Removal of an azo-metal complex textile dye from colored aqueous solutions using an agro-residue

The pine leaves which are an agricultural residue were used in its natural form as biosorbent for the removal of Acid Yellow 220 (AY 220) dye from aqueous solutions. The sorption experiments were carried out as a function of solution pH, biosorbent dosage, biosorbent size, dye concentration, temperature, contact time and ionic strength. The sorption isotherms closely followed the Langmuir model. The monolayer sorption capacity of the pine leaves for AY 220 was found as 40.00 mg g^{− 1}. It was shown that pseudo-second order equation could best describe the sorption kinetics. The thermodynamic data indicated that the sorption system was spontaneous, endothermic and physical process. Based on the results of present investigation, the pine leaves could be used as a suitable alternative biosorbent for the elimination of AY 220 from aqueous solutions.     

Remarkably efficient removal of toxic bromate from drinking water with a porphyrin–viologen covalent organic framework

The presence of carcinogenic bromate (BrO₃⁻) in drinking water became a global concern and efforts towards its removal mainly focused on addressing the source. Herein, we rationally designed a porphyrin-based covalent organic framework (PV-COF) with a cationic surface to provide electrostatic interactions and a porphyrin core to induce hydrogen bonding interactions for the efficient removal of BrO₃⁻ from water. Through H-bonding and electrostatic interactions, PV-COF exhibited an exceptional bromate removal efficiency (maximum adsorption capacity, Q_max: 203.8 mg g⁻¹) with the fastest uptake rate (k_ads) of 191.45 g mg⁻¹ min⁻¹. The bromate concentration was reduced to far below the allowed concentration in drinking water (10 ppb) within 20 minutes. We studied the relationship between bromate adsorption and COF surface modification by metalation of the porphyrinic core or neutralization of the viologen linkers by chemical reduction. The bromate adsorption mechanism was studied by EDAX mapping and molecular simulations, and it was found that ion exchange and hydrogen bonding formation drive the adsorption. Importantly, PV-COF could be easily recycled several times without compromising its adsorption efficiency.

A cationic COF removes carcinogenic bromate with a remarkable rate constant of 191.45 g mg⁻¹ min⁻¹.     

Equilibrium and Kinetic Modelling of Adsorption of Phosphorus on Calcined Alunite

The adsorption of phosphorus onto calcined alunite has been studied. Its equilibrium isotherm has been measured. The isotherm was determined by shaking 1.0 g calcined alunite, particle size range 90–150 m, with 100 mL phosphorus solution of initial concentrations from 0.5 to 2.5 mmol/L. The water bath shaking a constant rate of 200-rpm was used and the temperature maintained at 298 ± 2 K. A contact time of 120 min was required to achieve equilibrium. The experimental isotherm data were analyzed using the Langmuir, Freundlich, Temkin and Dubinin-Radushkevich equations. The monolayer adsorption capacity is 1.355 mmol P per g calcined alunite. Three simplified kinetic models including a pseudo first-order equation, pseudo second-order equation and intraparticle diffusion equation were selected to follow the adsorption process. Kinetic parameters, rate constants, equilibrium sorption capacities and related correlation coefficients, for each kinetic model were calculated and discussed. It was shown that the adsorption of phosphorus could be described by the pseudo second-order equation.     

Synthesis and applications of poly(acryl<Emphasis Type="Italic">p</Emphasis>-aminobenzenesulfonamideamidine-<Emphasis Type="Italic">p</Emphasis>-aminobenzenesulfonylamide) chelating fiber for pre-concentrating and separating trace Bi(III), Hg(III), Au(III) and Pd(IV) from solution samples

