Determination of critical micelle concentration (CMC) of nonionic surfactants by donor-acceptor interaction with lodine and correlation of CMC with hydrophile-lipophile balance and other parameters of the surfactants

The nonionic surfactants form donor-acceptor complexes with iodine in aqueous medium. The spectral absorption and the shift in the λ_max of l₂ upon complexation have been exploited to determine the critical micelle concentration (CMC) of Tweens, Brijs, and Triton X-100. The CMC values obtained closely agree with those determined by other methods, including measurements of static surface tension, differential refractive index, and iodine solubilization. The spectral characteristics of the complex salt Kl₃ can be utilized as well to derive similar information. The CMC and the spectral shift can be correlated with the weight fraction of the polyoxyethylene groups and the hydrophile-lipophile balance (HLB) in various ways, with the parameters in these relationships depending on the series to which the surfactant belong. Because both CMC and HLB depend on temperature, the results and the relations obtained are temperature-dependent; those presented are with reference to 298 K.     

非离子表面活性剂定量结构-性质相关性的研究

用量子化学参数来描述非离子表面活性剂的分子结构，研究分子的结构与临界胶束浓度(cmc)和表面张力(rcmc)的定量构效关系，建立了定量模型。其中，采用量子化学AM1方法和B3LYP／／6—31G^*方法计算了44个非离子表面活性剂化合物的电子结构特征，选取了7种量化参数和疏水链的烷基碳原子数，利用多元回归分析方法建立方程。回归结果表明，分子轨道能量(EHOMO)和电荷参数对cmc和rcmc影响较大，它们分别反映了非离子表面活性剂分子与水分子问的价键作用和静电作用。     

Synthesis and surface activity of nonionic surfactants containing fluorocarbon hydrophobes

Nonionic surfactants having polydisperse polyoxyethylene chains and highly fluorinated hydrophobes were synthesized via a complex reaction route and their adsorption at water/air interfaces studied. They exhibit high surface activity and decrease both effectively and efficiently the surface tension of their aqueous solutions. The effect of the length of the polyoxyethylene chain upon surfactant surface activity is relatively low. Lower values of surface tension, below 30 mN m^?1, are obtained for surfactants having a low degree of ethoxylation. Surfactants having two terminal highly fluorinated hydrophobes are less surface active than analogues with one terminal hydrophobe.     

Fluorescence technique for the determination of low critical micelle concentrations

A technique for determining low critical micelle concentrations (CMC) by means of a hydrophobic fluorescence probe has been developed. The amount of the fluorescent probe at the CMC is so small that the effect of the probe on micelle formation is negligible. The fluorescence intensity was measured at fixed dye/surfactant ratios, and it decreased with concentration. A quantity proportional to fluorescent quantum yield was calculated and found to be high for concentrations of surfactant above the CMC and almost zero below the CMC, giving a distinct break in the quantum yield vs. the concentration curve.     

Contrasts in the surface activity of polyoxypropylene and polyoxybutylene-based block copolymer surfactants

Previous studies have shown that polyoxybutylene surfactant hydrophobes are less polar than polyoxypropylene hydrophobes. Polyoxyalkylene hydrophobes can be modified by ethoxylation to give terminal polyoxyethylene block hydrophilic groups. Polyoxybutylene/polyoxyethylene copolymer surfactants exhibit differentiated interfacial tensions, and wetting and foaming properties when compared to structurally equivalent polyoxypropylene/polyoxyethylene copolymers. There have been no reported comparisons, however, of polyoxybutylene/polyoxyethylene copolymers and polyoxypropylene/polyoxyethylene analogues in terms of fundamental parameters, such as critical micelle concentration, area per molecule at the interface, efficiency, and effectiveness. In one phase of this work, four polyoxybutylene/polyoxyethylene block copolymer surfactants were compared to structurally analogous polyoxypropylene/polyoxyethylene materials. Findings showed that polyoxybutylene/polyoxyethylene copolymers exhibited enhanced cotton wetting and lower surface and interfacial tensions compared to polyoxypropylene/polyoxyethylene analogues. Polyoxybutylene-based surfactants were typically one order of magnitude better in their ability to reduce surface tension at interface saturation. Polyoxybutylene/polyoxyethylene copolymers pack more efficiently at the interface, as evidenced by a smaller area per molecule at the interface. Critical micelle concentration values were also lower for polyoxybutylene/polyoxyethylene copolymers. A second phase of experiments focused on the surface activity of polyoxypropylene/polyoxyethylene triblock copolymers with higher molecular weight hydrophobes. Enhanced surface activity was found when compared to lower-molecular weight polyoxypropylene/polyoxyethylene copolymers.     

