Surfactant analysis with differential pulse tensammetry

Differential pulse polarograms of surfactants exhibit tensammetric (adsorption/desorption) peaks. The dependence of peak current on bulk concentration of a surfactant is at first linear but reaches a saturation limit at higher concentrations. Even with commerical instrumentation, in which the current measuring sequence is such that charging current is minimized, differential pulse tensammetry is a viable analytical method. The optimum pulse amplitude depends on the surfactant. Sensitivity can be increased by using a long drop time or a stationary mercury electrode. Sensitivity and resolution from interfering faradaic processes were improved by modifying the current measuring sequence of a commercial instrument. This modification involved decreasing the delay time between application of the pulse and the second current sampling period and decreasing the second current sampling period itself.     

Tensammetry with accumulation on the hanging mercury drop electrode : Part 4. The behaviour of oxyethylated alcohols (polyoxyethylene n-alkyl monoethers)

The behaviour of polydispereed oxyethylated alcohols having a well-defined n-alkyl radical is described. Surfactants 6-14, 10-10, 10-14, 18-14, 18-10 and 18-6 (the first number denotes the number of carbon atoms in the n-alkyl radical, and the second one the average number of oxyethylene subunits) were examined. The conditions included 5 or 10 min of adsorptive preconcentration of surfactants at concentrations lower than the c.m.c value. Only negative tensammetric peaks were examined. The relationships between the peak height and the preconcentration potential were investigated for potentials more negative than - 1.0 V vs. SCE. More hydrophilic surfactants (i.e., 6-14, 10-10 and 10-14) form one wide tensammetric peak. The relationship of this peak to the preconcentration potential is simple and is similar to the negative branch of the adsorption isotherm. More hydrophobic surfactants (i.e., 18-6, 18-10 and 18-14) form a narrow peak, caused by the monomer form of the surfactant. If the threshold concentration of surfactants 18-6 and 18-10 is exceeded, a second very narrow peak appears, which is caused by the premicellar form of the surfactant formed at concentrations lower than the c.m.c. The dependences of the peak height on the preconcentration potential for surfactants 18-6, 18-10 and 18-14 are complicated; each plot shows a maximum, but the curves greatly depend on the surfactant concentration, which makes the choice of preconcentration potential difficult. Within the 10-(30-50) μg l^?1 range of surfactant concentration, the plots of peak height vs. surfactant concentration are approximately linear. Results for the lowest concentrations are very imprecise because of strong adsorption of the surfactants on the surface of the cell.     

Reactant adsorption in differential pulse polarography: Effects of adsorptive depletion of reactant,non-linear adsorption isotherms and uncompensated resistance

Digital simulation techniques are applied to the diagnosis of the ways in which the peak currents and wave shapes of differential pulse polarograms are affected by the adsorption of reactants or products. The changes in the polarograms introduced by the items mentioned in the title are examined and their magnitudes calculated and compared with experimental polarograms. Some implications of the results in analytical applications of differential pulse polarography are described.     

Comparison of the utility of several tensammetric techniques for the determination of traces of surfactants after preconcentration at the hanging mercury drop electrode

After preconcentration of surfactants at the HMDE, four tensammetric signals were examined to establish the optimum conditions for the determination of ultratraces of surfactants in alkaline, neutral and acidic media. The signals studied were: (1) the depth of the depression occuring on the curves obtained in a.c. fundamental tensammetry; and (2–4) the height of the peaks on the curves obtained in a.c. fundamental tensammetry, a.c. second-harmonic tensammetry and differential pulse tensammetry, respectively. The lowest detection limits found for Triton X-100 and a polyethylene glycol (PEG-4000) were 10 and 2 μg dm^-3, respectively. Traces of surfactants found in supporting electrolytes (ca. 25 μg dm^-3) gave desorption peaks at potentials around ?1 V. These contaminants had no significant effect on the peaks on Triton X-100 and PEG-4000 and they affected the SDS peak markedly. The reproducibility of the results obtained for SDS was poorer than for Triton or PEG.     

Square‐Wave Voltammetry of Electroinactive Surfactants

Under the influence of previously published and some new theoretical results, potential‐ dependent adsorption and desorption of model electroinactive surfactants Triton X‐100 (T‐X‐100 or polyethylene glycol p‐(1,1,3,3‐tetramethylbutyl)‐phenyl ether) and sodium dodecyl sulfate (SDS) on the static mercury drop electrode (SMDE) were studied by square‐wave voltammetry (SWV). Although (according to the theory) the resulting current – potential curve should consist of two highly separated peaks, only desorption signal could be seen on each experimentally obtained voltammogram, most probably because of the limitations concerning the available potential range. Different properties of the recorded peak are in good agreement with the theory indicating that square‐wave voltammetry could be treated as a potential tool for tensammetric studies of electroinactive surface active substances.     

