共查询到18条相似文献，搜索用时 390 毫秒
1.
高岭石表面的酸碱性质 总被引：5，自引：0，他引：5
采用双位模式（即假定高岭石表面存在＞AIOH和＞SiOH基团）拟合高岭石表面的酸碱滴定数据并描述表面上发生的质子化反应，Al位和Si位的表观常数拟合值分别为pKal,Al=1.78、pKa2,Al=8.47和pKa2,Si=5.12，它们的酸性比对应的（氢）氧化物表面位的更强。高岭石的总表面位密度远大于氧化铝和二氧化硅，其原因很可能是溶液中的质子或羟离子能够渗入高岭石的层间，与层间的羟基发生反应。此外，Al位密度也比Si位大近一个数量级，这种与理论化学式偏离的现象可受多种因素的影响。高岭石表面总体在pH低于4.0时带正电荷，在pH高于4.0时带负电荷。正电荷仅由＞AlOH基团通过质子化作用形成＞AlOH2^ 表面化合态来提供，而负电荷则由＞AlOH和＞SiOH基团的去质子化作用产生，分别形成＞AlO^-和＞SiO^-表面化合态。 相似文献
2.
高岭石水溶液的界面反应特征 总被引：2，自引：1，他引：1
高岭石的表面荷电性、溶解及其对 Cu2 、 Pb2 的吸附等实验结果表明, 高岭石的零净质子电荷点 pHPZNPC=5.2,但端面 >AlOH的 pHPZNPC在 6.5～ 7.0之间,而 >SiOH的 pHPZNPC < 2.3;然而,在 pH 2～ 10范围,ζ电位均为负值,即电动电荷等于零对应的 pH (pHIEP) < 2;且在 pH < 4溶解时, Al溶出率比 Si高,表明高岭石表层形成富 Si贫 Al层.随着溶液 pH由酸性往碱性的变化,重金属离子的吸附表现为离子交换与表面配位模式并存,并发生规律性的变化:在 pH < 6.5时主要表现为离子交换吸附,在 pH < 4时由于受到高岭石 Al的高溶出及较高的离子强度影响,高岭石对 Cu2 、 Pb2 的吸附率较低,但在 pH 5～ 6附近吸附率有明显的提升,并且有个吸附平台;在 pH > 6.5时,主要表现为离子交换和表面配位均为重要的吸附机制,若 pH再升高或重金属离子浓度过高时甚至发生表面沉淀.研究还表明,溶液 pH与离子强度影响高岭石水界面反应过程,表面溶解与质子化反应改变高岭石的表面性质,包括表面荷电性和表面位化合形态,因而调控 Cu2 、 Pb2 的界面吸附行为. 相似文献
3.
阳山伊利石表面化学特性及化合态 总被引：1，自引：0，他引：1
用非连续酸碱滴定法和氯化铵-乙醇法测定表明,2M1型伊利石的pHzpc＝6.5,阳离子交换量CEC＝11.0×105mol/g.应用恒容双表面位模式,通过多元非线性拟合计算表明,伊利石表面铝醇基＞AlOH浓度N1,Al＝4.0×10-5mol/g,质子化常数pKal,Al＝5.95和pKa2,Al＝9.45,硅醇基＞SiOH的Nt.si＝0.53×10-5mol/g,pKa2,si＝3.85.同时发现,在伊利石表面酸碱特性研究中,当溶液pH＜4时,须考虑伊利石表面阳离子与溶液质子之间的交换反应,测定表明交换反应常数Kx＝0.42. 相似文献
4.