Poly(acrylp-aminobenzenesulfonamideamidine-p-aminobenzenesulfonylamide) chelating fiber containing "S", "N", and "O" elements was synthesized from polyacrylonitrile fiber and p-aminobenzene sulfonamide and used to enrich and separate trace Bi(III), Hg(III), Au(III), and Pd(IV) ions from wastewater and ore sample solution. The enrichment acidity, flow rate, elution conditions, reuse, interference ions, saturated adsorption capacity, constant of adsorption rate, analytical accuracy, and actual samples on chelating fiber were investigated by means of inductively coupled plasma optical emission spectrometry (ICP-OES) with satisfactory results. Solutions of 100 ng mL^–1 of Bi(III), Hg(III), Au(III), and Pd(IV) ions can be enriched quantitatively by this chelating fiber at a rate of 1.0 mL min^–1 at pH 4 and desorbed quantitatively with 20 mL of 0.25 M HCl and 2% CS(NH₂)₂ solution at 50 °C (with recovery 97%). When the chelating fiber was reused for 20 times, the recoveries of the analyzed ions enriched by the fiber were still over 95% (except for Hg(III)). One thousand-fold excesses of Mn²⁺, Ca²⁺, Zn²⁺, Mg²⁺, Fe³⁺, Cu²⁺, Ni²⁺, Al³⁺, and Ba²⁺ ions and thousands-fold excesses of Na⁺ and K⁺ cause little interference in the pre-concentration and determination of the analyzed ions. The saturated adsorption capacity of Bi(III), Hg(III), Au(III), and Pd(IV) was 4.850×10^–4, 3.235×10^–4, 2.807×10^–4, and 3.386×10^–4 mol g^–1, respectively. The constants of adsorption rate were 0.409 min^–1 for Bi, 0.122 min^–1 for Hg, 0.039 min^–1 for Au, and 0.080 min^–1 for Pd. The relative standard deviations (RSDs) for the enrichment and determination of 10 ng mL^–1 Bi(III), Hg(III), Au(III), and Pd(IV) were lower than 2.3%. The results obtained for these ions in actual samples by this method were basically in agreement with the given values with average errors of less than 1.0%. FT-IR spectra shows that the existence of –SO₂–Ar, –H₂N–Ar, O=C–NH–, HN=C–NH–, and –HN–SO₂ functional groups are verified in the chelating fiber. From the FT-IR spectroscopy, we can see that Hg(III), Au(III), and Pd(IV) are mainly combined with nitrogen and sulfur (or oxygen), and Bi(III) is mainly combined with nitrogen (or oxygen) of the groups to form a chelating complex.     

Application of Functionalized DVB-co-GMA Polymeric Microspheres in the Enhanced Sorption Process of Hazardous Dyes from Dyeing Baths

Intensive development of many industries, including textile, paper, plastic or food, generate huge amounts of wastewaters containing not only toxic dyes but also harmful auxiliaries such as salts, acid, bases, surfactants, oxidants, heavy metal ions. The search for effective pollutant adsorbents is a huge challenge for scientists. Synthesis of divinylbenzene copolymer with glycidyl methacrylate functionalized with triethylenetetramine (DVB-co-GMA-TETA) resin was performed and the obtained microspheres were evaluated as a potential adsorbent for acid dye removal from dyeing effluents. The sorption capacities were equal to 142.4 mg/g for C.I. Acid Green 16 (AG16), 172 mg/g for C.I. Acid Violet 1 (AV1) and 216.3 mg/g for C.I. Acid Red 18 (AR18). Non-linear fitting of the Freundlich isotherm to experimental data was confirmed rather than the Langmuir, Temkin and Dubinin-Radushkevich. The kinetic studies revealed that intraparticle diffusion is the rate-limiting step during dye adsorption. Auxiliaries such as Na₂SO₄ (5–25 g/L), CH₃COOH (0.25–1.5 g/L) and anionic surfactant (0.1–0.5 g/L) present in the dyeing baths enhance the dye adsorption by the resin in most cases. Regeneration of DVB-co-GMA-TETA is possible using 1 M NaCl-50% v/v CH₃OH.     

Comparative study of acid yellow 119 adsorption onto activated carbon prepared from lemon wood and ZnO nanoparticles loaded on activated carbon

