Solubility silver chloride

Adding the common ion greatly decreases the silver chloride solubility. 

The silver-silver chloride electrode. The silver chloride reference electrode is not generally suitable as an electrode of the second kind because of the large solubility of AgCl in many aptotic solvents from formation of anionic complexes with chloride ion. In many cases the silver chloride solubility will essentially be that of the added chloride. This contributes significantly to the junction potential in cells with liquid junction and makes the electrode unsuitable for precise potentiometric work. 

Note that Equilibrium 11-28 and thus Equilibrium 11-27 shift to the left with added chloride ion, whereas Equilibria 11-29 and 1 1-30 shift to the right under the same circumstance. The consequence of these opposing eflects is that a plot of silver chloride solubility as a function of concentration of added chloride exhibits a minimum. Example 11 -9 illustrates how this behavior can be described in quantitative terms. 

Determine the equilibrium constant for the dissolution and dissociation of silver chloride in water, and the silver chloride solubility in water. 

Silver. Hydrochloric acid precipitates white silver chloride, soluble in ammonium hydroxide. 

This equation represents the solubility product of silver chloride. Solubility products are generally used to describe the solubility and equilibria of sparingly soluble salts in aqueous solutions. Solubility products of a number of substances are given in Table 1.3. It is important to remember that use of solubility product relations based on concentrations assumes that the solution is saturated, in equilibrium, and ideal (the activity coefficient is equal to one), and is therefore an approximation, except with very dilute solutions of one solute. 

Characters and Tests.—Small, white, crystalline grains, or transparent cubic crystals, free from moisture purely saline taste soluble in water. Its aqueous solution mixed with hydrochloric acid and platinic chloride yields no precipitate, showing that it is neither an ammonium nor a potassium-salt. It imparts a yellow, colour to fiame, indicating that sodium is present and its aqueous solution gives with silver nitrate a white precipitate (silver chloride) soluble in ammonia, but Soluble in boiling nitric acid, proving the salt to be a chloride. 

Addition of silver nitrate to a solution of a chloride in dilute nitric acid gives a white precipitate of silver chloride, AgCl, soluble in ammonia solution. This test may be used for gravimetric or volumetric estimation of chloride the silver chloride can be filtered off, dried and weighed, or the chloride titrated with standard silver nitrate using potassium chromate(VI) or fluorescein as indicator. 

Addition of silver nitrate to a solution of a bromide in nitric acid produces a cream-coloured precipitate of silver bromide, soluble in ammonia (but not so readily as silver chloride). The reaction may be used quantitatively, as for a chloride. 

Silver chloride is readily soluble in ammonia, the bromide less readily and the iodide only slightly, forming the complex cation [Ag(NH3)2]. These halides also dissolve in potassium cyanide, forming the linear complex anion [AglCN) ] and in sodium thiosulphate forming another complex anion, [Ag(S203)2] ... 

It was known in the sixteenth century that silver salts were photosensitive, but it was not until the beginning of the nineteenth century, when Herschel found that silver chloride was soluble in sodium thiosulphate, that photography became possible. 

To determine which halogen is present, take 1-2 ml. of the filtrate from the sodium fusion, and add dilute sulphuric acid until just acid to litmus. Add about 1 ml. of benzene and then about 1 ml. of chlorine water and shake. A yellowish-brown colour in the benzene indicates bromine, and a violet colour iodine. If neither colour appears, the halogen is chlorine. The result may be confirmed by testing the solubility of the silver halide (free from cyanide) in dilute ammonia solution silver chloride is readily soluble, whereas the bromide dissolves with difficulty, and the iodide not at all. 

Reference Electrodes and Liquid Junctions. The electrical cincuit of the pH ceU is completed through a salt bridge that usually consists of a concentrated solution of potassium chloride [7447-40-7]. The solution makes contact at one end with the test solution and at the other with a reference electrode of constant potential. The Hquid junction is formed at the area of contact between the salt bridge and the test solution. The mercury—mercurous chloride electrode, the calomel electrode, provides a highly reproducible potential in the potassium chloride bridge solution and is the most widely used reference electrode. However, mercurous chloride is converted readily into mercuric ion and mercury when in contact with concentrated potassium chloride solutions above 80°C. This disproportionation reaction causes an unstable potential with calomel electrodes. Therefore, the silver—silver chloride electrode and the thallium amalgam—thallous chloride electrode often are preferred for measurements above 80°C. However, because silver chloride is relatively soluble in concentrated solutions of potassium chloride, the solution in the electrode chamber must be saturated with silver chloride. 