高岭石对重金属离子的吸附机理及其溶液的pH条件 总被引：14，自引：0，他引：14
高岭石对Cu^2+,Pb^2+离子的吸附实验及高岭石的溶解实验表明,高岭石对重金属离子的吸附有别于石英单一表面配位模式,离子交换和表面配位模式并存,并随溶液pH由酸性往碱性的变化发生规律性的演替：pH<6.5时主要表现为外圈层配位的离子交换吸附,且在pH<4时由于受到高岭石表层中铝的高溶出及溶液中较高离子强度的影响,高岭石对Cu^2+,Pb^2+离子的吸附率较低,pH为5～6时由于高岭石端面的荷电性为近中性,吸附率则有明显的提升并且表现为一个吸附平台;pH>6.5时离子交换和表面配位均为重要吸附机制,pH再升高时沉淀机制则起着重要作用。研究表明,pH调控高岭石-水界面溶解与质子化-去质子化反应过程,并影响着Cu^2+,Pb^2+离子的吸附行为。最后采用Sverjensky(1993)表面配位的物理模型对吸附结果作了描述。 相似文献
5.
高岭土的化学成分与表面电性研究 总被引：4，自引：0，他引：4
在前人工作的基础之上 ,研究了高岭土中高岭石的晶体结构、化学成分与表面电性之间的关系。硬质和软质高岭土具有相近的表面零电点 (pzc)值 ,几种硬质高岭土的 pzc值的变化范围为 2 .6～ 3 .8。pzc值与其中的SiO2 的重量百分含量呈正相关 ,与Al2 O3的呈负相关。高岭石的结晶度指数 (CI)并不是决定高岭石pzc值的主要因数。在较宽的pH值范围 ,硬质高岭土比软质高岭土的电位低。在高岭石晶体端面上的等电点 ( pH 7.3± )处 ,高岭土表面的Zeta电位与TFe的重量百分含量呈负相关性 ,与高岭石的结晶度指数 (CI)呈正相关。 相似文献
6.
考察酸性条件特别是在近中性 pH范围内胡敏酸对高岭石吸附铜离子的强化作用。研究表明 ,胡敏酸的加入可以提高高岭石对铜离子的吸附率 ,甚至在pH 5～ 6附近高岭石对铜离子的吸附率也从约 5 0 %提高到约 6 5 %。当 pH <4时 ,由于高岭石表面铝的高溶出或胡敏酸阴离子基团离解程度降低等因素 ,使其表面对胡敏酸的吸附率有所降低 ,但与高岭石样品相比 ,胡敏酸高岭石复合体对铜离子的吸附仍然有明显的增加。胡敏酸对高岭石吸附铜离子的强化机制是 ,高岭石端面形成了Al—HA—Cu三元配合物 (B型 ) ,与传统的诸如pH、离子强度与离子初始浓度等介质条件影响不同。在 pH >7时高岭石端面及腐殖质基团去质子化增强 ,因而静电排斥降低了高岭石对胡敏酸的吸附 ,从而使得胡敏酸对铜离子在高岭石表面上的吸附作用有所减弱 ,此时可能出现胡敏酸铜及氢氧化铜的沉淀 ,铜离子的表观吸附率可能不会有明显变化 相似文献
7.
针铁矿/水界面反应性的实验研究 总被引：1，自引：0，他引：1
选择针铁矿对Pb2+、Cu2+、Cd2+等3种重金属离子的吸附实验,开展矿物/水界面反应性研究.金属离子(M2+)在矿物-水溶液间分配有多种表面反应机制,这些表面反应发生作用的条件主要取决于吸附质水化学性质和矿物表面荷电性,因此,溶液pH值是影响矿物/水界面反应性的关键因素.在不同pH值条件下, 表面羟基可通过发生质子化或去质子化反应而使得矿物表面产生荷电性并发生改变,而金属离子的水解则可显著加快金属羟基配合物的形成,从而进一步增强了矿物/水界面反应.本实验条件下针铁矿表面对重金属离子的吸着量随pH值升高而升高,在一个较窄的pH值范围内吸附率急剧升高,呈S形分布.针铁矿对3种不同的重金属离子的吸附能力的强弱顺序是Cu2+＞Pb2+＞Cd2+.无论是Langmuir方程还是Freundlich方程,都能较好拟合针铁矿对重金属离子的等温吸附过程.Freundlich方程的n值均在0.1～0.5之间,说明重金属离子在针铁矿表面的吸附并不能简单地归结为单配位或双配位模式,可能存在着多种吸附结合形态.表观吸附常数KM值的变化规律,说明重金属离子与针铁矿表面反应模式及其表面吸附形态发生了变化,具体的吸附形态还有待谱学研究进一步证实. 相似文献
8.