Activated carbon from lemon wood (AC) and ZnO nanoparticles loaded on activated carbon (ZnO‐NP‐AC) were prepared and their efficiency for effective acid yellow 199 (AY 199) removal under various operational conditions was investigated. The dependence of removal efficiency on variables such as AY 199 concentration, amount of adsorbent and contact time was optimized using response surface methodology and Design‐Expert. ZnO nanoparticles and ZnO‐NP‐AC were studied using various techniques such as scanning electron microscopy, X‐ray diffraction and energy‐dispersive X‐ray analysis. The optimum pH was studied using one‐at‐a‐time method to achieve maximum dye removal percentage. Small amounts of the proposed adsorbents (0.025 and 0.025 g) were sufficient for successful removal of AY 199 in short times (4.0 and 4.0 min) with high adsorption capacity (85.51 and 116.29 mg g^?1 for AC and ZnO‐NPs‐AC, respectively). Fitting the empirical equilibrium data to several conventional isotherm models at optimum conditions indicated the appropriateness of the Langmuir model with high correlation coefficient (0.999 and 0.978 for AC and ZnO‐NPs‐AC, respectively) for representation and explanation of experimental data. Kinetics evaluation of experiments at various time intervals revealed that adsorption processes can be well predicted and fitted by pseudo‐second‐order and Elovich models. This study revealed that the combination of ZnO nanoparticles and AC following simple loading led to significant improvement in the removal process in short adsorption time which was enhanced by mixing the media via sonication.     

Influence of the mineral matter content on the rate of heat release from Turkish lignites

In this study, combustion curves of twenty-five original and demineralized Turkish lignite samples were obtained through use of a differential thermal analyser. The lignite samples were demineralized by treatment with hydrochloric and hydrofluoric acids. Samples of 20 mg were heated up to 1074 K at a constant rate of 10 K min^–1 in a 40 cm³ min^–1 flow of dry air. The rates of heat release from the original and demineralized samples were compared and are discussed.     

Sorption of hafnium on hydrous titanium oxide using radiotracer technique

The sorption of hafnium on hydrous titanium oxide (TiO₂·1.94 H₂O) has been studied in detail. Maximum sorption of hafnium can be achieved from a pH 7 buffer solution containing boric acid and sodium hydroxide using 50 mg of the oxide after 30 minutes shaking. The value ofk _d, the rate constant of intraparticle transport for hafnium sorption, from 0.01M hydrochloric and perchloric acid and pH 7 buffer solutions has been found to be 17 mmole·g^–1·min^–2. The kinetics of hafnium sorption follows Lagergren equation in 0.01M HCl solution only. The values of the overall rate constantK=6.33·10^–2 min^–1 and of the rate constant for sorptionk ₁=6.32·10^–2 min^–1 and desorptionk ₂=2.28·10^–5 min^–1 have been evaluated using linear regression analysis. The value of correlation factor() is 0.9824. The influence of hafnium concentration on its sorption has been examined from 4.55·10^–5 to 9.01·10^–4 M from pH 7 buffer solution. The sorption data followed only the Langmuir sorption isotherm. The saturation capacity of 9.52 mmole·g^–1 and of a constant related to sorption energy have been estimated to be 2917 dm³·mole^–1. Among all the additional anions and cations tested only citrate ions reduce the sorption significantly. Under optimal experimental conditions selected for hafnium sorption, As(III), Sn(V), Co(II), Se(IV) and Eu(III) have shown higher sorption whereas Mn(II), Ag(I) and Sc(III) are sorbed to a lesser extent. It can be concluded that a titanium oxide bed can be used for the preconcentration and removal of hafnium and other metal ions showing higher sorption from their very dilute solutions. The oxide can also be employed for the decontamination of radioactive liquid waste and for pollution abatement studies.     

Adsorption of Acid Blue 193 from aqueous solutions onto Na-bentonite and DTMA-bentonite

Dodecyltrimethylammonium bromide-modified bentonite (DTMA-bentonite) was prepared and tested as an adsorbent for an acid dye (Acid Blue 193, AB193) removal from aqueous solution in comparison with Na-bentonite. The effect of various experimental parameters was investigated using a batch adsorption technique. In this manner, the adsorption isotherms, adsorption kinetics, and temperature and pH effects upon Acid Blue 193 adsorption on Na-bentonite and DTMA-bentonite were thoroughly examined. Results show that a pH value of 1.5 is favorable for the adsorption of Acid Blue 193. The isothermal data could be well described by the Freundlich equation. The dynamical data fit well with the pseudo-second-order kinetic model. The adsorption capacity of DTMA-bentonite (740.5 mg g(-1)) was found to be around 11 times higher than that of Na-bentonite (67.1 mg g(-1)) at 20 degrees C. Thermodynamic parameters such as activation energy (E(a)) and change in the free energy (DeltaG(0)), the enthalpy (DeltaH(0)), and the entropy (DeltaS(0)) were also evaluated. The overall adsorption process was exothermic but it is only spontaneous at 20 degrees C. The results indicate that Na-bentonite and DTMA-bentonite could be employed as low-cost alternatives to activated carbon in wastewater treatment for the removal of color which comes from textile dyes.     

