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1.
Vitis vinifera (grape) leaf litter, an abundant agricultural waste in South Africa was chemically modified with H3PO4 and carbonized for use as biosorbent. Characterization and the potential application of the adsorbent in simultaneous removal of 4-nitrophenol and 2-nitrophenol from aqueous solutions were investigated. The adsorbent was characterized using FTIR, SEM and EDX elemental microanalysis. The EDX and FTIR analysis revealed the presence of surface oxygen moieties capable of binding to adsorbate molecules while the SEM micrographs showed the development of pores and cavities in the adsorbent. Batch adsorption experiments were conducted at a varying contact time, adsorbent dosage, pH and initial adsorbate concentration to investigate optimal conditions. The maximum adsorption capacity of the adsorbent was 103.09 and 103.10 mg/g for 4-nitrophenol and 2-nitrophenol, respectively. The adsorption process was best fitted into Freundlich isotherm while the adsorption kinetics followed a pseudo-second-order model. Liquid film and intra-particle diffusion contributed to the adsorption process. Thermodynamic parameters of ΔG°, ΔH° and ΔS° were evaluated. The adsorption was exothermic, feasible and spontaneous. The results suggest a possible application of grape leaf litter as a precursor for activated carbon and for cheaper wastewater treatment technologies.  相似文献   

2.
Acacia nilotica was used for the adsorption of Reactive Black 5 (RB5) dye from an aqueous solution. Both the raw and activated (with H3PO4) carbon forms of Acacia nilotica (RAN and ANAC, respectively) were used for comparison. Various parameters (including dye concentration, contact time, temperature, and pH) were optimized to obtain the maximum adsorption capacity. RAN and ANAC were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The maximum experimental adsorption capacities for RAN and ANAC were 34.79 and 41.01 mg g?1, respectively, which agreed with the maximum adsorption capacities predicted by the Langmuir, Freundlich, and Dubinin–Radushkevich equilibrium isotherm models. The adsorption data of ANAC showed a good fit to the isotherm models based on the coefficient of determination (R 2): Langmuir type II (R 2 = 0.99) > Freundlich (R 2 = 0.9853) > Dubinin–Radushkevich (R 2 = 0.9659). This result suggested monolayer adsorption of RB5 dye. The adsorption of RB5 dye followed pseudo-second-order kinetics. The RAN adsorbent reflected an exothermic reaction (enthalpy change, ΔH = ?0.006 kJ mol?1) and increased randomness (standard entropy change, ΔS = 0.038 kJ mol?1) at the solid–solution interface. In contrast, ANAC reflected both exothermic [?0.011 kJ mol?1 (303–313 K)] and endothermic [0.003 kJ mol?1 (313–323 K)] reactions. However, the ΔS value of ANAC was lower when the RB5 adsorption increased from 313 to 323 K. The negative values for the Gibbs free energy change at all temperatures indicated that the adsorption of RB5 dye onto RAN and ANAC was spontaneous in the forward direction.  相似文献   

3.
Understanding bacterial surface reactivity requires many different lines of investigation. Toward this end, we used isothermal titration calorimetry to measure heats of proton adsorption onto a Gram positive thermophile Bacillus licheniformis at 25, 37, 50, and 75 °C. Proton adsorption under all conditions exhibited exothermic heat production. Below pH 4.5, exothermic heats decreased as temperature increased above 37 °C; above pH 4.5, there was no significant difference in heats evolved at the temperatures investigated. Total proton uptake did not vary significantly with temperature. Site-specific enthalpies and entropies were calculated by applying a 4-site, non-electrostatic surface complexation model to the calorimetric data. Interpretation of site-specific enthalpies and entropies of proton adsorption for site L1, L2, and L4 are consistent with previous interpretations of phosphoryl, carboxyl, and hydroxyl/amine site-identities, respectively, and with previous calorimetric measurements of proton adsorption onto mesophilic species. Enthalpies and entropies for surface site L3 are not consistent with the commonly inferred phosphoryl site-identity and are more consistent with sulfhydryl functional groups. These results reveal intricacies of surface reactivity that are not detectable by other methods.  相似文献   

