Effects of Molecular Structure and Temperature on Micellization of Cationic Ammonium Gemini Surfactants in Aqueous Solution

Micellization of four cationic quaternary ammonium gemini surfactants, having a diethyl ether or hexyl spacer with the alkyl chain lengths of 12 and 16 carbon atoms, was studied using isothermal titration microcalorimetry (ITC) and electrical conductivity measurements in the temperature range from 298.15 to 313.15 K. In this temperature range, where surfactants are normally applied, the temperature almost does not influence the critical micelle concentration (CMC) and the degree of micelle ionization (α) values of the gemini surfactants, and the replacement of a hexyl spacer by a diethyl ether spacer leads to a slight decrease in the CMC and α values. However, as the alkyl chain length increases from 12 to 16 carbon atoms, the CMC values significantly decrease from 0.99–1.19 mM to 0.020–0.057 mM. In particular, the enthalpy of micellization (ΔH_mic ) and the associated thermodynamic parameters show obvious changes with varying temperature and molecular structure. ΔH_mic becomes much more exothermic at higher temperature or for the surfactants with a more hydrophilic spacer. Moreover, the heat capacity change of micellization (ΔC _{P, mic} ) is less exothermic for the surfactants with a more hydrophilic spacer or a longer alkyl chain. The enthalpy–entropy compensation data show that the surfactants with longer alkyl chains have a more stable micellar structure.     

Adsorption of some anionic surfactants on barite and at solution/Air interfaces

The adsorption behavior of synthesized anionic surfactants with the chemical structure RO-Ph-N=N-Ph-SO₃Na, where R is an octyl, dodecyl, or cetyl group, was analyzed by using a modified version of the Frumkin adsorption isotherm. The values of thermodynamic parameters (including free energy of micellization, ΔG _mic, and of adsorption, ΔG _ads) at the solution/air interface and the solid/liquid interface were calculated, and the relation between the adsorption of the surfactants at these interfaces was investigated. Studies of the surface properties of these synthetic surfactants showed that the length of the hydrocarbon chain of these surfactants plays a major role in determining their surface and thermodynamic properties and that there is a good relationship between the effectiveness of adsorption of the surfactant and its efficiency as a collector.     

Counterion-coupled gemini (Cocogem) surfactants based on dodecylisopropylol amine and dicarboxylic acids: synthesis,characterization and evaluation as biocide against SRB

New cocogem surfactants were synthesized by interaction of dodecylisopropylol amine with dicarboxylic (oxalic, succinic, adipic, sebacic, tartaric, maleic, fumaric, isophthalic) acids. By tensiometric method, the surface activity of aqueous solutions of the synthesized cocogem surfactants at the border with air was studied and, by conductometric method, the specific electrical conductivity of these solutions was determined. The degree of counterion binding (β), critical micelle concentration (CMC), effectiveness of surface tension reduction (π_CMC), surface excess concentration (Γ_max), area per molecule at the interface (A_min), changes of Gibbs free energies of adsorption (ΔG_ad) and micellization (ΔG_mic) have been calculated. The character of change of the colloidal-chemical indices depending on spacer-group nature and length has been clarified. So, with an elongation of the spacer group and when passing from cis-form to trans-form, the value of CMC decreases. The obtained cocogem surfactants exhibit a considerable bactericidal effectiveness against sulfate-reducing bacteria. The bactericide properties of the cocogem surfactants containing in the spacer chain a saturated hydrocarbon fragment and benzene ring are stronger than for the others.     

Synthesis and Physico-Chemical Properties of Sodium 3-Oxo-2-(3-(4-sulphonatophenyl)triaz-2-enyl)octadecanoate Anionic Surfactant

The novel anionic surfactant sodium 3‐oxo‐2‐(3‐(4‐sulphonatophenyl)triaz‐2‐enyl)octadecanoate (SSTO) was prepared from renewable raw materials; glycine and palmitic acid. Surface and bulk properties of SSTO were investigated by surface tension and electrical conductivity techniques at 298, 308, 318 and 328 K. Surface properties including critical micelle concentration (CMC), maximum surface excess concentration (Γ_max), minimum area per molecule (A_min), surface tension at CMC (γ_CMC), effectiveness of surface tension reduction (Π_CMC), efficiency of surface adsorption (pC₂₀), and degree of counterion dissociation (α) were determined. The thermodynamic parameters of micellization (ΔG°_mic, ΔH°_mic and ΔS°_mic) and adsorption (ΔG°_ad, ΔH°_ad and ΔS°_ad) were also investigated at 298, 308, 318 and 328 K. The effect of 3 wt% n‐propanol, n‐butanol and n‐pentanol on surface tension and conductivity at 298 K was also determined.     