Spectrophotometric determination of manganese with derivatives of 1,3,3-trimethyl-2-[3-(1,3,3-trimethyl-1,3- H-indol-2-ylidene)propenyl]-3 H-indolium

A new, simple, rapid, and sensitive spectrophotometric method has been developed for the determination of manganese in sewage. The method is based on the reaction of manganese with derivatives of 1,3,3-trimethyl-2-[3-(1,3,3-trimethyl-1,3-H-indol-2-ylidene)propenyl]-3H-indolium to form a colored ion associate with a sensitive absorption maximum at 560 nm. The appropriate reaction conditions have been established: pH 8.5–10.0, 1.25–2.3×10^–3 mol L^–1 1-nitroso-2-naphthol, and 1.6–2.4×10^–4 mol L^–1 dye reagent. Beer's law is obeyed for manganese concentrations up to 4.2 mg L^–1. The limit of detection is 0.01 mg L^–1 Mn²⁺; the molar absorptivity of the ion associate was 7.5×10⁴ L mol^–1 cm^–1. The effect of various foreign ions was examined. A reaction mechanism is suggested. The developed procedure was tested for determination of manganese in sewage with satisfactory precision and accuracy.     

Biosorption of americium-241 by Saccharomyces cerevisiae

The biosorption of radionuclide ²⁴¹Am from solution by Saccharomyces cerevisiae (S. cerevisiae), and the effects of experimental conditions on the adsorption were investigated. The preliminary results showed thatS. cerevisiae is a very efficient biosorbent. An average of more than 99% of the total ²⁴¹Am could be removed by S. cerevisiae of 2.1 g/l (dry weight) from ²⁴¹Am solutions of 17.54–4386.0 mg/l (2.22 MBq/l–555 MBq/l) with adsorption capacities of 7.45–1880.0 mg/g biomass (dry weight) (0.94 MBq/g–237.9 MBq/g). The adsorption equilibrium was achieved within 1 hour and the optimum pH ranged 1–3. No significant differences on ²⁴¹Am adsorption were observed at 10–45 °C, or in solutions containing Au³⁺ or Ag⁺, even 2000 times above ²⁴¹Am concentration. The relationship between concentrations and adsorption capacities of ²⁴¹Am indicated the biosorption process should be described by the Freundlich adsorption isotherm.     

Quartzite an efficient adsorbent for the removal of anionic and cationic dyes from aqueous solutions

Quartzite obtained from local source was investigated for the removal of anionic dye congo red (CR) and cationic dye malachite green (MG) as an adsorbent from aqueous solution in batch experiment. The adsorption process was studied as a function of dye concentration, contact time, pH and temperature. Adsorption process was described well by Langmuir and Freundlich isotherms. The adsorption capacity remained 666.7 mg/g for CR dye and 348.125 mg/g for MG dye. Data was analyzed thermodynamically, ΔH⁰ and ΔG⁰ values proved that adsorption of CR and MG is an endothermic and spontaneous process. Adsorption data fitted best in the pseudo-first order kinetic model. The adsorption data proved that quartzite exhibits the best adsorption capacity and can be utilized for the removal of anionic and cationic dyes.     

Ion adsorption behaviour of hydroxyapatite with different crystallinities

This study aimed to correlate crystallinity of hydroxyapatite (HA) with the ion adsorption behaviour of the material. Hydroxyapatite powders of various crystallinities (X_c) and specific surface area (SSA) were prepared by precipitation following heat treatment. Adsorption experiments were carried out by using (i) multi-component ion solutions containing a broad range of light and heavy ions to study competitive adsorption and (ii) lead and zinc solutions with concentrations up to 250 ppm to determine the adsorption isotherms of the material. While as-prepared HA powders of low crystallinity (X_c = 0%) and a high SSA of 170 m²/g showed quantitative removal for divalent Pb, Zn, Be, U, Bi, V, Al, Cu and Ga ions, calcined powders with higher crystallinity (X_c = 65–95%) and lower SSA between 5 and 30 m²/g led to a quantitative removal only for a few elements (Pb, Bi, Ga). The time and concentration dependant ion removal capacity for Pb²⁺ and Zn²⁺ single element solutions showed quantitative removal even after short immersion times of less than 10 min for as-prepared HA powders. XRD analysis of the powders after ion adsorption revealed the presence of pyromorphite (Pb₅(PO₄)₃OH) and hopeite (Zn₃(PO₄)₂) phases, respectively.     