铜(Ⅱ)在高岭石表面的吸附 总被引：7，自引：1，他引：6
在天然水体系中,铜、铅、镉等重金属元素的形态分布、迁移、归宿和生物有效性强烈取决于重金属元素在水体颗粒物表面的分配趋势.本文对铜(Ⅱ)在常见的重要粘土矿物--高岭石表面的吸附进行了实验和模式研究,结果表明,在同时考虑自由水合离子CU2+和羟基金属离子CuOH+与高岭石表面络合的情况下,单一表面基团、无静电表面络合模式能很好地描述铜(Ⅱ)的吸附行为.拟合得到的CuoH+的络合常数比Cu2+的大得多. 铜(Ⅱ)在高岭石表面的吸附量随pH值的升高而增加.吸附铜的两种表面化合态,>SOCu+和>SOCuOH的浓度在实验的pH范围内,也随pH值升高而增加,并且以>SOCu+为主. 相似文献
9.
五氯苯酚在矿物表面吸附——实验、表面反应模式及其环境意义 总被引：4，自引：0，他引：4
利用批量平衡技术研究了石英、高岭石、伊利石、蒙脱石和铁氧化物对五氯苯酚(PCP)吸附的pH关系等温线和浓度关系等温线,发现所有矿物的pH关系等温线都表现出典型的峰形曲线特征,峰位在pH=5～6之间,依矿物不同而不同。基于矿物表面羟基位化合态和PCP的化合态考虑,提出一种包含表面络合反应和表面静电吸附反应的模式,对pH关系等温线计算拟合发现有很好的相关性。模式计算还表明,石英和层状硅酸盐矿物对PCP吸附以表面络合反应为主,而氧化铁矿物则包含表面络合反应和表面静电吸附反应,但以后者占主导,其反应平衡常数比前者大1～3个数量级。高岭石和氧化铁矿物的浓度吸附等温线可用Langmuir方程很好拟合,最大吸附量的大小顺序是赤铁矿>纤铁矿>针铁矿>高岭石>石英>蒙脱石≈伊利石,并可以用矿物表面羟基位浓度和反应机制加以解释。PCP在矿物表面可观的吸附量说明矿物表面吸附对憎水性可离解有机化合物(HIOCs)在天然水相体系和沉积中的迁移转化过程起着相当重要的作用。 相似文献
10.
《矿物学报》2017,(6)
综合多种测试方法,考察了研磨对茂名高岭石粒径、形貌与微结构等理化性质的影响。重点采用~(29)Si、~(27)Al MAS NMR光谱考察了研磨过程中结构脱羟、Si、Al配位环境变化、新活性位点形成等微结构演变等。结果表明:研磨初期,高岭石六方片层遭到破碎,颗粒粒径逐渐减小,比表面积在研磨1 h达到最大(43.8 m~2/g);此后,颗粒发生团聚,比表面积减小,样品脱羟量和表面吸附水含量均逐渐增加。核磁Si谱和Al谱分别在化学位移-100.5和14.8处出现新的信号,归属于四面体Si与八面体Al相连顶氧质子化作用而产生的Q~3 Si-OH~+-Al结构。研磨导致高岭石脱羟,Al配位状态从AlⅥ经由AlⅤ逐渐向AlⅣ转变。 相似文献
11.
The aqueous interfacial chemistry of kaolinite and Na-montmorillonite samples was investigated by potentiometric measurements using acid/base continuous titrations and batch experiments at 25 and 60 °C. Using the batch experimental method, a continuous drift of pH was observed reflecting the mineral dissolution. Consequently, the continuous titration method appears to be the best way of studying solid surface reactions. For each clay mineral, the net proton surface excess/consumption was calculated as a function of pH and ionic strength (0.025, 0.1 and 0.5 M). At 25 °C, and according to the literature data, the pH corresponding to zero net proton consumption for montmorillonite appears to depend on ionic strength, whereas the value for kaolinite is constant and close to 5. Similar results are obtained at 60 °C, which suggests that the point of zero net proton consumption for clay minerals does not depend on temperature, at least up to 60 °C. On the other hand, the temperature rise induces a slight increase of the net proton surface excess. Finally, the diffuse double layer formalism (DDLM) is used to model the experimental data. The model involves two processes: the protonation/deprotonation of two types of edge sites (aluminol and silanol) and H+/Na+ exchange reactions on basal surfaces, while a tiny proportion of the negative structural charge remains uncompensated. This last process maintains a negative surface potential whatever the pH of the solution, which is in agreement with electrokinetic data. 相似文献
12.