Tensammetric determination of non-ionic surfactants combined with BiAS separation procedure (Wickbold) 2. Optimisation of the precipitation and investigation of interferences

The precipitation step in the developed procedure (BiAS-ITM) was optimised with the aim of achieving a lower detection limit. Losses during filtration using Triton X-100 as representative non-ionic surfactant (NS), the indirect tensammetric method (ITM) and adsorptive stripping tensammetry (AdST) for the determination of the concentration of the surfactant in the precipitate and in the filtrate were investigated. The G4 glass filter recommended up to now was found to be insufficiently effective and a source of loss. The new version of the procedure developed works within the range 2-1000 mug of NS in the sample, and thus two orders of magnitude lower than the former version of the procedure, showing satisfactory recovery and precision. The detection limit (3 x S.D.) was found to be below 1.5 mug in the sample. Interferences of anionic surfactants (ASs) e.g. sodium dodecylbenzenesulphonate and sodium lauryl sulphate, lipids, e.g. glycerol trioleate (GTO), and chlorophyll were investigated. GTO and AS show no effect on the BiAS-ITM results although strong adsorption of ASs on the glass filter as well as a slight adsorption on the precipitate was found. Chlorophyll does not interfere with the determination up to 30 mug in the sample, whereas higher concentrations produce results that are too high.     

A review on experimental studies of surfactant adsorption at the hydrophilic solid-water interface

The progresses of understanding of the surfactant adsorption at the hydrophilic solid-liquid interface from extensive experimental studies are reviewed here. In this respect the kinetic and equilibrium studies involves anionic, cationic, non-ionic and mixed surfactants at the solid surface from the solution. Kinetics and equilibrium adsorption of surfactants at the solid-liquid interface depend on the nature of surfactants and the nature of the solid surface. Studies have been reported on adsorption kinetics at the solid-liquid interface primarily on the adsorption of non-ionic surfactant on silica and limited studies on cationic surfactant on silica and anionic surfactant on cotton and cellulose. The typical isotherm of surfactants in general, can be subdivided into four regions. Four-regime isotherm was mainly observed for adsorption of ionic surfactant on oppositely charged solid surface and adsorption of non-ionic surfactant on silica surface. Region IV of the adsorption isotherm is commonly a plateau region above the CMC, it may also show a maximum above the CMC. Isotherms of four different regions are discussed in detail. Influences of different parameters such as molecular structure, temperature, salt concentration that are very important in surfactant adsorption are reviewed here. Atomic force microscopy study of different surfactants show the self-assembly and mechanism of adsorption at the solid-liquid interface. Adsorption behaviour and mechanism of different mixed surfactant systems such as anionic-cationic, anionic-non-ionic and cationic-non-ionic are reviewed. Mixture of surface-active materials can show synergistic interactions, which can be manifested as enhanced surface activity, spreading, foaming, detergency and many other phenomena.     

Differential pulse polarographic determination of hydrocortisone in pharmaceutical preparations

Differential pulse polarograms of hydrocortisone recorded from acetate buffer pH 4.6 exhibit a well-defined peak at —1.25 V vs. SCE and the peak current is proportional to the concentration in the range 10^-5–8 × 10^-5 M. The electrode reaction involves one electron and one hydrogen ion. A simple rapid method is proposed for the determination of hydrocortisone in creams and ointments. The procedure does not involve time-consuming extractions, but it is not applicable to samples containing surfactants like polyethyleneglycol which are more strongly adsorbed on the electrode than hydrocortisone. Because degradation in the side chain of hydrocortisone is not detected polarographically, the method is suitable for production control but not for stability tests.     

The Use of Differential Pulse and D.C. Polarography in the Analysis of Solutions Containing Surfactants

Abstract

Peak currents in differential pulse polarography (DPP) are often used for quantitative analysis. In the presence of surfactants, peak currents depend not only on the concentration of the electroactive species, but also on that of the surfactant. In the presence of surfactants of biological origin, limiting currents obtained by d.c. polarography are often less sensitive to the effects of surfactants and are more suitable for quantitative analysis than DPP peak currents. Effects of surfactants on DPP curves were demonstrated for 4-nitrobenzoic acid in the presence of oligomers resulting from washing lignin preparations with water. In the study of adsorption of nitro compounds on lignin, d.c. polarographic curves yielded reliable adsorption isotherms whereas DPP peak currents indicated erroneously much stronger adsorption of nitro compounds on lignin.     

