Analytical Chem istry - DePauw University

366 Analytical Chemistry 2.0primaryadsorption layerinert cation+ –– –+ –++–+ –+ + AgCl–+ –+ + +––+ – –inert anionchemicallyadsorbed Ag +secondaryadsorption layerprecipitateparticle(a)(b)(c)+ –– –+ –++–+ –+ + AgCl–+ –+ + +––+ – –+ – +– –+ + ––+–+ AgCl +––++ +––+ – + –+ ––– +++ ––++ –+ AgCl–+–+ + +– –+ – –+– +– +–++––++AgCl+–––+ ++––+ +––– +– ++++ +– + AgCl–– + ++– –––+ –+ ––+ +––– –+ –+–+ –– + +–AgCl +– ++++ + ––+––++––+ –+–+– ++–AgCl–++––– ++– +–– – + –+–+ –– + +AgCl + –– + +– + + +–+ – –precipitatecoagulatedprecipitateparticleparticlesparticleFigure 8.6 Two methods for coagulating a precipitate of AgCl. (a) Coagulation does not happen due to the electrostaticrepulsion between the two positively charged particles. (b) Decreasing the charge within the primary adsorption layer, byadding additional NaCl, decreases the electrostatic repulsion, allowing the particles to coagulate. (c) Adding additionalinert ions decreases the thickness of the secondary adsorption layer. Because the particles can approach each other moreclosely, they are able to coagulate.into larger particles that are easier to filter. Surface adsorption of excess latticeions, however, provides the precipitate’s particles with a net positive ora net negative surface charge. Electrostatic repulsion between the particlesprevents them from coagulating into larger particles.Let’s use the precipitation of AgCl from a solution of AgNO 3 usingNaCl as a precipitant to illustrate this effect. Early in the precipitation,when NaCl is the limiting reagent, excess Ag + ions chemically adsorb tothe AgCl particles, forming a positively charged primary adsorption layer(Figure 8.6a). The solution in contact with this layer contains more inertanions, NO 3 – in this case, than inert cations, Na + , giving a secondary adsorptionlayer with a negative charge that balances the primary adsorptionlayer’s positive charge. The solution outside the secondary adsorption layerremains electrically neutral. Coagulation cannot occur if the secondaryadsorption layer is too thick because the individual particles of AgCl areunable to approach each other closely enough.We can induce coagulation in three ways: by decreasing the number ofchemically adsorbed Ag + ions, by increasing the concentration of inert ions,or by heating the solution. As we add additional NaCl, precipitating moreof the excess Ag + , the number of chemically adsorbed silver ions decreases