Dana R. Rosenberg 《Geochimica et cosmochimica acta》2003,67(2):223-229
Siderophores are Fe(III)-specific ligands produced by many aerobic microorganisms under conditions of iron stress. This study examined adsorption of the commercial trihydroxamate siderophore, desferrioxamine B (DFO-B), to an iron-containing kaolinite (0.1 bulk wt.% Fe) and examined DFO-B effects on initial kaolinite dissolution and iron release rates. Adsorption experiments were conducted at pH 3 to 8 in 0.01-M NaClO4 in the dark and at 22°C; batch initial dissolution experiments were conducted to 96 h.The adsorption envelope (i.e., adsorption as a function of pH) of DFO-B on kaolinite was consistent with cation-like behavior, with adsorption increasing above kaolinite’s pHpznpc of 4.9. DFO-B enhanced aluminum release from kaolinite at pH 3 to 7, relative to HNO3, which is consistent with the ligand’s high binding affinity for Al. Correlation between DFO-B adsorption and aluminum release suggested a surface-controlled, ligand-promoted dissolution mechanism. DFO-B had no effect relative to HNO3 on silicon release at pH 3 and 5, but moderately enhanced silicon release at pH 7. DFO-B enhanced iron release from kaolinite, with dissolved iron concentrations in the 10-ppb range at 96-h reaction time. These results show that kaolinite may serve as a source of iron to aerobic microorganisms in iron-limited conditions and that siderophores may affect kaolinite dissolution and iron content. 相似文献
13.
Dissolution experiments of a tholeiite basalt glass carried out at different pH and T (up to 300°C) using a rotatingdisc apparatus show that, depending on pH and T, dissolution can be controlled by one of the following steps: (1) surface reaction; (2) transport of reactants in solution; and (3) mixed reaction. The activation energies of these different processes were found to be 60, 9 and 15–50 kJ mol−1, respectively. Taking account of these results, it appears likely that surface reactions are not rate limiting for the hydrolysis of most crystalline silicate minerals in hydrothermal and metamorphic processes, and that caution should be exercised when predicting rate of reactions at high temperatures solely on the basis of activation energies measured at low temperatures.
Comparison of experimental and theoretical potentiometric titrations of the basalt glass and its constituent oxides indicates that the adsorption of H+ and OH− ions at the basalt surface is metal cation specific and that the net adsorption can be predicted from the sole knowledge of the acidity constants of the network-forming constituent oxides. We found that in the acidic pH region dissolution is promoted by the adsorption of H+ on al and Fe surface sites while in the basic region, dissolution is promoted by the adsorption of OH− on Si sites. The combination of the two distinct types of surface sites, Al and Fe on the one hand, and Si on the other hand, results in a dissolution rate minimum at a pH-value between the pHzpc of the two groups of oxide components. Linear regressions with a slope n=3.8 are observed both in acid and alkaline solutions in logarithmic plots of the rate of dissolution vs. the surface charge. The value of n, which represents the number of protonation or hydroxylation steps prior to metal detachment, has been found equal to the mean valence of the network-forming metals.
Combining concepts of surface coordination chemistry with transition state theory afforded characterisation of the activated complexes involved in basalt dissolution processes. From the values obtained for the thermodynamic properties of activation for basalt dissolution it is assumed that the activated complexes formed during the H2O-promoted dissolution of the basalt glass are more tightly bonded than those formed during H+- or OH−-promoted dissolution. 相似文献
14.