季铵盐型Gemini表面活性剂在金表面的吸附行为

以邻苯二酚(CC)为电化学探针, 利用循环伏安、交流阻抗等方法研究了不同阳离子Gemini表面活性剂(C16H33(CH3)2N-C4H8-N(CH3)2C16H33 (C16-C4-C16)、C12H25(CH3)2N-C4H8-N(CH3)2C12H25 (C12-C4-C12)、C8H17(CH3)2N-C4H8-N(CH3)2C8H17 (C8-C4-C8))在金电极表面的吸附性能. 结果表明, CC在KNO3溶液中可产生两对峰; 当向溶液中加入阳离子Gemini表面活性剂时, 第一对峰降低, 第二对峰升高, 峰电位差变大; 碳链长的表面活性剂对CC的氧化还原峰的影响较大. 同样, 碳链长的表面活性剂使电极界面的阻抗增大较多, 使石英晶片的频率变化较大. 根据CC的第一个氧化峰的面积随表面活性剂吸附的变化, 估测了它们的吸附模式. 发现这三种表面活性剂在金电极表面的吸附基本符合Langmuir吸附模型.     

Adsorption of mixtures of nonionic sugar-based surfactants with other surfactants at solid/liquid interfaces II. Adsorption of n-dodecyl-beta-D-maltoside with a cationic surfactant and a nonionic ethoxylated surfactant on solids

Synergy and antagonism between sugar-based surfactants, a group of environmentally benign surfactants, and cationic surfactants and nonionic ethoxylated surfactants have been investigated in this study with solids which adsorbs only one or other when presented alone. Sugar-based n-dodecyl-beta-D-maltoside (DM) does not adsorb on silica by itself. However, in mixtures with cationic dodecyltrimethylammonium bromide (DTAB) and nonionic nonylphenol ethoxylated decyl ether (NP-10), DM adsorbs on silica through hydrophobic interactions. In contrast, although DM does adsorb on alumina, the presence of NP-10 reduces the adsorption of DM as well as that of the total surfactant adsorption. Such synergistic/antagonistic effects of sugar-based n-dodecyl-beta-D-maltoside (DM) in mixtures with other surfactants at solid/liquid interfaces were systematically investigated and some general rules on synergy/antagonism in mixed surfactant systems are identified. These results have implications for designing surfactant combinations for controlled adsorption or prevention of adsorption.     

Polarographic determination of α-amylase activity

The enzyme α-amylase splits blue starch in fragments bearing electroactive groups which exhibit two waves in the pulse polarograms. This behaviour is the basis of the polagraphic determination of bacterial and human serum α-amylase activity. The differential pulse mode is more sensitive by a factor of 25 as compared with normal pulse polarography. With serum α-amylase, protein adsorption disturbs the determination of low activities.     

An electrochemical study of the stability of cytochrome c3 from Desulfovibrio desulfuricans Norway strain

The electrochemical behaviour of cytochrome c₃ from Desulfovibrio desulfuricans, Norway strain, remains unchanged within the pH range 5–9.5. Differential pulse polarography peaks disappear at pH < 5 and two transitions are noted at alkaline pH (10.5 and 12). In denaturation experiments, guanidinium chloride has a more marked effect than urea on differential pulse polarography and cyclic voltammetry peaks.The study of absorption spectra shows that the δ band at 351 nm of the oxidized form increases above pH ∼ 10.Neither absorption spectra nor polarograms are modified after the treatment of cytochrome c₃ for 10 min at 100°C.It is concluded that hydrogen bonds must play a prominent role in maintaining the tertiary structure of the protein. Cytochrome c₃ from D. desulfuricans Norway is a particularly stable molecule as regards pH, denaturing agents, temperature and ageing.     

Determination of bacitracin by differential pulse polarography.

Differential pulse polarograms of pharmaceutical-grade bacitracin exhibit a well-defined double wave at the dropping mercury electrode over the entire pH range 1–8. The current is diffusion-controlled and proportional to the concentration as well as to the biological activity of the sample. The concentration of bacitracin and of zinc—bacitracin can be determined by pulse polarography with a standard deviation less than 2%. The biologically inactive oxidation product (bacitracin F) is reduced at less negative potentials and can easily be determined in the presence of the biologically active components of bacitracin.     

