Iuliano Mauro, Ciavatta Liberato, De Tommaso Gaetano
Dipartimento di Chimica dell'Università Federico II, Via Cinthia 45, 80126 Naples, Italy.
J Colloid Interface Sci. 2007 Jun 15;310(2):402-10. doi: 10.1016/j.jcis.2007.02.061. Epub 2007 Mar 21.
Adsorption of hydrogen ions from aqueous NaCl solutions at the Pyrex glass-water interface was investigated by acid-base titration (glass electrode) at 25 degrees C and at the ionic strengths 0.010, 0.030, 0.10, 1.0, and 3.0 mol dm(-3). The pH values ranged from 2 to 7. The Pyrex samples had a specific surface area of 19.2x10(3) m(2)kg(-1) and a porous structure (pores 2.4 nm thick, 280 nm long). The reactions were found to be extremely slow but showed good reversibility. The potentiometric data, due to the small effect of ionic strength on the equilibria, were fitted with a simple nonelectrostatic model based on strong specific interactions of medium ions with deprotonated silanol, >SiO(-), and boranol, >BO(-), as well as with protonated sites. The acid-base properties are described by the reactions and equilibrium constants at the infinite dilution reference state: >SiONa + H(+) <==> >SiOHNa(+), logbeta110Si=3.1+/-0.2; >SiONa + 2H(+) + Cl(-) <==> >SiOH(2)Cl + Na(+), logbeta201Si=6.75+/-0.15; >SiONa + H(+) <==> >SiOH + Na(+), logbeta100Si=1.8+/-0.2, >BONa + H(+) <==>>BOH + Na(+), logbeta100B=6.4+/-0.2; >BONa + H(+) <==> >BOHNa(+), logbeta110B=6.6+/-0.2; >BONa + 2H(+) <==> >BOH(+)(2) + Na(+), logbeta200B=11.56+/-0.15.
通过酸碱滴定法(玻璃电极),在25℃以及离子强度分别为0.010、0.030、0.10、1.0和3.0 mol dm⁻³的条件下,研究了派热克斯玻璃 - 水界面处氢离子从NaCl水溶液中的吸附情况。pH值范围为2至7。派热克斯样品的比表面积为19.2×10³ m²kg⁻¹,具有多孔结构(孔径2.4 nm,孔长280 nm)。发现反应极其缓慢,但具有良好的可逆性。由于离子强度对平衡的影响较小,电位数据采用基于介质离子与去质子化硅醇(>SiO⁻)、硼醇(>BO⁻)以及质子化位点之间强特异性相互作用的简单非静电模型进行拟合。酸碱性质通过无限稀释参考状态下的反应和平衡常数来描述:>SiONa + H⁺ ⇌ >SiOHNa⁺,logβ₁₁₀Si = 3.1 ± 0.2;>SiONa + 2H⁺ + Cl⁻ ⇌ >SiOH₂Cl + Na⁺,logβ₂₀₁Si = 6.75 ± 0.15;>SiONa + H⁺ ⇌ >SiOH + Na⁺,logβ₁₀₀Si = 1.8 ± 0.2,>BONa + H⁺ ⇌ >BOH + Na⁺,logβ₁₀₀B = 6.4 ± 0.2;>BONa + H⁺ ⇌ >BOHNa⁺,logβ₁₁₀B = 6.6 ± 0.2;>BONa + 2H⁺ ⇌ >BOH₂⁺ + Na⁺,logβ₂₀₀B = 11.56 ± 0.15。