Investigation of the surface of Ni-Pd catalysts by IR spectroscopy

The reaction of carbon monoxide with the surface of Ni, Pd, and Ni-Pd catalysts, deposited on -Al₂O₃, was investigated at 25°C by IR spectroscopy in conjunction with an adsorption volumetric technique. The IR spectra contained the following absorption bands (v, cm^–1): 2020–2100 (AB1) (linear and subcarbonyl forms of adsorbed CO); 1945–1985 (AB2) (bridging); 1920–1940 (AB3) with a shoulder at 1870–1885 (AB4) (bridging and many-center). In the spectrum of Ni the absorption band AB5 appears at 1770–1780 (CO-Ni⁺). It appears with surface coverage a 1.3 mole CO/mole M. The optical density (A) of AB1 for Ni₉₇Pd₃ is appreciably higher than for the other investigated samples. In the Ni-Pd catalysts the intensity of AB2 in relation to AB1 is higher than in nickel. The introduction of K⁺ ions into the support of the bimetallic sample reduces the optical density of AB1. In modified Ni-Pd-K the AB3 and AB4 bands disappear.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1276–1282, June, 1992.     

Spectrofluorimetric determination of aluminium in silicon and in electronic grade reagents

Summary A sensitive spectrofluorimetric method is based on the complexation of Al with the dye Mordant Black 17 or Calcon (CI 15705). The complex solution in n-propyl alcohol (1.5×10^–4 mol/l) is mixed (5:20) with 1 mol/l acetic acid — sodium acetate buffer (pH 4.8) and maintained at 40°C for 60 min. The fluorescence intensity is measured at Ex=565 nm, Em=610 nm: The calibration curve for Al was found to be linear in the range 0 to 60 ng×ml^–1 with a standard deviation of =1.5 and an Al detection limit of 3 ng×ml^–1. The interferences due to more than 40 ions were investigated; the presence of Fe³⁺, Cr³⁺, Co²⁺, Cu²⁺, Ti⁴⁺, VO²⁺, ZrO²⁺, WO ₄ ^2– , MoO ₄ ^2– , CrO ₄ ^2– and particularly F^–, must be avoided or masked during the determination of Al. The sample of silicon/silicon dioxide was treated with a mixture of conc. HF and HNO₃ (2:1), followed by digestion and distillation at 90°C to eliminate the matrix as fluorosilicic acid. A small residue of AlF₃ was decomposed with HClO₄. In SiO₂ anodized layers (25–250 g) the minimum detection of Al was estimated to be 10¹⁸ At×cm^–3, in monocrystalline silicon (25–250 mg) 10¹⁶ At×cm^–3. The method can also be employed to determine the presence of Al in the residues by distillation of a small quantity (5–10g) of many solvents or reagent solutions. Presented at: IX. Congresso Nazionale — Div Chim Anal (S.C.I.) Ferrara 1990     

Langmuir Aggregation of Bordeaux R on a Cationic Surfactant and Its Application to Sensitive Quantitative Determination of Copper

The microphase adsorption-spectral correction (MPASC) technique has been applied to the study of the interaction between cetyl trimethylammonium bromide (CTMAB) and the dye Bordeaux R (BR) at pH 9.6. The aggregation of BR on the CTMAB surface obeys the Langmuir adsorption isotherm. The aggregation of BR on CTMAB accelerates the complexation between Cu(II) and BR. Results at 25°C show that the adsorption constant of the CTMAB–BR 1:1 aggregate is 6.80 × 10⁴. In the presence of CMTAB, the Cu–Br complex with a mole ratio of 2:1 has a cumulative stability constant of 1.08 × 10¹¹. The cooperative adsorption and complexation have been applied successfully in a sensitive determination of trace amounts of copper.     