4.
Removal of dyes by low-cost adsorbents is an effective method in wastewater treatment. Iranian natural clays were determined to be effective adsorbents for removal of a basic dye (methylene blue) from aqueous solutions in batch processes. Characterizations of the clays were carried out by X-ray diffraction, Brunauer–Emmett–Teller surface area analysis and field-emission scanning electron microscopy. Effects of the operational parameters such as adsorbent dosage, initial dye concentration, solution pH and temperature were investigated on the adsorption performance. Adsorption isotherms like Langmuir, Freundlich and Temkin were used to analyze the adsorption equilibrium data and Langmuir isotherm was the best fit. Adsorption kinetics was investigated by pseudo-first-order, pseudo-second-order and intraparticle diffusion models and the results showed that the adsorption system conforms well to the pseudo-second-order model. The thermodynamic parameters of adsorption (ΔS°, ΔH° and ΔG°) were obtained and showed that the adsorption processes were exothermic.  相似文献   

5.
Nanosilica particles modified by Schiff base ligands 3-methoxy salicylaldimine propyl triethoxysilane (MNS1), 5-bromo salicylaldimine propyl triethoxysilane (MNS2) and 3-hydroxy salicylaldimine propyl triethoxysilane (MNS3) were prepared, and their potential for separation of copper, lead, zinc, cadmium, cobalt and nickel ions from aqueous solutions was examined. The effect of parameters influencing adsorption efficiency including aqueous-phase pH, amount of adsorbent, stirring time and initial concentration of the metal ions was assessed and discussed. Although MNS1 and MNS3 removed lead ions efficiently, all adsorbents showed strong selectivity toward copper ions. It was shown that, under some circumstances, MNS3 decreased the amount of other ions, particularly cobalt, in the aqueous phase. The adsorbents were also applied for removal of copper and lead ions from real samples. Possible quantitative desorption of the metal ions loaded onto the adsorbents suggests their multiple uses in adsorption–desorption process. Investigation of temperature dependency of the process led to determination of the ΔH°, ΔS° and ΔG° values. This investigation indicates that the adsorption of copper ions onto the all studied adsorbents and lead ions onto MNS1 and MNS3 is endothermic. The Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherms were tested to describe the equilibrium data. Pseudo-first-order, pseudo-second-order, Elovich and intra-particle diffusion equations were applied to study the kinetics of copper and lead adsorption onto the modified nanoparticles. This investigation indicates that the process for all adsorbents follows pseudo-second-order kinetics and suggests a chemisorption mechanism for the adsorption processes by the studied adsorbents.  相似文献   

6.
Glasses and crystals of compositions MgCaSi2O6, CoCaSi2O6 and NiCaSi2O6 were studied by high temperature solution calorimetry, x-ray diffraction, and pycnometry. These data were combined with trace element distribution data to obtain values for ΔAG0, ΔH0, ΔS0, and ΔV0 for M-Mg exchange reactions. Enthalpies of vitrification increase in the order Co, Mg, Ni as do volumes of vitrification and apparent melting points. The mixing of Co and Mg, Ni and Mg, and Co and Ni is almost ideal in crystals and glasses, with small negative heats of mixing and small volume changes. The exchange reactions MgCaSi2O6 (xl) + MCaSi2O6 (liq) = MgCaSi2O6 (liq) + MCaSi2O6 (xl) are exothermic for Ni and endothermic for Co. The volumes and entropies of the exchange reaction are small.  相似文献   