Jeremy B. Fein Jean-François Boily Drew Gorman-Lewis 《Geochimica et cosmochimica acta》2005,69(5):1123-1132
To provide constraints on the speciation of bacterial surface functional groups, we have conducted potentiometric titrations using the gram-positive aerobic species Bacillus subtilis, covering the pH range 2.1 to 9.8. Titration experiments were conducted using an auto-titrator assembly, with the bacteria suspended in fixed ionic strength (0.01 to 0.3 M) NaClO4 solutions. We observed significant adsorption of protons over the entire pH range of this study, including to the lowest pH values examined, indicating that proton saturation of the cell wall did not occur under any of the conditions of the experiments. Ionic strength, over the range studied here, did not have a significant effect on the observed buffering behavior relative to experimental uncertainty. Electrophoretic mobility measurements indicate that the cell wall is negatively charged, even under the lowest pH conditions studied. These experimental results necessitate a definition of the zero proton condition such that the total proton concentration at the pH of suspension is offset to account for the negative bacterial surface charge that tends towards neutrality at pH <2.The buffering intensity of the bacterial suspensions reveals a wide spread of apparent pKa values. This spread was modeled using three significantly different approaches: a Non-Electrostatic Model, a Constant Capacitance Model, and a Langmuir-Freundlich Model. The approaches differ in the manner in which they treat the surface electric field effects, and in whether they treat the proton-active sites as discrete functional groups or as continuous distributions of related sites. Each type of model tested, however, provides an excellent fit to the experimental data, indicating that titration data alone are insufficient for characterizing the molecular-scale reactions that occur on the bacterial surface. Spectroscopic data on the molecular-scale properties of the bacterial surface are required to differentiate between the underlying mechanisms of proton adsorption inherent in these models. The applicability and underlying conceptual foundation of each model is discussed in the context of our current knowledge of the structure of bacterial cell walls. 相似文献
15.
Proton binding constants for the edge and basal surface sites of kaolinite were determined by batch titration experiments at 25 °C in the presence of 0.1 M, 0.01 M and 0.001 M solutions of NaNO3 and in the pH range 3-9. By optimizing the results of the titration experiments, the ratio of the edge sites to the basal surface sites was found to be 6:1. The adsorption of Cd(II), Cu(II), Ni(II), Zn(II) and Pb(II) onto kaolinite suspensions was investigated using batch adsorption experiments and results suggested that in the lower pH range the metallic cations were bound through non-specific ion exchange reactions on the permanently charged basal surface sites (X−). Adsorption on these sites was greatly affected by ionic strength. With increasing pH, the variable charged edge sites (SOH) became the major adsorption sites and inner-sphere specifically adsorbed monodentate complexes were believed to be formed. The effect of ionic strength on the extent of adsorption of the metals on the variable charged edge sites was much less than those on the permanently charged sites. Two binding constants, log K(X2Me) and log K(SOMe), were calculated by optimizing these constants in the computer program FITEQL. A model combining non-specific ion exchange reactions and inner-sphere specific surface complexations was developed to predict the adsorption of heavy metals onto kaolinite in the studied pH range. Linear free energy relationships were found between the edge site binding constants and the first hydrolysis constants of the metals. 相似文献
16.
The effects of organic acids on the dissolution of silicate minerals: A case study of oxalate catalysis of kaolinite dissolution 总被引：1，自引：0，他引：1
Jordi Cama 《Geochimica et cosmochimica acta》2006,70(9):2191-2209
Most studies agree that the dissolution rate of aluminosilicates in the presence of oxalic and other simple carboxylic acids is faster than the rate with non-organic acid under the same pH. However, the mechanisms by which organic ligands enhance the dissolution of minerals are in debate. The main goal of this paper was to study the mechanism that controls the dissolution rate of kaolinite in the presence of oxalate under far from equilibrium conditions (−29 < ΔGr < −18 kcal mol−1). Two types of experiments were performed: non-stirred flow-through dissolution experiments and batch type adsorption isotherms. All the experiments were conducted at pH 2.5-3.5 in a thermostatic water-bath held at a constant temperature of 25.0, 50.0 or 70.0 ± 0.1 °C. Kaolinite dissolution rates were obtained based on the release of silicon and aluminum at steady state. The results show good agreement between these two estimates of kaolinite dissolution rate. At constant temperature, there is a general trend of increase in the overall dissolution rate as a function of the total concentration of oxalate in solution. The overall kaolinite dissolution rates in the presence of oxalate was up to 30 times faster than the dissolution rate of kaolinite at the same temperature and pH without oxalate as was observed in our previous study. Therefore, these rate differences are related to differences in oxalate and aluminum concentrations. Within the experimental variability, the oxalate adsorption at 25, 50, and 70 °C showed the same dependence on the sum of the activities of oxalate and bioxalate in solution. The change of oxalate concentration on the kaolinite surface (Cs,ox) as a function of the sum of the activities of the oxalate and bioxalate in solution may be described by the general adsorption isotherm:
17.