Kinetic Study of Erbium Ion Adsorption on Activated Charcoal from Aqueous Solutions

The kinetics of the adsorption of erbium ions on activated charcoal from aqueous solutions has been studied in the temperature range of 10 to 40∘C. It was observed that the diffusion of erbium ions in to the pores of activated charcoal controls the kinetics of the adsorption process, and the values of intra-particle diffusion rate constant, k_d (g/g ⋅ min^1/2) were evaluated as 0.7 × 10⁻³ to 1.6 × 10⁻³ in the temperature range studied. Various thermodynamic parameters Δ H, Δ G and Δ S were also computed from values of the equilibrium constant K_C. The results showed that the adsorption of erbium ions on activated charcoal is an endothermic process.     

Adsorption of crystal violet dye from aqueous solution using mesoporous materials synthesized at room temperature

In this work, batch adsorption experiments are carried out for crystal violet dye using mesoporous MCM-41 synthesized at room temperature and sulfate modified MCM-41 prepared by impregnation method using H₂SO₄ as sulfatising agent. The surface characteristics, pore structure, bonding behavior and thermal degradation of both the MCM-41 samples are characterized by nitrogen adsorption/desorption isotherms, X-ray diffraction (XRD) patterns, Fourier transform infrared (FT-IR) spectroscopy and thermo gravimetric analysis (TGA). The adsorption isotherm, kinetics and thermodynamic parameters are investigated for crystal violet (CV) dye using the calcined and sulfated MCM-41. Results are analysed using Langmuir, Freundlich and Redlich-Peterson isotherm models. It is found that the Freundlich model is an appropriate model to explain the adsorption isotherm. The highest adsorption capacity achieved is found to be 3.4×10⁻⁴ mol g⁻¹ for the sulfated MCM-41. The percentage removal of crystal violet dye increases with increase in the pH for both the MCM-41 adsorbents. Kinetics of adsorption is found to follow the second-order rate equation. From the thermodynamic investigation, it is evident that the adsorption is exothermic in nature.     

Interfacing capillary electrophoresis and surface-enhanced resonance Raman spectroscopy for the determination of dye compounds

The at-line coupling of capillary electrophoresis (CE) and surface-enhanced resonance Raman spectroscopy (SERRS) was optimized for the separation and subsequent spectroscopic identification of charged analytes (dye compounds). Raman spectra were recorded following deposition of the electropherogram onto a moving substrate. To this end a new interface was developed using a stainless steel needle as a (grounded) cathode. The outlet end of the CE capillary was inserted into this metal needle; CE buffer touching the needle tip served as the electrical connection for the CE separation. A translation table was used to move the TLC plate at a constant speed during the deposition. The distance between the tip of the fused silica column and the TLC plate was kept as small as possible in order to establish a constant bridge-flow, while avoiding direct contact. The dyes Basic Red 9 (BR9), Acid Orange 7 (AO7) and Food Yellow 3 (FY3) were used as test compounds. After CE separation in a 20 mM borate buffer at pH 10, after deposition, concentrated silver colloid was added to each analyte spot, followed by irradiation with 514.5 nm light from an argon ion laser to record the SERRS signal using a Raman microscope. Different types of silver colloids were tested: Lee–Meisel type (citrate), borate, and gold-coated silver. BR9 (positively charged) gave much more intense SERRS spectra than the two negatively charged dyes. For BR9 and AO7 the citrate-coated Lee–Meisel colloid yielded the most intense SERRS spectra. The CE–SERRS system was used to separate and detect the negatively charged dyes. Silver colloid and nitric acid (to improve adsorption) were added post-deposition. Even though their chemical structures are very similar, AO7 and FY3 could be readily distinguished based on their SERRS spectra. The limits of detection (S/N=3) of the CE–SERRS system ranged from 6.7×10^–5 M (2.6×10^–12 mol injected) for FY3 down to 1.8×10^–6 M (7.0×10^–14 mol injected) for BR9.D. Arráez Román and E. Efremov contributed equally to this work.     