7.
ATR-FTIR spectroscopy is used to understand the adsorption of uranyl-citrate complexes to Al2O3. Spectral data indicate that uranyl-citrate complexes partially dissociate upon adsorption, allowing full or partial hydrolysis of the uranyl ion. Kads values determined for free citrate adsorption are similar to those for citrate in uranyl-citrate complexes, indicating that the complexation of uranyl by citrate does not significantly affect the ability of citrate to bond with the surface. The isotherm data also indicate enhanced citrate adsorption to Al2O3 in the presence of uranyl, suggesting that uranyl may be the central link between two citrate ligands, and that uranyl is associated with the surface through a bridging citrate ligand. Finally, uranyl-citrate complexes interact with citrate adsorbed to Al2O3 through outer sphere interactions.  相似文献   

8.
In this study, teff (Eragrostis tef) straw has been chemically treated and tested as an adsorbent for Cr(VI) removal. Chemically treatment of teff straw was done by NaOH, H3PO4 and ZnCl2 solutions. Scanning electron micrograph and X-ray diffraction were used for anatomical characterization, whereas Fourier transform infrared spectroscopy was used for surface change characterization of adsorbents. Effects of different experimental parameters like pH (2–12), initial Cr(VI) concentration (100–900 mg/L), adsorbent dose (2.5–20 g/L), contact time (15–360 min) and temperature (288–318 K) were studied. Temperature increment was found to stimulate the adsorption process. Langmuir isotherm was found to give better representation over wide range of temperature for untreated, H3PO4- as well as ZnCl2-treated teff straw, and Freundlich isotherm best represented the isotherm data for NaOH-treated teff straw. Maximum Cr(VI) adsorption capacity of untreated, NaOH-, H3PO4- and ZnCl2-treated teff straw was found to be 86.1, 73.8, 89.3 and 88.9 mg/g, respectively. Respective values of average effective diffusion coefficient (D e) were found to be 2.8 × 10?13, 2.59 × 10?14, 1.32 × 10?13 and 1.14 × 10?13 m2/s, respectively. The negative value of ΔG o for all the adsorbents indicates Cr(VI) spontaneous adsorption. Isosteric heat of adsorption (ΔH st,a) was found to vary with surface coverage (θ). ΔH st,a increased for untreated, H3PO4- and ZnCl2-treated teff straw, and decreased steadily with θ for NaOH-treated teff straw.  相似文献   

9.
In the present study, adsorption of lead (II) ions from aqueous solution by alluvial soil of Bhagirathi River was investigated under batch mode. The influence of solution pH, sorbent dose, initial lead (II) concentration, contact time, stirring rate and temperature on the removal process were investigated. The lead adsorption was favored with maximum adsorption at pH 6.0. Sorption equilibrium time was observed in 60 min. The equilibrium adsorption data were analyzed by the Freundlich, Langmuir, Dubinin–Radushkevich and Temkin adsorption isotherm models. The kinetics of lead (II) ion was discussed by pseudo first-order, pseudo second-order, intra-particle diffusion, and surface mass transfer models. It was shown that the adsorption of lead ions could be described by the pseudo second-order kinetic model. The activation energy of the adsorption process (E a) was found to be ?38.33 kJ mol?1 using the Arrhenius equation, indicating exothermic nature of lead adsorption onto alluvial soil. Thermodynamic parameters, such as Gibbs free energy (?G 0), the enthalpy (?H 0), and the entropy change of sorption (?S 0) have also been evaluated and it has been found that the adsorption process was spontaneous, feasible, and exothermic in nature. The results indicated that alluvial soil of Bhagirathi River can be used as an effective and low cost adsorbent to remove lead ions from aqueous solutions.  相似文献   