Structural and Physicochemical Properties of a Polymerizable Surfactant Synthesized from <Emphasis Type="Italic">N</Emphasis>-Methylol Acrylamide

A new polymerizable nonionic surfactant with reactive vinyl groups has been synthesized from N‐methylol acrylamide using a two‐step procedure. The structure of the surfactant molecule was characterized by Fourier transform infrared, ¹H nuclear magnetic resonance and mass spectroscopy. The surface active properties alongside its self‐assembly properties were investigated by surface tension, electrical conductivity, and fluorescence spectroscopy measurements. As compared with other nonionic surfactants, this study showed that this polymerizable surfactant possesses slightly a higher critical micelle concentration (CMC) value and the surface tension value at CMC. The obtained CMC values were compatible among measurements, ca. 0.02–0.038 M. The evidence of micelle formation also provided by the zeta potential measurements and the obtained zeta potential values showed that the polymerizable surfactant solutions had limited stability. The hydrolysis stability and solubility of the polymerizable surfactant were also investigated. The solubility results have shown that it was soluble in polar solvents while insoluble in nonpolar solvents both at room temperature and 40 °C. The acidic and basic hydrolysis of the surfactant increased as the temperature increased and the hydrolysis stability was 180 min (basic medium) and 55 min (acidic medium) at 80 °C.     

A correlation for the estimation of critical micellization concentrations and temperatures of polyols in aqueous solutions

An empirical correlation is presented for the estimation of critical micellization concentrations (CMC) and critical micellization temperatures (CMT) for poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) copolymers in aqueous solutions. The CMC and CMT are expressed as a function of the polyol molecular weight, composition, and temperature (for CMC determination) or concentration (in the case of CMT). The correlation was developed from experimental CMT data for a set of 12 polyols that covered a wide range of molecular weights (2900–14600) and poly(ethylene oxide) contents (30–80 wt%) and is based on a simple expression for the standard free energy of micellization. Such a correlation should be useful to practitioners of the field as it allows easy prediction of CMC and CMT for a wide range of polyols with a minimal number of input parameters.     

Mixed monolayer and mixed micelle formation in binary mixture of surfactants—Systems for trioxyethylenated dodecyl sulfonate and some polyoxyethylenated fatty alcohol ether nonionic surfactants