Mechanism of methylene blue dye adsorption on siliceous minerals

Summary The present experiments were undertaken to establish the mechanism of methylene blue dye adsorption from aqueous solution on common siliceous minerals found in petroleum reservoir formations. Three minerals (a montmorillonite, a kaolinite, and a silica-sand flour) were prepared so that all thecec sites on the mineral surfaces were occupied by sodium (²³Na +²²Na). Methylene blue (Cl^–) dye adsorption isotherms were measured on these three minerals prepared in the sodium form. Measurement of the transmittance of the equilibrium solutions and measurement of the gamma-counting activity (²²Na) of the equilibrium solutions permitted a quantitative determination of dye cation adsorption and of sodium cation displacement.In the case of the clays (montmorillonite and kaolinite) the saturation dye adsorption capacity must be attributed to two mechanisms: first, to cation exchange resulting from isomorphous substitution in the alumino-silicate lattice and, second, to an adsorption mechanism which might be either physical (van der Waals) adsorption or chemisorption (hydrogen bonding) with the surface SiOH and AlOH of the aluminosilicate lattice.Dye adsorption on silica is due to the physical or chemisorption mechanisms alone. It was demonstrated that the distribution of this type of adsorption site on the two clays after correction for the distribution of thecec sites ranged from 4.9 to 6.1×10^–8 me/cm² and was in good agreement with the value 5.1×10^–8 me/cm² for the total adsorption sites on silica.In spite of the existence of mechanisms other than cation exchange, methylene blue dye adsorption can nonetheless be used as a rapid, approximate method for estimation ofcec of siliceous sediments owing to the fortuitous circumstance that in a saturated monomolecular layer of dye adsorbate the effective coverage area of the dye molecule approximates the area available per exchange site on the common clay minerals, e. g., montmorillonite and kaolinite.

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Zusammenfassung Die beschriebenen Untersuchungen wurden durchgeführt, um den Mechanismus der Adsorption von Methylenblau aus wäßriger Lösung an bekannten Silikaten, wie sie in erdölführenden Schichten gefunden werden, aufzuklären. Drei Minerale, ein Montmorillonit, ein Kaolinit und ein mehliger Silicium-Sand, wurden so behandelt, daß alle Kation-Austauschstellen (Cation Exchange Capacity) auf den Oberflächen des Minerales von Natrium besetzt waren (²³Na +²²Na). Isothermen der Adsorption des Farbstoffes Methylenblau-Chlorid wurden an den Natrium-Formen dieser Minerale aufgenommen. Die Messung der Lichtdurchlässigkeit der Lösung im Gleichgewicht und die Messung der Gamma-Aktivität (²²Na) dieser Gleichgewichtslösung erlaubten es, quantitativ die Adsorption von Farbstoff-Kation und den Ersatz von Natrium-Kation festzustellen.Im Falle der Tone, Montmorillonit und Kaolinit, muß die Sättigungsfähigkeit der Farbstoffadsorption zwei Mechanismen zugeschrieben werden: in erster Linie dem Kationenaustausch, der sich aus der isomorphen Substitution im Gitter des Aluminiumsilikates herleitet, in zweiter Linie einem Adsorptionsmechanismus, der entweder aus physikalischer Adsorption (van der Waals) oder Chemisorption (Wasserstoffbindung) mit den Oberflächengruppen SiOH und AlOH des Aluminosilikatgitters besteht.Farbstoffadsorption an Siliciumdioxid kann nur der physikalischen oder der aktivierten Adsorption zugeschrieben werden. Es wurde gezeigt, daß die Verteilung dieser Art von Adsorptionsstellen an den beiden Tonen von 4,9–6,1×10^–8 Milliäquivalenten pro cm² reichte (nach Korrekturen für die Verteilung der Kationen-Austauschstellen). Das stimmt sehr gut mit dem Wert 5,1×10^–8 Milliäquivalenten pro cm² für alle Adsorptionsstellen an Siliciumdioxid überein.Obwohl es einen anderen Mechanismus als den Kationenaustausch gibt, kann doch die Adsorption von Methylenblau als schnelle Feldmethode dazu dienen, die Kationen-Austauschstellen (cec) von Silikatsedimenten abzuschätzen. Und zwar, einmolekulare Bedeckung mit adsorbiertem Farbstoff vorausgesetzt, weil die vom Farbstoffmolekül effektiv bedeckte Fläche der zugänglichen Fläche pro Austauschstelle entspricht; jedenfalls bei gewöhnlichen Tonmineralen wie Montmorillonit und Kaolinit.

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Publication No. 358, Exploration and Production Research Laboratory, Shell Development Company (a Division of the Shell Oil Company), Houston, Texas.