A method for comparing surface activity of organic compounds with reference to their structural influence by tensammetry

Summary The critical concentrations, , corresponding more negative peaks and concentrations required to just to remove the less negative peak,, have been determined for a number of organic compounds, known to give tensammetric peaks. It is concluded that the values of and, thus obtained, can be used successfully for comparing the surface activity of a series of closely related organic compounds in aqueous solution. When peak potential of less cathodic surfactant is close to the potential of more cathodic surfactants (whose surface activities are to be compared), the comparison for surface activity cannot be made by this method.     

Reactant adsorption in pulse polarography: Part IV. Influences of product adsorption

The influences of the reactant adsorption on maxima in pulse polarograms for quasi-reversible redox reactions at a stationary, planar electrode have been analysed theoretically. Some criteria for the estimation of the reversibility of the redox reaction from the adsorbed state are proposed.     

Competitive adsorption of surfactants at air/water interfaces

The zeta potential of an air bubble suspended in an aqueous solution of mixed fluorocarbon and hydrocarbon anionic surfactants is studied over a wide range of concentrations and mixture compositions. The zeta potential is related to surfactant ion adsorption. The two surfactants, which exhibit an antipathy manifested by micellar demixing, compete for surface sites. The total surfactant adsorption is reduced when both surfactants are present. Adsorption phenomena are closely correlated to the micellar phase diagram.     

Estimation of non-ionic, surface-active substances in aqueous solutions by means of the Controlled Growth Mercury Electrode

In this paper, a quick and simple tensammetric method of estimation of non-ionic surfactants (NS) in aqueous solutions is proposed. The method makes use of the variation in the differential capacity of double layer in relation to the time of accumulation (C(d)-t(acc)) of non-ionic surfactants at the hanging mercury drop electrode, generated by a single, very quick opening of the valve. Under such conditions, the capacity current measured at the potential of maximum adsorption diminishes with accumulation time of non-ionic surfactants. The proposed method, which was verified for model surfactant (Triton X-100), may also be applied in the determination of other NS. Modifications in construction of the CGME electrode and its improved metrological parameters played an important role in the presented procedure. In addition, other measurements were performed using standard electrochemical techniques, whereby current-time and differential capacity-potential curves were recorded. Satisfactory results were obtained in the determination of Triton X-100 in the range from 0.05 to 20 mg L(-1) (R.S.D.=6%, recovery=94-103%, r=0.999, DL=0.15 mg L(-1)). Applicability of the method was presented using the water samples from Bia?ka and Dunajec rivers, from which NS were removed by addition of fumed silica.     

Inhibition of the electrode reaction in the presence of surfactants studied by differential pulse polarography: Cadmium(II) in seawater in the presence of the Triton-X-100

The inhibition of the electrode reaction of Cd(II) in seawater as supporting electrolyte in the presence of the non-ionic surfactant T-X-100 was studied by differential pulse polarography in a wide concentration range of surfactant (10^?7?5×10^?4 mol dm^?3). The kinetic parameters, the rate constant k_s and the transfer coefficient α of the electrode reaction were estimated from the shape and the height of the corresponding differential pulse polarograms, using theoretical curves obtained by digital simulation.     

Effect of interactions between the adsorbed species on the properties of single and mixed-surfactant monolayers at the air/water interface

Experimental data on surface tension available from the literature and generated in the present study are analyzed to estimate the applicability of adsorption models, based on the Frumkin equation, to nonionic and ionic surfactants and their mixtures. Optimization programs based on the least-squares method in media of Delphi V and Pascal VII are used. The effect of interactions between the adsorbed species on surface tension is considered in all cases. The results are compared to those obtained with the simpler Szyszkowski equation, employed in numerous studies of nonionic surfactants, when interactions are neglected. Cases where the Frumkin model can be successfully employed with ionic surfactants and mixtures are presented and the conditions of its applicability are analyzed. Related characteristic quantities (maximum adsorption, standard free energy of surfactant adsorption, energy of interaction between adsorbed species, standard free energy of counterion adsorption, degree of coverage by surfactant/counterion associates) are established as a function of: The properties of an adsorption layer from a mixture of nonionic and ionic surface-active species are compared to those of the single surfactants.