10.
Arsenite adsorption on galena (PbS) and sphalerite (ZnS)   总被引：1，自引：0，他引：1  
Arsenite, As(III), sorption on galena (PbS) and sphalerite (ZnS) was investigated as a function of solution composition and characterized using X-ray absorption spectroscopy (XAS). Adsorption conformed to a Langmuir isotherm except at the highest surface loadings, and it was not strongly affected by changes in ionic strength. Arsenite sorbed appreciably only at pH > ∼5 for PbS and pH ∼4.5 for ZnS, behavior distinct from its adsorption on other substrates. Arsenite adsorption on PbS and ZnS resulted in the conversion from As-O to As-S coordination. Arsenite does not adsorb through ligand-exchange of surface hydroxyl or sulfhydryl groups. Rather, it forms a polynuclear arsenic sulfide complex on ZnS and PbS consistent with the As3S3(SH)3 trimer postulated by Helz et al. (1995) for sulfidic solutions. This complex was unstable in the presence of oxidizing agents and synchrotron light—it quickly converted to As(V), which was largely retained by the surface. These data illustrate the complexity of As(III) adsorption to even simple sulfide minerals.  相似文献   

11.
The adsorption of hydrogen sulfide (ΓH2S) and protons (ΓH+) on the surface of crystalline sulfur was investigated experimentally in H2S-bearing solutions at temperatures of 25, 50, and 70°C, NaCl concentrations of 0.1 and 0.5 mol/dm−3 and log CH+ values in the range −2.3 to −5. At all temperatures, the dominant process on the surface of the sulfur was deprotonation, and the average values of ΓH2S were very close to the highest values determined for ΓH+. This finding, combined with the lack of detectable proton adsorption in H2S-free solutions, suggests that proton adsorption/desorption on the surface of sulfur occurs through formation of ≡ S − H2S complexes in the presence of H2S.We propose that this complexation represents sulfidation of the sulfur surface, a process analogous to hydroxylation of oxide surfaces, and that the sulfidation can be described by the reaction: ≡ S + H2S = ≡SSH20 β° The deprotonation of the ≡ SH° complex occurs via the reaction: ≡ SSH20 = ≡SSH− + H+ β− Values of 2.9, 2.8, and 2.9 (± 0.23) were obtained for −log β− at 25, 50, and 70°C, respectively. These data were employed to estimate the second dissociation constant for hydrogen sulfide in aqueous solutions using the extrapolation method proposed by Schoonen and Barnes (1988) and yielded corresponding values for the constant of 17.4 ± 0.3, 15.7, and 14.5, respectively. The value for 25°C is in very good agreement with the experimentally determined values of Giggenbach (1971) at 17 ± 0.1; Meyer et al. (1983) at 17 ± 1; Licht and Manassen (1987) at 17.6 ± 0.3; and Licht et al. (1990) at 17.1 ± 0.3.  相似文献   

12.
《Applied Geochemistry》2002,17(5):649-656
Adsorption of Mo on to hydrous TiO2 (anatase) particles was investigated. Batch experiments were conducted at 19 and 90 °C over a pH range of 2 to 12 and Mo concentrations ranging from approximately 10−6 to 10−4 M. The extent of sorption was strongly dependent on pH and surface loading. Maximum sorption was observed in the acidic pH range at low surface loading. Adsorption behavior was described using the empirical Langmuir adsorption model. A constant capacitance surface complexation model was also used to fit the adsorption isotherms using a ligand exchange reaction for a hydroxyl surface site on anatase. Comparison of experimental data at two different temperatures (19 and 90 °C) indicates that Mo sorption in the acidic pH range decreases with increasing temperature.  相似文献   