Synthesis, Surface, Thermodynamic Properties of Some Biodegradable Vanillin-Modified Polyoxyethylene Surfactants

Four water-soluble non-ionic ethoxylated surfactants based on vanillin were synthesized (VE₁₅, VE₂₀, VE₄₀, and VE₆₀). The chemical structures of these surfactants were confirmed using FT-IR and ¹H-NMR spectra. The molecular weights of the compounds were determined using viscosity measurements and gel permeation chromatography. Surface tension as a function of the concentration of the surfactant in aqueous solution was measured at 25, 40 and 55?°C. From these measurements, the critical micelle concentration (CMC), effectiveness (??_cmc), efficiency (pC₂₀), maximum surface (??_max) excess and minimum surface area (A _min), were calculated. The surface activity measurements showed their high tendency towards adsorption and micellization and their good surface tension reduction, and low interfacial tension. The emulsion stability measurements showed the applicability of these surfactants as emulsifying agents. The thermodynamic parameters of micellization (??G _mic, ??H _mic, ??S _mic) and adsorption (??G _ads, ??G _ads, ?S _ads) showed their tendency towards adsorption at the interfaces and also micellization in the bulk of their solutions. The biodegradability of the prepared surfactants was tested in river water using die-away method and showed their readily biodegradation in the open environment.     

The relationship of the environmental effect of surfactants to their interfacial properties

In an investigation of possible relationships between interfacial properties of surfactants and their environmental effect, using several anionic and nonionic surfactants, a linear correlation was found between the parameters, ΔG ⁰ _ad/A _min, and rotifer toxicity. ΔG ⁰ _ad is a standard free energy of adsorption at the air/aqueous solution interface, and A _min is the minimal hydrated cross-sectional area of the surfactant molecule. Both quantities were evaluated from surface tension data. This correlation is much better than attempted correlations of the toxicity with the negative logarithm of the critical micelle concentration (−log CMC) or with ΔG ⁰ _ad or A _min alone. The ΔG ⁰ _ad/A _min correlation with rotifer toxicity is also better than the correlation with the analogous parameter, Δ _s ^| G _ads ^0| A_min, obtained from adsorption isotherms of the surfactants on a solid immobilized membrane simulating a cell membrane. The data support our hypothesis that toxicity is determined both by adsorption tendency and ease of cell membrane penetration.     

Synthesis and Surface Active Properties of tri[(N‐alkyl‐N‐ethyl‐N‐Sodium carboxymethyl)‐2‐Ammonium bromide ethylene] Amines

Trimeric betaine surfactants tri[(N‐alkyl‐N‐ethyl‐N‐sodium carboxymethyl)‐2‐ammonium bromide ethylene] amines were prepared with raw materials containing tris(2‐aminoethyl) amine, alkyloyl chloride, lithium aluminium hydride, sodium chloroacetate, and bromoethane by alkylation, Hoffman degradation reaction, carboxymethylation and quaternary amination reaction. The chemical structures of the prepared compounds were confirmed by FTIR, ¹H NMR, MS and elemental analysis. With the increasing length of the carbon chain, the values of their critical micelle concentration initially decreased. Surface active properties of these compounds were superior to general carboxylate surfactants C₁₀H₂₁CHN⁺(CH₃)₂COONa. The minimum cross‐sectional area per surfactant molecule (A_min), standard Gibbs free energy adsorption (ΔG_ads) and standard Gibbs free energy micellization (ΔG_mic) are notably influenced by the chain length n, and the trimeric betaine surfactants have greater ability to adsorb at the air/water interface than form micelles in solution. The efficiency of adsorption at the water/air interface (pC₂₀) of these surfactants increased with the increasing length of the alkyl chain. Their foaming properties, wetting ability of a felt chip, and lime‐soap dispersing ability were also investigated.     