The interaction and synergism of some polyoxyethylenated fatty alcohol ether (POE) nonionic surfactants (C₁₂E₂, C₁₂E₃, C₁₀E₅, C₁₀E₇, where C_x indicates number of carbon atoms in the chain and E_y indicates number of oxyethylene glycol ethers) with trioxyethylenated dodecyl sulfonate (C₁₂E₃S) in mixed monolayer formation at the surface and in mixed micelle formation in aqueous solutions were studied at 25 and 40°C by calculating interaction parameters (β_α, β_M) from surface tension-concentration data by use of Rosen's equations based on the nonideal solution theory. All the systems investigated adapt reasonably well to the nonideal model, with negative values of β_σ and β_M (where M means micelle and σ refers to the air-liquid interface) indicating a favorable interaction between the mixed surfactants. Either at a monolayer or in a mixed micelle, the attractive interaction becomes stronger when the alkyl chain in the POE surfactant is longer, i.e., when the POE becomes more hydrophobic. The interaction increases in the order C₁₀E₇<C₁₀E₅<C₁₂E₃, C₁₂E₂. For the two C₁₀E _n (n= 5,7)/C₁₂E₃S systems, as temperature increases from 25 to 40°C, the interaction increases in a mixed micelle, but it decreases in a mixed monolayer. Synergism in mixed micelle formation exists for C₁₂E₃S/C₁₀E _n mixtures when X₁ ^M , the mole fraction of POE in a mixed micelle, is ≈0.4–0.8, whereas synergism does not occur in the systems of C₁₂E₃S/C₁₂E _m due to the large difference between CMC₁ and CMC₂, i.e., large |In(C ₁ ^M /C ₂ ^M )| value (where CMC=critical micelle concentration). The degree of synergism in mixed micelle formation is temperature independent and is 0.23, 0.18, and close to zero for C₁₀E₅/C₁₂E₃S, C₁₀E₇/C₁₂E₃S, and C₁₂E _m (m=2,3)/C₁₂E₃S systems, respectively. Synergism in surface tension reduction effectiveness occurs in C₁₂E₃S/C₁₂E₂ and C₁₂E₃S/C₁₂E₃ systems. The mole fractions of POE in the solution phase are 0.302 and 0.333 for the two mixtures at the point of maximum synergism.     

New coupling method without heavy metals for the synthesis of a new class of fatty acid methyl ester oligoglycoside ethers

A new method, using poly-O-acetyl-β-d-glycopyranosylbromide, methyl 9-or methyl 12-hydroxyoctadecanoate and triethylamine as catalyst, is described for the synthesis of a new class of nonionic surfactants. Chemical structures were identified using ¹H and ¹³C nuclear magnetic resonance spectroscopy including two-dimensional techniques and Fourier transforming infrared. Critical micelle concentrations and surface tension profiles of these O-alkyl-β-d-glycosides in water were determined.     

Replacement of the foam index test with surface tension measurements

The foam index test is the method usually employed to determine the degree of fly ash interference with air entrainment agents in concrete. The test involves the use of commercial air-entraining agents (AEAs) and visual observation of foam stability. These facts reduce the reproducibility of the test, because commercially available AEAs vary in strength, and the criteria for foam stability are operator dependent. Therefore, it is of interest to develop a reproducible method, which is able to determine the fly ash quality with respect to air entrainment in concrete. This paper presents efforts toward the development of a new method based on dynamic surface tension measurements, using the bubble pressure method, on filtrate from a fly ash and cement suspension. A pure surfactant is added to the suspension as a substitute for a commercial AEA. The new method and the foam index test have been compared on fly ashes acquired from power plants in Denmark and the U.S. The results reveal a good relationship between the two methods, but the new method requires further work before a finished procedure is accomplished. Finally, it has been shown that changes in temperature affect both test methods.     

Synthesis and surface properties of new dicephalic saccharide-derived surfactants

A new group of nonionic dicephalic saccharide amides, N-dodecyl-N,N-bis[(3-d-gluconylamido)propyl]-amine, N-dodecyl-N,N-bis[(3-d-glucoheptonylamido)propyl]-amine, and N-alkyl-N,N-bis[(3-lactobionylamido)propyl]amines (alkyl: n-C₁₂H_25′ n-C₁₆H_33′, n-C₁₈H₃₇) were synthesized and characterized. Their structure and purity were confirmed by means of ¹H and ¹³C nuclear magnetic resonance analysis and electrospray ionization mass spectrometry. Carbon spectra were verified using a DEPT experiment. The surface and interfacial properties such as critical micelle concentration (CMC), standard free energy of micellization, ΔG _CMC, surface excess concentration, Γ_CMC, and surface area demand per molecule, A _CMC, were determined. The tertiary nitrogen atom seems to have a surprising effect on surfactnat packing at the interface.     

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.