13.
We have performed experiments to determine the effects of pressure, temperature and oxygen fugacity on the CO2 contents in nominally anhydrous andesitic melts at graphite saturation. The andesite composition was specifically chosen to match a low-degree partial melt composition that is generated from MORB-like eclogite in the convective, oceanic upper mantle. Experiments were performed at 1–3 GPa, 1375–1550?°C, and fO2 of FMQ ?3.2 to FMQ ?2.3 and the resulting experimental glasses were analyzed for CO2 and H2O contents using FTIR and SIMS. Experimental results were used to develop a thermodynamic model to predict CO2 content of nominally anhydrous andesitic melts at graphite saturation. Fitting of experimental data returned thermodynamic parameters for dissolution of CO2 as molecular CO2: ln(K 0) = ?21.79?±?0.04, ΔV 0?=?32.91?±?0.65 cm3mol?1, ΔH 0?=?107?±?21 kJ mol?1, and dissolution of CO2 as CO3 2?: ln(K 0 ) = ?21.38?±?0.08, ΔV 0?=?30.66?±?1.33 cm3 mol?1, ΔH 0?=?42?±?37 kJ mol?1, where K 0 is the equilibrium constant at some reference pressure and temperature, ΔV 0 is the volume change of reaction, and ΔH 0 is the enthalpy change of reaction. The thermodynamic model was used along with trace element partition coefficients to calculate the CO2 contents and CO2/Nb ratios resulting from the mixing of a depleted MORB and the partial melt of a graphite-saturated eclogite. Comparison with natural MORB and OIB data suggests that the CO2 contents and CO2/Nb ratios of CO2-enriched oceanic basalts cannot be produced by mixing with partial melts of graphite-saturated eclogite. Instead, they must be produced by melting of a source containing carbonate. This result places a lower bound on the oxygen fugacity for the source region of these CO2-enriched basalts, and suggests that fO2 measurements made on cratonic xenoliths may not be applicable to the convecting upper mantle. CO2-depleted basalts, on the other hand, are consistent with mixing between depleted MORB and partial melts of a graphite-saturated eclogite. Furthermore, calculations suggest that eclogite can remain saturated in graphite in the convecting upper mantle, acting as a reservoir for C.  相似文献   

14.
Using the four-channel automatic photoelectric photometer of the Sternberg Astronomical Institute’s Tien Shan Mountain Observatory, we have acquired accurate (σobs≈0.004m) W BV R brightness measurements for the eclipsing binary AR Cas during selected phases before eclipse ingress and after egress, as well as at the center of minima. A joint analysis of these measurements with other published data has enabled us to derive for the first time a self-consistent set of physical and geometrical parameters for the star and the evolutionary age of its components, t=(60±3)×106 years. We have found the period of the apsidal motion (Uobs=1100±160 years, \(\dot \omega _{obs} = 0^\circ .327 \pm 0^\circ .049\) years?1) and the apsidal parameter of the primary, logk 2,1 obs =?2.41±0.08, with the apsidal parameter being in good agreement with current models of stellar evolution. There is an ultraviolet excess in the primary’s radiation, Δ(U?B)=?0.12m and Δ(B?V)=?0.06m, possibly due to a metal deficiency in the star’s atmosphere.  相似文献   

15.
《Geochimica et cosmochimica acta》1999,63(13-14):1969-1980
The solubility of ettringite (Ca6[Al(OH)6]2(SO4)3 · 26H2O) was measured in a series of dissolution and precipitation experiments at 5–75°C and at pH between 10.5 and 13.0 using synthesized material. Equilibrium was established within 4 to 6 days, with samples collected between 10 and 36 days. The log KSP for the reaction Ca6[Al(OH)6]2(SO4)3 · 26H2O ⇌ 6Ca2+ + 2Al(OH)4− + 3SO42− + 4OH− + 26H2O at 25°C calculated for dissolution experiments (−45.0 ± 0.2) is not significantly different from the log KSP calculated for precipitation experiments (−44.8 ± 0.4) at the 95% confidence level. There is no apparent trend in log KSP with pH and the mean log KSP,298 is −44.9 ± 0.3. The solubility product decreased linearly with the inverse of temperature indicating a constant enthalpy of reaction from 5 to 75°C. The enthalpy and entropy of reaction ΔH°r and ΔS°r, were determined from the linear regression to be 204.6 ± 0.6 kJ mol−1 and 170 ± 38 J mol−1 K−1. Using our values for log KSP, ΔH°r, and ΔS°r and published partial molal quantities for the constituent ions, we calculated the free energy of formation ΔG°f,298, the enthalpy of formation ΔH°f,298, and the entropy of formation ΔS°f,298 to be −15211 ± 20, −17550 ± 16 kJ mol−1, and 1867 ± 59 J mol−1 K−1. Assuming ΔCP,r is zero, the heat capacity of ettringite is 590 ± 140 J mol−1 K−1.  相似文献   