Synthesis,Characterization, Surface,and Thermodynamic Studies of Alkyl Tetrachloroferrates: Performance Evaluation of Their Nanostructures as Biocides

Decyl and dodecylamino tetrachloroferrates were synthesized and characterized using Fourier-transform infrared spectroscopy (FTIR), elemental analysis, X-ray diffraction (XRD), nuclear magnetic resonance (¹H-NMR), and atomic absorption spectroscopy (AAS). The surface properties of the cationic surfactants including critical micelle concentration, effectiveness, minimum surface area, and maximum surface excess were determined using surface tension measurements. The effectiveness of surface tension reduction (π_cmc) was found to increase as the hydrophobic chain length increases with values of 30 and 34 mN m⁻¹ for C₁₀ and C₁₂, respectively. Moreover, the effect of temperature on micellization was determined over the range of 35–55 °C. Thermodynamic parameters (ΔG°, ΔS°, and ΔH°) were calculated and the results indicate a spontaneous process for both micellization and adsorption. The nanoparticles (NC₁₀ and NC₁₂) of the prepared surfactants were obtained using the ball mill technique. The particle size and morphology of the nanoparticles were determined using transmission electron microscope measurements. The antibacterial study of the nanoparticle surfactants revealed their strong efficiency against fungi and different pathogenic bacteria compared with the original surfactants.     

Synthesis,surface active and thermal properties of novel imidazolium cationic monomeric surfactants

A series of long chain water soluble cationics have been synthesized by using renewable raw materials like fatty alcohols and epichlorohydrin. The surface activity of the molecules has been determined by measurement of their conductance and surface tension in aqueous solution. The dynamics of surface activity of these surfactants have also been investigated in the presence of sodium halides, NaCl and NaBr by surface tension measurement. A series of useful parameters like critical micelle concentration (cmc), surface tension at the cmc (γ_cmc), adsorption efficiency (pC20), effectiveness of surface tension reduction (Π_cmc), Gibbs free energy of the micellization (ΔG_0 mic) and Gibbs free energy of adsorption (ΔG_0 ads) have been determined from the measurements obtained by surface tension and conductivity method. Further with the application of the Gibbs adsorption isotherm, maximum surface excess concentration (θ_max) and minimum surface area/molecule (A_min) at the air–water interface were also estimated. Thermal stability of these long chain cationics has been measured by thermal gravimetric analysis under nitrogen atmosphere. Analysis of thermal stability measurement indicated that the thermal stability of these long chain imidazoliums increase with an increase in chain length.     

Investigation of α‐iron oxide‐coated polymeric nanocomposites capacity for efficient heavy metal removal from aqueous solution

In the present study, PS@α‐Fe₂O₃ nanocomposites were prepared by chemical microemulsion polymerization approach and the ability of magnetic beads to remove Cu(II) ions from aqueous solutions in a batch media was investigated. Various physico‐chemical parameters such as pH, initial metal ion concentration, temperature, and equilibrium contact time were also studied. Adsorption mechanism of Cu²⁺ ions onto magnetic polymeric adsorbents has been investigated using Langmuir, Freundlich, Sips and Redlich–Petersen isotherms. The results demonstrated that the PS@α‐Fe₂O₃ nanocomposite is an effective adsorbent for Cu²⁺ ions removal. The Sips adsorption isotherm model (R² > 0.99) was more in consistence with the adsorption isotherm data of Cu(II) ions compared to other models and the maximum adsorbed amount of copper was 34.25 mg/g. The adsorption kinetics well fitted to a pseudo second‐order kinetic model. The thermodynamic parameters (ΔH°, ΔS°, and ΔG°) were calculated from the temperature dependent sorption isotherms, and the results suggested that copper adsorption was a spontaneous and exothermic process. POLYM. ENG. SCI., 55:2735–2742, 2015. © 2015 Society of Plastics Engineers     

Adsorption Characteristics of Atrazine on Granulated Activated Carbon and Carbon Nanotubes

Adsorption of atrazine (ATZ) from aqueous solutions by granular activated carbon (GAC) and carbon nanotubes (CNT) was studied in a batch‐mode adsorption system at different initial concentrations of ATZ (1.0–30.0 mg L^–1) and at three temperatures of 288, 296 and 304 K. The adsorption isotherms of Langmuir, Freundlich, Polanyi–Manes, and Brunauer–Emmett–Teller (modified) were used to model the process. The adsorption kinetics followed a pseudo‐second‐order kinetic model. The thermodynamic parameters ΔH⁰, ΔS⁰, and ΔG⁰ of the adsorption were estimated. The thermodynamic parameters indicate that the adsorption process is spontaneous and exothermic.     