The raw precious metal concentrate is totally dissolved in hydrochloric acid—chlorine solution to form the soluble chloride ions of each of the metals. Silver remains as insoluble silver chloride and can be filtered off. Gold, in the form of [AuClJ, is extracted with, eg, tributyl phosphite or methyl isobutyl ketone. Base metals are also extracted in this step, and are removed from the organic phase by scmbbing with dilute hydrochloric acid (HCl). Iron powder is then used to reduce the gold species and recover them from the organic phase. 

Ammonia forms a great variety of addition or coordination compounds (qv), also called ammoniates, ia analogy with hydrates. Thus CaCl2 bNH and CuSO TNH are comparable to CaCl2 6H20 and CuSO 4H20, respectively, and, when regarded as coordination compounds, are called ammines and written as complexes, eg, [Cu(NH2)4]S04. The solubiHty ia water of such compounds is often quite different from the solubiHty of the parent salts. For example, silver chloride, AgQ., is almost iasoluble ia water, whereas [Ag(NH2)2]Cl is readily soluble. Thus silver chloride dissolves ia aqueous ammonia. Similar reactions take place with other water iasoluble silver and copper salts. Many ammines can be obtained ia a crystalline form, particularly those of cobalt, chromium, and platinum. 

Silver Bromide. Silver bromide, AgBr, is formed by the addition of bromide ions to an aqueous solution of silver nitrate. The light yellow to green-yeUow precipitate is less soluble in ammonia than silver chloride, but it easily dissolves in the presence of other complexing agents, such as thiosulfate ions. 

Silver Chloride. Silver chloride, AgCl, is a white precipitate that forms when chloride ion is added to a silver nitrate solution. The order of solubility of the three silver halides is Cl" > Br" > I. Because of the formation of complexes, silver chloride is soluble in solutions containing excess chloride and in solutions of cyanide, thiosulfate, and ammonia. Silver chloride is insoluble in nitric and dilute sulfuric acid. Treatment with concentrated sulfuric acid gives silver sulfate. 

Halide Complexes. Silver hahdes form soluble complex ions, AgX and AgX , with excess chloride, bromide, and iodide. The relative stabihty of these complexes is 1 > Br > Cl. Complex formation affects solubihty greatiy. The solubihty of silver chloride in 1 A/ HCl is 100 times greater than in pure water. 

Qualitative. The classic method for the quaUtative determination of silver ia solution is precipitation as silver chloride with dilute nitric acid and chloride ion. The silver chloride can be differentiated from lead or mercurous chlorides, which also may precipitate, by the fact that lead chloride is soluble ia hot water but not ia ammonium hydroxide, whereas mercurous chloride turns black ia ammonium hydroxide. Silver chloride dissolves ia ammonium hydroxide because of the formation of soluble silver—ammonia complexes. A number of selective spot tests (24) iaclude reactions with /)-dimethy1amino-henz1idenerhodanine, ceric ammonium nitrate, or bromopyrogaHol red [16574-43-9]. Silver is detected by x-ray fluorescence and arc-emission spectrometry. Two sensitive arc-emission lines for silver occur at 328.1 and 338.3 nm. 

This material can be used only in seawater or similar chloride-containing electrolytes. This is because the passivation of the silver at discontinuities in the platinum is dependent upon the formation of a film of silver chloride, the low solubility of which, in seawater, inhibits corrosion of the silver. This anode, consisting of Pt-lOPd on Ag, was tried as a substitute for rapidly consumed aluminium, for use as a trailing wire anode for the cathodic protection of ships hulls, and has been operated at current densities as high as 1 900 AmHowever, the use of trailing anodes has been found inconvenient with regard to ships manoeuvrability. 

Similar measurements were made for the heat of precipitation of silver iodide,5 which is even less soluble in water than silver chloride. As shown in Table 33 in Sec. 102, a saturated solution of Agl at 25°C contains only 9.08 X 10-9 molcs/liter, as compared with 1.34 X 10-6 for AgCl. By calorimetric measurement the heat of precipitation of Agl at 25°C was found to be 1.16 electron-volts per ion pair, or 20,710 cal/mole. 

Iron(III) nitrate is soluble, but silver chloride is not When these two solutions are mixed, silver chloride precipitates. 

Calculate the solubility (in grams per liter) of silver chloride in the following. 

For example, sodium chloride continues to dissolve in water at 20°C until the concentration is about six moles per liter. The solubility of NaCl in water is 6 M at 20°C. In contrast, only a minute amount of sodium chloride dissolves in ethyl alcohol at 20°C. This solubility is 0.009 M. Even in a single liquid, solubilities differ over wide limits. The solids calcium chloride, CaCl2, and silver nitrate, AgNOa, have solubilities in water exceeding one mole per liter. The solid called silver chloride, AgCl, has a solubility in water of only 10 5 mole per liter. 