16.
The speciation of water in silicate melts   总被引：1，自引：0，他引：1  
Previous models of water solubility in silicate melts generally assume essentially complete reaction of water molecules to hydroxyl groups. In this paper a new model is proposed that is based on the hypothesis that the observed concentrations of molecular water and hydroxyl groups in hydrous silicate glasses reflect those of the melts from which they were quenched. The new model relates the proportions of molecular water and hydroxyl groups in melts via the following reaction describing the homogeneous equilibrium between melt species: H2Omolecular (melt) + oxygen (melt) = 2OH (melt). An equilibrium constant has been formulated for this reaction and species are assumed to mix ideally. Given an equilibrium constant for this reaction of 0.1–0.3, the proposed model can account for variations in the concentrations of molecular water and hydroxyl groups in melts as functions of the total dissolved water content that are similar to those observed in glasses. The solubility of molecular water in melt is described by the following reaction: H2O (vapor) = H2Omolecular (melt).These reactions describing the homogeneous and heterogeneous equilibria of hydrous silicate melts can account for the following observations: the linearity between fH2O and the square of the mole fraction of dissolved water at low total water contents and deviations from linearity at high total water contents; the difference between the partial molar volume of water in melts at low total water contents and at high total water contents; the similarity between water contents of vapor-saturated melts of significantly different compositions at high pressures versus the dependence on melt composition of water solubility in silicate melts at low pressures; and the variations of viscosity, electrical conductivity, the diffusivity of “water,” the diffusivity of cesium, and phase relationships with the total dissolved water contents of melts.This model is thus consistent with available observations on hydrous melt systems and available data on the species concentrations of hydrous glasses and is easily tested, since measurements of the concentrations of molecular water and hydroxyl groups in silicate glasses quenched from melts equilibrated over a range of conditions and total dissolved water contents are readily obtainable.  相似文献   

17.
A theoretically substantiated technique has been elaborated for the precise determination of minor contents of smectite layers in the dioctahedral mixed-layer structures with a disordered alternation of K-bearing micaceous and ethylene glycol-saturated smectite layers. It is shown that observed positions of the possible mixed-layer mica–smectite structures in the d(003)obs–d(007)obs or 2θ(003)obs–2θ(007)obs diagrams are distributed along a set of parallel straight lines. Data points of each straight line correspond to the mixed-layer structures with one and the same content of smectite layers. A complete matching of theoretical model was recorded in the positions of d(003)obs–d(007)obs and 2θ(003)obs–2θ(007)obs pairs of the basal reflections determined in diffractograms simulated for 160 two-component mixed-layer mica–smectite structures differing in the thickness of alternating layers and their relative content. We studied samples of the dioctahedral K-bearing micas of the glauconite, illite, and aluminoceladonite composition with different thickness of micaceous layers. Positions of the mixed-layer structures of the studied samples on the 2θ(003)obs–2θ(007)obs and d(003)obs–d(007)obs plots make it possible to visually determine the content of smectite layers in each structure accurate to 0.5%. The content of smectite layers in the studied samples varied from 2 to 15%. We obtained equations relating the thickness of smectite and micaceous layers for a specified content of smectite layers. They make it possible to determine the thickness correlation between specified mica and smectite layers. Analogous equations can be used to calculate the Wsm value in each sample for specified experimental values of d(001)mc and d(001)sm and d(003)obs or d(007)obs. The Wsm values coincide within an error limit of 0.2% with those based on the visual estimates in plots.  相似文献   

