IV) (–R_ce) increase with increasing concentration of SDS, above its critical micelle concentration (cmc), when the surfactant molecules are organized. R_p was found to be proportional to [AN]^1.5 and [CA]^0.5. With other organic substrates, R_p follows the increasing order of sorbitol ≥ mannitol > glycerol > CA. But it was found to decrease considerably in the presence of cationic surfactant (CTAB), and nonionic surfactant (Triton-X-100) had no effect on the rate. –R_ce varies linearly with [Ce(IV)] and [CA]. Both R_p and –R_ce increase with increasing temperature. The overall activation energy was found to be 18.31 and 13.72 kcal/mol in the absence and presence of 0.015M SDS, respectively. The chain length of the polyacrylonitrile has also increased with increasing SDS concentration. © 1996 John Wiley & Sons, Inc.     

Solution properties of mixed surfactant system sodium dodecyl sulfate and alkyl polyoxyethylene ether system

The effect of oxyethylene groups in a nonionic surfactant on the solution properties of anionicnonionic systems is described; these systems are sodium dodecyl sulfate (SDS)—hexadecyl polyoxyethylene ethers (C₁₆POE_n, where n=10, 20, 30 and 40). The degree of ionic dissociation of the mixed micelles decreases with increasing numbers of oxyethylene groups in the nonionic surfactant. As polyoxyethylene chain lengths increase, the electrical conductivities of the mixed surfactant solutions decrease, in spite of the decrease in activation energy for conduction. The radius of the mixed micelle with the electric double layer is larger for a nonionic surfactant having a shorter polyoxyethylene chain length than for one having a long polyoxyethylene chain. This may be attributed to the fact that the mixed micelle is formed more easily by a nonionic surfactant with a shorter polyoxyethylene chain length than by one with a longer chain.     

Extraction of Piperine from Piper Nigrum (Black Pepper) by Aqueous Solutions of Surfactant and Surfactant + Hydrotrope Mixtures

Abstract

The effect of combining butyl benzene sulfonate as hydrotrope with a surfactant in aqueous solutions is investigated for isolation of piperine, an alkaloid, from black pepper. The standard free energy change associated with piperine solubilization in the aqueous solutions of surfactant and hydrotrope individually and in their mixtures is determined from the solubility of piperine in these solutions. A combination of sodium dodecyl sulfate (SDS) and the hydrotrope gives increased percentage extraction of piperine as compared to the hydrotrope alone. The piperine purity recovered from aqueous solutions was higher as compared to the purity of piperine recovered using organic solvents. The piperine crystallized from aqueous solutions of surfactants and hydrotrope also showed cleaner surfaces and uniform structures with sharp edges, unlike the particles crystallized from organic solvents.     

Tuning of Cloud Point by the Nature of Surfactant Headgroup: Influence of Counterion and Additives

Work was performed to distinguish the role of sulfonate (–SO₃ ^?) and sulfate (–OSO₃ ^?) with respect to the micellization and clouding phenomenon in ionic surfactant solutions. The clouding phenomenon is a recent addition to the conventional one observed with nonionic surfactants. Three ionic surfactants [sodium dodecylsulfate (SDS), sodium dodecylbenzenesulfonate (SDBS), and sodium dodecylsulfonate (SDSo)] are chosen and the effects of added tetra-n-pentylammonium bromide (TPeAB) and benzyl tributylammonium bromide (BTAC) have been studied on micellization and clouding behaviors in aqueous solution. Based on critical micelle concentration (CMC) and cloud point (CP) measurements, the following order has been observed: SDBS < SDS < SDSo. Though both SDBS and SDSo contain sulfonate groups, they are found at the two ends of the ordering. Therefore, the role of the phenyl ring is also having importance in clouding phenomena. For a typical surfactant, TPeAB was found to be more effective than BTAC. Based on the CP studies, two compositions of SDSo + TPeAB/BTAC were chosen and the effects of different additives (carbohydrate, amino acid, and l-ascorbic acid) on the CP were investigated. Additive may either decrease or increase CP, depending on the structure of the counterion or additive. The present work shows a few novelties: (1) headgroup/counterion dependence of CP and (2) hydrophobicity of counterion/surfactant has an important bearing on the phenomenon. The data can be utilised in improving cloud point extraction methodologies (CPEMs).     