Synthesis and study of the surface properties of long-chain alkylnaphthalene sulfonates

Long-chain alkylnaphthalene sulfonates were synthesized by means of a Wurtz-Fittig reaction, and the basic properties were studied in water at 30°C. Through surface tension measurements, the following values were determined: the critical micelle concentration (CMC) and the surface tension at the CMC (γ_CMC). The following values were calculated: area per molecule at the CMC (A_CMC), standard free energy change of micellization (ΔG _mic ^o ), standard free energy of adsorption (ΔG _ad ^o ), and the “efficiency” of a surfactant in reducing surface tension (pC₂₀). The micelle aggregation numbers were measured through steady-state fluorescence-quenching methods. As the chain length of the hydrocarbon of n-alkylnaphthalene sulfonate increased, the Krafft temperature increased, the surface tension decreased, the value of CMC decreased, pC₂₀ increased, ΔG _ad ^o and ΔG _mic ^o became more negative, and the micelle aggregation number increased. The results showed that sodium α-(n-decyl)naphthalene sulfonate (DNS) had a high pC₂₀, low Krafft temperature, and lower CMC than other surfactants in this study. Thus, DNS and the other n-alkylnaphthalene surfactants studied exhibit desirable properties that may be of value in some fields such as detergency, oil recovery, and dyes.     

Synthesis and some studies on fluorinated cationic surfactants: surface and biocidal activities

Three fluorinated cationic surfactants were prepared by condensing N-(2-bromoethyl)perfluoroalkylamides with stoichiometric amounts of pyridine, triethanolamine, and triethylamine to produce three quaternary ammonium salts. The surface and biocidal properties of these surfactants were investigated to find the relation between the structure of the hydrophilic portion of the compounds and their efficiency as biocides. The properties studied included critical micelle concentration (CMC), effectiveness (II_CMC), surface excess concentration (T_max), and area occupied by a molecule (A_min). Free energies of micellization (ΔG _mic ^o) and adsorption (ΔG _ads ^o) of the surfactants in aqueous solution were calculated. The minimal inhibitory concentrations of the prepared compounds were tested against five strains as representative group of microorganisms.     

Evaluation of a functionalized copolymer as adsorbent on direct dyes removal process: Kinetics and equilibrium studies

Functionalized polymeric microbeads were investigated as adsorbent for the removal of three direct dyes from aqueous solutions. The effects of different experimental parameters, such as initial dye concentration, temperature, and solution pH on the adsorption process were investigated. The adsorption process can be conducted with very good result at normal working conditions: neutral pH and normal temperature. The maximum percentage removal obtained was 99.11% for the symmetrical disazo dye, 90.14% for asymmetrical disazo dye, and 98.53% for trisazo dye. The adsorption kinetics followed the pseudo‐second‐order equation for all three investigated dyes in all working conditions. The experimental data were fitted to Langmuir, Freundlich, Sips, and Redlich–Peterson isotherm models, and the best fit was obtained with Sips model. Thermodynamic parameters (ΔH°, ΔS°, and ΔG°) revealed that dye adsorption is an endothermic and spontaneous process. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Adsorptive removal of cationic dye from aqueous solutions by ZnO/ZnMn2O4 nanocomposite

The ZnO/ZnMn₂O₄ nanocomposite (ZnMn) was used as adsorbent for the removal of cationic dye Basic Yellow 28 (BY28) from aqueous solutions. The adsorbent was characterized by X-ray diffraction, scanning electron microscope, TEM, Fourier transform infrared ray, BET, particle size distribution and zeta potential measurements. The adsorption parameters, such as temperature, pH and initial dye concentration, were studied. Kinetic adsorption data were analyzed using the pseudo-first-order, pseudo-second-order and intraparticle diffusion kinetic models. The Langmuir and Freundlich isotherm models were applied to fit the equilibrium data. The maximum adsorption capacity of BY28 was 48.8 mg g^?1. Various thermodynamic parameters, such as ΔG°, ΔH° and ΔS°, were calculated.     