18.
Thermodynamic simulation of the system living matter (algae, zooplankton, or green plants) + mineral matter (25% carbonates + 75% clay minerals) + standard seawater at temperatures and pressure corresponding to diagenesis indicates that kerogen can be synthesized, together with hydrocarbons and carbon dioxide, in the reaction mix. The removal of CO2(g) and N2(g) from the system is favorable for the reaction Δ1C292H288O12 (s; H/C = 0.99, O/C = 0.041) → Δ2C128H68O7 (s; H/C = 0.53, O/C = 0.055) + xСH4(aq) + yCO2(aq) + zH2O, whose constant and stoichiometric coefficients were calculated based on the simulation results. It is demonstrated that a pressure increase is favorable, while a temperature increase is not, for the procedure of this reaction at P-T parameters of diagenesis: log K =–567 (20°C, 35 bar), 1170 (20°C, 200 bar),–1530 (20°C, 60 bar), and +1030 (20°C, 600 bar).  相似文献   

19.
《Applied Geochemistry》2000,15(8):1203-1218
Ca6[Al(OH)6]2(CrO4)3·26H2O, the chromate analog of the sulfate mineral ettringite, was synthesized and characterized by X-ray diffraction, Fourier transform infra-red spectroscopy, thermogravimetric analyses, energy dispersive X-ray spectrometry, and bulk chemical analyses. The solubility of the synthesized solid was measured in a series of dissolution and precipitation experiments conducted at 5–75°C and at initial pH values between 10.5 and 12.5. The ion activity product (IAP) for the reaction Ca6[Al(OH)6]2(CrO4)3·26H2O⇌6Ca2++2Al(OH)−4+3CrO2−4+4OH−+26H2O varies with pH unless a CaCrO4(aq) complex is included in the speciation model. The log K for the formation of this complex by the reaction Ca2++CrO2−4=CaCrO4(aq) was obtained by minimizing the variance in the IAP for Ca6[Al(OH)6]2(CrO4)3·26H2O. There is no significant trend in the formation constant with temperature and the average log K is 2.77±0.16 over the temperature range 5–75°C. The log solubility product (log KSP) of Ca6[Al(OH)6]2(CrO4)3·26H2O at 25°C is −41.46±0.30. The temperature dependence of the log KSP is log KSP=A−B/T+D log(T) where A=498.94±48.99, B=27,499±2257, and D=−181.11±16.74. The values of ΔG0r,298 and ΔH0r,298 for the dissolution reaction are 236.6±3.9 and 77.5±2.4 kJ mol−1. the values of ΔC0P,r,298 and ΔS0r,298 are −1506±140 and −534±83 J mol−1 K−1. Using these values and published standard state partial molal quantities for constituent ions, ΔG0f,298=−15,131±19 kJ mol−1, ΔH0f,298=−17,330±8.6 kJ mol−1, ΔS0298=2.19±0.10 kJ mol−1 K−1, and ΔC0Pf,298=2.12±0.53 kJ mol−1 K−1, were calculated.  相似文献   

20.
The adsorption of monocarboxylates (acetate, benzoate, and cyclohexanecarboxylate) at the water/goethite interface was studied as a function of pH and ionic strength by means of quantitative adsorption measurements and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. ATR-FTIR spectra were obtained of suspensions prepared in both H2O and D2O. In order to identify the number of predominating surface complexes and to improve the resolution of overlapping peaks the ATR-FTIR spectra were subjected to a 2D correlation spectroscopic analysis. The adsorption envelopes of acetate, benzoate, and cyclohexanecarboxylate are similar and depend strongly on pH and ionic strength, but the pH dependence is also correlated to the slightly different pKa values of the monocarboxylic acids. At the molecular level, the ATR-FTIR spectroscopic results reveal two surface complexes: one solvent-surface hydration-separated ion pair and one surface hydration-shared ion pair. The former predominates at circumneutral pH values while the latter forms mainly in the acidic pH range. We find no evidence for direct inner-sphere coordination between the carboxylic oxygens and the Fe(III) ions present at the surface. The identification of surface hydration-shared ion pairs emphasizes the importance of comparatively strong ionic hydrogen-bonding interactions for adsorption processes at the water/goethite interface.  相似文献   

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