Silver chloride is a solid that shows this effect. This solid does not dissolve readily in water. When solid silver chloride is placed in water, very little solid enters the solution and there is only a very slight increase in the conductivity of the solution. Yet there is a real and measurable increase—ions are formed. Careful measurements show that even though silver chloride is much less soluble in water than sodium chloride, it is like sodium chloride in that all the solid that does dissolve forms aqueous ions. The reaction is... 

Though both silver nitrate and sodium chloride have high solubility in water, silver chloride is very slightly soluble. What will happen if we mix a solution of silver nitrate and sodium chloride Then, we will have a solution that includes the species present in a solution of silver chloride, Ag+(aq) and Cl (ag), but now they are present at high concentration The Ag+(agJ came from reaction (8) and the Cl (aq) came from reaction (6) and their concentrations far exceed the solubility of silver chloride. The result is that solid will be formed. The formation of solid from a solution is called precipitation ... 

We have seen in Experiment 8 that silver chloride has low solubility in water. This is also true for silver bromide and silver iodide. In fact, these low solubilities provide a sensitive test for the presence of chloride ions, bromide ions, and iodide ions in aqueous solutions. If silver nitrate... 

Despite this detailed familiarity with equilibrium, there is one facet we have not considered at all. What determines the equilibrium constant Why does one reaction favor reactants and another reaction favor products What factors cause sodium chloride to have a large solubility in water and silver chloride to have a low solubility Why does equilibrium favor the reaction of oxygen with iron to form FejAi (rust) but not the reaction of oxygen with gold As scientists, we cannot resist wondering what factors determine the conditions at equilibrium. 

Expression (2) applies to a solubility equilibrium, provided we write the chemical reaction to show the important molecular species present. In Section 10-1 we considered the solubility of iodine in alcohol. Since iodine dissolves to give a solution containing molecules of iodine, the concentration of iodine itself fixed the solubility. The situation is quite different for substances that dissolve to form ions. When silver chloride dissolves in water, no molecules of silver chloride, AgCl, seem to be present. Instead, silver ions, Ag+, and chloride ions, Cl-, are found in the solution. The concentrations of these species, Ag+ and Cl-, are the ones which fix the equilibrium solubility. The counterpart of equation (7) will be... 

The solubility of silver chloride is so low that all but a negligible amount of it is precipitated when excess sodium chloride solution is added to silver nitrate solution. What would be the weight of the precipitate formed when 100 ml of 0.5 M NaCl is added to 50.0 ml of 0.100 M AgNOs ... 

The solubility product of AgCl is 1.4 x 10-4 at 100°C. Calculate the solubility of silver chloride in boiling water. 

The negative voltage shows that the state of equilibrium favors the reactants more than the products for the reaction as written. For standard conditions, the reaction will not tend to occur spontaneously. However, if we place Ag(s) in 1 M H+, the Ag+ concentration is not 1 M— it is zero. By Le Chatelier s Principle, this increases the tendency to form products, in opposition to our prediction of no reaction. Some silver will dissolve, though only a minute amount because silver metal releases electrons so reluctantly compared with H2. It is such a small amount, in fact, that no silver chloride precipitate forms, even though silver chloride has a very low solubility. 

That some silver does dissolve to form Ag+ can be verified experimentally by adding a little KI to the solution. Silver iodide has an even lower solubility than does silver chloride. The experiment shows that the amount of silver that dissolves is sufficient to cause a visible precipitate of Agl but not of AgCl. This places the Ag+ ion concentration below 10-10 M but above 10-17 M. Either of these concentrations is so small that we can consider our prediction for the standard state to be applicable here too—silver metal does not dissolve appreciably in 1 M HC1. In general, the question of whether a prediction based upon the standard state will apply to other conditions depends upon how large is the magnitude of °. If ° for the overall reaction is only one- or two-tenths volt (either positive or negative), then deviations from standard conditions may invalidate predictions that do not take into account these deviations. 

In a linear complex, the coordination number is 2, corresponding to one group on each side of the central atom. The silver-ammonia complex, which generally forms when a very slightly soluble silver salt such as silver chloride dissolves in aqueous ammonia, is an example, as shown in Figure 22-6. Another example of a linear com-... 

A plausible deduction of the solubility product relation is the following. When excess of a sparingly soluble electrolyte, say silver chloride, is shaken up with... 

Example 1. The solubility of silver chloride is 0.0015 g per L. Calculate the solubility product. 

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