Solubilization of Ni Imidazole Complex in Micellar Media of Anionic Surfactants,Sodium Dodecyl Sulfate and Sodium Stearate

The solubilization and physicochemical behavior of a coordination complex of nickel, namely [Ni(im)₆]F₂·5H₂O [hexakis(imidazole)nickel(II) fluoride pentahydrate], in aqueous micellar media of anionic surfactants, i.e., sodium dodecyl sulfate (SDS) and sodium stearate (SS), were investigated by using UV–Vis spectroscopy and electrical conductivity measurements. Spectroscopic techniques were used for the computation of binding constant (K_b), partition coefficient (K_x), change in free energy of binding (ΔG_b), and change in free energy of partition (ΔG_p), whereas electrical conductivity data was helpful to calculate thermodynamic parameters of micellization of surfactants in the presence of the Ni complex, i.e., standard entropy of micellization (ΔS_m), free energy (ΔG_m), and enthalpy of micellization (ΔH_m). It is evident from the results that solubilization of the Ni complex takes place because of electrostatic as well as hydrophobic interactions. The presence of the Ni complex in micellar media increases the critical micelle concentration of both surfactants owing to the structure‐breaking effect.     

A New Approach to the Dissolution Tests Management to Obtain Kinetic and Thermodynamic Data: Release of a Model Drug from Glyceryl Behenate Matrix Tablets

This study is focused on the use of glyceryl behenate as a lipophilic excipient of matrix tablets providing controlled drug release. The aim of this study is to evaluate activation energy (EA) and changes of the thermodynamic parameters (ΔH, ΔS, ΔG) of a dissolution process. These values, which have not yet been published, can lead to better understanding of a drug release mechanism and can extend the use options of glyceryl behenate in the pharmaceutical industry. Values of ΔH, ΔS, ΔG and E_A, providing an overall thermodynamic view on the studied matrix tablets, are evaluated based on the temperature-dependences of the release rate constant of a model drug (temperature range 25 - 45 °C). The studied lipophilic matrix tablets contain 10% to 50% of glyceryl behenate. Dissolution testing is carried out in an aqueous solution of HCl with addition of NaCl (pH1.2). Positive values of ΔH in the range of 3.83 to 56.13 kJ mol^-1 and positive values of ΔG indicate that the dissolution of the studied glyceryl behenate matrix tablets is an endothermic process which does not proceed spontaneously (in a temperature range of 25 - 45 °C). The negative slope of the linear curves of enthalpy-entropy compensation confirms the entropy-driven dissolution. Practical Applications : A better understanding of the dissolution process is an important aspect, e.g., in the field of drug formulation strategy. In this study, it is confirmed that the influence of temperature on the model drug release rate is negligible for tablets containing more than 40% of glyceryl behenate. It is an important result for drug design due to the reduction of risk of a possible dose dumping effect induced by temperature and the prevention of in vivo therapeutic failure.     

Cationic Imidazolium Monomeric Surfactants: Their Synthesis and Surface Active Properties

A series of long-chain ester-based water-soluble cationics have been synthesized by using renewable raw materials like fatty acids and halogenated alcohols. The surface activity of the molecules has been determined by measurement of their conductance and surface tension in aqueous solution. The dynamics of surface activity of these surfactants have also been investigated in the presence of sodium halides (NaCl and NaBr) by surface tension measurement. A series of useful parameters like critical micelle concentration (CMC), surface tension at the CMC (γ_CMC), adsorption efficiency (pC₂₀), effectiveness of surface tension reduction (Π_CMC), Gibbs free energy of the micellization (ΔG _0mic) and Gibbs free energy of adsorption (ΔG _0ads) have been determined from the measurements obtained by surface tension and conductivity methods. Further with the application of the Gibbs adsorption isotherm, maximum surface excess concentration (Γ_max) and minimum surface area/molecule (A_min) at the air–water interface were also estimated. Thermal stability of these long chain cationics have been measured by thermal gravimetric analysis under a nitrogen atmosphere. Analysis of thermal stability measurement indicated that the thermal stability of these long chain imidazoliums increases with an increase in chain length.     

Adsorption of ethoxylated alkylphenol–formaldehyde polymeric surfactants at the aqueous solution–air interface

The adsorption behaviour of some ethoxylated alkylphenol–formaldehyde polymeric non-ionic surfactants, at the aqueous solution–air interface, was investigated by measuring the surface tension (γ) as a function of concentration (C) at four temperatures. By applying the Gibbs adsorption equation to the γ versus C data, the adsorption isotherms of these polymeric surfactants were obtained. Surface concentration (Λ) of the investigated polymeric non-ionics was found to increase with decreasing temperature and decreasing hydrophobic group (R) chain length, while varying the length of polyoxyethylene chain (%EO) appeared to have an insigificant effect. Effects of temperature, %EO and chain length R on the surface pressure (π) of the surfactant solutions were also investigated.