5._Cation_exchange_阳离子交换2概述.pptVIP

* H+与阳离子交换的不同，H+会导致化学风化，导致矿物发生变化。 * 可变电荷：矿物的末端羟基，产生负电荷吸引溶液中的阳离子，pH值决定可变电荷的多少。pH高，带负电荷；pH低，带正电荷——PZC零电荷点 * Cl-=表面正电荷的吸附；Na+=表面负电荷的吸附 * 有机质偏离有机酸 * 因为偏离所以加一个修正系数 * * 与理想的阳离子交换偏离的也很远 * 5. Cation exchange (part 2) Processes and models Diffuse double layer (DDL) Diffuse double layer (DDL) DDL contains all exchangeable cations Higher concentration in solution ? higher concentration in DDL Higher concentration in DDL ? smaller DDL Boltzmann equation ci=ci,0 exp (-ziψ/kT) Diffuse double layer (DDL) DDL larger for monovalent（一价的） cations than for divalents（二价的） In salt affected soils (NaCl; Na+ monovalent cation!) ? Clay minerals cannot coagulate（凝聚）, due to repulsion forces (inside DDL: net negative charge) Salt affected soils become structureless, with poor hydrological properties Clay layers in subsoils, deposited from seawater are often unstable Soils affected by Ca-salts: better structured Cation exchange: Difference in valence NA and NB indicate equivalent (当量) fraction exchange sites for A and B, respectively. Gaines-Thomas equation Problem: Effect of dilution; Concentration – Charge Effect Dilution ? Increase adsorption of higher charged ions Concentration-Charge Effect In areas with high precipitation (降水): increased tendency for exchangeable multivalent (多价的) cations In ”dry” areas: tendency for exchangeable monovalent (一价的) cations: ”salt affected” soils with high contents of exchangeable Na 交换性盐基（me/100g) Ca2+ Mg2+ K+ Na+ CEC 红壤 0.63 0.17 0.15 0.16 1.09 盐土 10.6 12.1 39.15 ？ Problem Calculate the cationic composition (in %) of the exchange complex of a clay soil (KCa/Na =5) in equilibrium with a solution containing A. 0.1 M NaCl and 0.05 M CaCl2 Nna+= 0.18, NCa2+= 0.82 B. 0.01 M NaCl and 0.005 M CaCl2 Nna+= 0.06, NCa2+= 0.94 Rate of ion exchange reactions Fast: At surface exposed to solutions Interlayer adsorption: Diffusion controlled (often not fully reversible可逆) Hydrolytic exchange Exchang