Effects of surfactants on acrylonitrile polymerization initiated by a Cr(VI)–cyclohexanone redox system: A kinetic study

The polymerization of acrylonitrile (AN) was kinetically studied with a Cr(VI)–cyclohexanone (CH) redox system as an initiator from 25 to 45° C in the presence of a surfactant. The rate of polymerization and the percentage of the monomer conversion increased as the concentration of the anionic surfactant [sodium dodecyl sulfate (SDS)] increased above its critical micelle concentration. However, the cationic surfactant (cetyltrimethylammonium bromide) reduced the rate considerably at higher concentrations, whereas the nonionic surfactant (TX‐100) had no effect on the rate. The effects of the Cr(VI), CH, AN, and H⁺ concentrations and the ionic strength on the rates were also examined. The presence of 0.015M SDS reduced the overall activation energy of the polymerization by 5.55 kcal/mol with respect to that in the absence of the surfactant. With increasing SDS concentration, the viscosity‐average molecular weight also increased. A suitable mechanistic scheme was proposed for the polymerization process. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1147–1153, 2004     

The effects of anionic and cationic surfactants on the hydrolysis of sodium barbital

Alkaline hydrolysis reactions of sodium barbital in micelles of sodium dodecyl sulfate (the anionic surfactant SDS), micelles of cetyl trimethylammonium bromide (the cationic surfactant CTAB), and mixed micelles of surfactant/n-C₅H₁₁OH/H₂O were studied by ultraviolet-visible spectrometry. The reaction rate and the activation energy of the hydrolysis of sodium barbital were calculated. The results showed that the rate of sodium barbital hydrolysis decreased with an increase in CTAB content, whereas it increased in the presence of SDS and n-C₅H₁₁OH. The different effects of CTAB and SDS on the hydrolysis of sodium barbital may be related to their interaction with sodium barbital.     

Rheological Investigation of Wormlike Micelles Based on Gemini Surfactant in EG–Water Solution

The self‐assembly behavior of gemini surfactants in ethylene glycol (EG)‐water (5/95, v/v) mixed solvent was investigated by rheological measurements at 10 °C. The influence of molecular structure of the gemini surfactant and added hydrotrope on the solution properties was studied. Sodium salicylate (NaSal) showed stronger ability to induce 2‐hydroxyl‐propanediyl‐α,ω‐bis‐(dimethyldodecylammonium bromide), referred to as 12‐3(OH)‐12, to form wormlike micelles than sodium benzoate. Less NaSal is required to promote a sphere to rod transition and to reach the peak viscosity. Moreover, the concentrations of hydrotrope and gemini surfactant are both lower than conventional single‐chain surfactant systems to reach a comparable viscosity. The strong hydrophobicity of gemini surfactants and hydrotropes is responsible for the high efficiency in forming wormlike micelles in EG/water systems. The geometric structure of gemini surfactants also plays a vital role in self‐assembly into wormlike micelles. Dimethylene‐1,2‐bis‐(dodecyl dimethylammonium bromide), referred to as 12‐2‐12, shows absolute superiority over 12‐3(OH)‐12 in constructing wormlike micelles. The present study will be helpful for developing de‐icing fluids and anti‐freezing solutions, which need rheology control in EG‐aqueous medium at low temperature.     

Studies on aggregation of AOT and NaDEHP via the energy transfer between AO and RB molecules

The aggregation behaviours of sodium bis(2-ethylhexyl)sulfosuccinate (AOT) and sodium bis(2-ethylhexyl)phosphate (NaDEHP) solutions are studied via the energy transfer of acridine orange (AO) and rhodamine B(RB) molecules. The approximate apparent energy transfer efficiency (ϕ_a) of the dye molecules reaches its maximum value when the concentrations of AOT and NaDEHP are far lower than their cmc. This might be caused by the formation of surfactant–dye mixtures. The anionic surfactants (SDS, AS, AOT and NaDHEP), cationic surfactant (CTAB) and nonionic surfactant (Triton-X-100) are chosen to investigate the effect of the structure of surfactant on the ϕ_a between AO and RB molecules. The results indicate that the effective energy transfer may occur in the anionic surfactant systems and it is not obvious in the nonionic and cationic surfactant systems.