Silver standard forms

Chloride is analyzed by some form of reaction with silver to form insoluble silver chloride. Direct titration of milk with silver nitrate yields erroneously high and variable results, and pre-ashing cannot be used because chloride is lost by volatilization. Satisfactory procedures involve adding an excess of standardized AgN03 directly to milk and back titrating with potassium thiocyanate (KSCN), using a soluble ferric salt as the indicator (Sanders 1939). 

Block (96) reported an analytical method for chloride-bromide mixtures utilizing DSC. The fact that the heat of fusion of an ideal solid solution of the type AWX — BmX or AmX — AWY is directly proportional to the concentration of solute ion was used to determine chloride-bromide mixtures in the concentration range 0-100%. Solutions containing both chloride and bromide are precipitated with silver nitrate, forming solid solutions of silver chloride-bromide. The heat of fusion of the mixed crystal is then determined, and the percent chloride or bromide obtained from a previously prepared standard curve. 

Eigure 11 illustrates the superior conductivity of P/M silver—nickel or silver—cadmium oxide contacts when compared with contacts made by standard melting techniques and formed from soHd-solution alloys. 

Analysis. The abiUty of silver ion to form sparingly soluble precipitates with many anions has been appHed to their quantitative deterrnination. Bromide, chloride, iodide, thiocyanate, and borate are determined by the titration of solutions containing these anions using standardized silver nitrate solutions in the presence of a suitable indicator. These titrations use fluorescein, tartrazine, rhodamine 6-G, and phenosafranine as indicators (50). 

This topic has been reviewed [2, pp 94, 100-111, 130-134] All of the standard approaches to the synthesis of a compound like methyl 2-fluorostearate from methyl 2-bromostearate result mall yield of the 2-fluoro ester and the unsaturated esters. Although silver fluoride is not a new reagent, its use moist in wet acetonitrile to convert methyl 2-bromostearate to its fluoro ester is a departure from the traditional set of anhydrous conditions (Procedure 6, p 194) [71] In contrast, silver tetrafluoroborate converts a-chloroketones to their respective fluoroketones under anhydrous conditions. The displacement of less activated halogen groups by silver tetrafluoroborate to form their respective fluorides is novel Although silver tetrafluoroborate could not be used to convert an aliphatic terminal dichloromethyl or trichloromethyl group to its corresponding fluoro derivative, it is an effective fluorine source in other situations [72] (Table 8)... 

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. 

Anion exchange resin. Proceed as in the previous experiment using 1.0 g, accurately weighed, of the air-dried strongly basic anion exchanger (e.g. Duolite A113, chloride form). Fill the 250 mL separatory funnel with ca 0.25M sodium nitrate solution, and allow this solution to drop into the column at the rate of about 2 mL per minute. Collect the effluent in a 500 mL conical flask, and titrate with standard 0.1M silver nitrate using potassium chromate as indicator. 

Theory. The anion exchange resin, originally in the chloride form, is converted into the nitrate form by washing with sodium nitrate solution. A concentrated solution of the chloride and bromide mixture is introduced at the top of the column. The halide ions exchange rapidly with the nitrate ions in the resin, forming a band at the top of the column. Chloride ion is more rapidly eluted from this band than bromide ion by sodium nitrate solution, so that a separation is possible. The progress of elution of the halides is followed by titrating fractions of the effluents with standard silver nitrate solution. 

The method may also be applied to the analysis of silver halides by dissolution in excess of cyanide solution and back-titration with standard silver nitrate. It can also be utilised indirectly for the determination of several metals, notably nickel, cobalt, and zinc, which form stable stoichiometric complexes with cyanide ion. Thus if a Ni(II) salt in ammoniacal solution is heated with excess of cyanide ion, the [Ni(CN)4]2 ion is formed quantitatively since it is more stable than the [Ag(CN)2] ion, the excess of cyanide may be determined by the Liebig-Deniges method. The metal ion determinations are, however, more conveniently made by titration with EDTA see the following sections. 

A commercial silver alloy in the form of wire or foil is suitable for this determination. Clean the alloy with emery cloth and weigh it accurately. Place it in a 250 mL conical flask, add 5 mL water and 10 mL concentrated nitric acid place a funnel in the mouth of the flask to avoid mechanical loss. Warm the flask gently until the alloy has dissolved. Add a little water and boil for 5 minutes in order to expel oxides of nitrogen. Transfer the cold solution quantitatively to a 100 mL graduated flask and make up to the mark with distilled water. Titrate 25 mL portions of the solution with standard 0.1 M thiocyanate. 

Discussion. Copper(II) ions are quantitatively reduced in 2M hydrochloric acid solution by means of the silver reductor (Section 10.140) to the copper(I) state. The solution, after reduction, is collected in a solution of ammonium iron(III) sulphate, and the Fe2+ ion formed is titrated with standard cerium(IV) sulphate solution using ferroin or AT-phenylanthranilic acid as indicator. 

NIRSystems, Inc., Application Note, Determination of active ingredients in solid (pharmaceutical) dosage forms utilizing solid-state standard additions, Silver Spring, Md. 

Lithium (Li) is a silver-colored soft metal, and the lightest of aU the metallic elements. li is oxidized by atmospheric nitrogen to form lijN. Though li melts at 453.7 K, its boiling point temperature is very much higher at 1620 K. A deep-violet flame is formed when Li is burned in air. Its standard potential is about 3.5 V and a relatively high electric current is formed when it is used in batteries. 

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