O.S. Pokrovsky R.E. Martinez S.V. Golubev E.I. Kompantseva L.S. Shirokova 《Applied Geochemistry》2008
The purpose of the present work is to extend our knowledge of metal–cyanobacteria interactions and to contribute to the database on adsorption parameters of aquatic microorganisms with respect to metal pollutants. To this end, the surface properties of the cyanobacteria (Gloeocapsa sp. f-6gl) were studied using potentiometric acid–base titration methods and ATR-FTIR (attenuated total reflection infrared) spectroscopy. The electrophoretic mobility of viable cells was measured as a function of pH and ionic strength (0.01 and 0.1 M). Surface titrations at 0.01–1.0 M NaCl were performed using limited residence time reactors (discontinuous titration) with analysis of Ca, Mg and dissolved organic C for each titration point in order to account for alkali-earth metal–proton exchange and cell degradation, respectively. Results demonstrate that the cell-wall bound Ca and Mg from the culture media contribute to the total proton uptake via surface ion-exchange reactions. This has been explicitly taken into account for net proton balance calculations. Adsorption of Zn, Cd, Pb and Cu was studied at 25 °C in 0.01 M NaNO3 as a function of pH and metal concentration. The proportion of adsorbed metal increases as a function of culture age with cells of 44 days old having the largest adsorption capacities. A competitive Langmuir sorption isotherm in conjunction with a linear programming method (LPM) was used to fit experimental data and assess the number of surface sites and adsorption reaction constants involved in the binding of metals to the cyanobacteria surface. These observations allowed the determination of the identity and concentration of the major surface functional groups (carboxylate, amine, phosphoryl/phosphodiester and hydroxyl) responsible for the amphoteric behavior of cyanobacterial cell surfaces in aqueous solutions and for metal adsorption. Results of this work should allow better optimizing of metal bioremediation/biosequestration processes as they help to define the most efficient range of pH, cell biomass and duration of exposure necessary for controlled metal adsorption on cyanobacteria cultures. It follows from comparison of adsorption model parameters between different bacteria that technological application of cyanobacteria in wastewater bioremediation can be as efficient as other biological sorbents. 相似文献
18.
Claire Chaïrat Eric H. Oelkers Jacques Schott 《Geochimica et cosmochimica acta》2007,71(24):5888-5900
The surface chemistry of fluorapatite in aqueous solution was investigated using electrokinetic techniques, potentiometric titrations, solubility measurements, and attenuated total reflection infrared spectroscopy. All methods indicate the formation of Ca/F depleted, P enriched altered layer via exchange reactions between H+ and Ca2+, and OH− and F− at the fluorapatite (FAP) surface. Observations suggest that this leached layer has a di-calcium phosphate (CaHPO4) composition and that it controls the apparent solubility of FAP. Electrokinetic measurements yield an iso-electric point value of 1 ± 0.5 consistent with a negatively charged FAP surface at pH > 1. In contrast, surface titrations give an apparent pH of point of zero charge of ∼7.7, consistent with a positively charged surface at pH < 7.7. These differences are shown to stem from proton consumption by both proton exchange and dissolution reactions at the FAP surface. After taking account for these effects, FAP surface charge is shown to be negative to at least pH 4 by surface titration analysis. 相似文献