CHAPTER 12 GROUP I CATIONS he tyweniatic analysia of the common cations is based upon the suc- ‘ceenive preciiitation of groups of ions, go that the total number of Tons can be Broken down into a small number of groups, each containing, number of related cations. The first of these separations is the precipi- tation of Group I, which is composed of those common cations whose \ : ble i 121 | Theoretical Discussion. The successful separation of a group of cations is determined by the relative solubility products of the com- Pounds formed by the cations with the precipitating anion. The insoluy ble chlorides of Group I are lead chloride, mercurous chloride, and silver ‘chloride, The sohttahis ‘products of these compounds are 1 10-* for \PbCls, 2 X 10-" for HgsCls, and 1.56 X 10-" for AgCl. To the begin. ning student; the term solubility product may not be as that of solubility. -Erom the above Sgures the solubility of lead chloride id calculated }abe appréximately 0.04 F, that of mercurous chloride to be 7.5 X 16-1 F, and that of silver chloride as 1.3. 10"' FA. rough com- parison of these solubilities aioe that lead ‘chloride is one thousand times more séluble than ailver chloride; and one hundred thousand times more soluble than mercurous chloride, Since the precipitating anion is “ih excead, ‘thd above sdlubilities are further decreased by common-ion Tine vi © values for the solubilities of Group I chlorides indicate that silver chloride and merourous chloride are almost completely Precipitated, whereas lead chloride i¢ always incompletely precipitated and in low con- centratidns may not be precipitated at all. After the ‘group separation is made, the ions within the group must be separated to the extent necessary for individuyl identification Again, in the cage of PpCla thers ja apoocseparation. VLead chloride is partially weparated {rom mercurous chloride and silver chloride because of an significant as in in solubility of lead chloride in hot water. ‘The solubility of PbCi in 0.678.g/100 mal of water at 0°C and 3.34 g/100 ml at 100°C. In other words, the solubility of lead chloride increases approximately five times in going throtgh this temperature range. Therefore, come PbCl; may be leached from the group precipitate by treating it witn hot water, 186186 . EXPERIMENTAL PROCEDURES provided that the water stays hot, but all the PbCl; is seldom removed, A portion of the undissolved PbC], may remain as @ white residue and cause some confusion in making the identification teste for silver and mercurous ions. Silver chloride is separated from mercurous chloride by ita solubility in ammonia, in which the soluble complex ion, Ag(NH,)s*, is formed. The efficiency of this separation depends upon the concentration of the this separation is clean, but the solubility of AgC! in ammonia water to form the soluble complex ion has « limiting value, and if the amount of AgCl is very large some of it may not be dissolved. Ammonia water not only reacts with AgCl, But it also serves as a medium for the suto-redox action of Hg:Cl: to produce mercury and mercuric aminochloride, both of which are insoluble. Metallic mercury, in a finely divided state, is black in color; therefore, a biack point proves the presence of HgsCls. 122 Analysis of Group I Cations. The analysis of this group is rela- tively simple. Three principal steps make up the procedures. First, Anaxysis or Group I Cations a eeceen ceaepines ‘snalysed (1) ina 10-ml teat tube and add 4 drope of 3 F | centrifuge. Tes fx cmasitecess ol opxcohatin 7 adding another drop of 3 F HC-2| to the upernatant liquid. ¢ Centrifuge/and remove centrifugate with a dropping tube. Thia centrifuge ia saved for 11-V. @ Precipitate remaining in the test = tube ia washed with 10 drope of eold water coataining 1 drop of 8 HCl. (8) Discard ‘wash water, ima Procedure’. Separation of Lead Chloride. White precipitate obtained in Procedure 1 may be Pol, AgCL, and HgsCis, Add 6-7 drupe of water and heat, with stirring: for 3min in water bath. ‘Contigo quickly Qos Toms eters a | while keeping mixture hot in « steam bath, Residue may contain AgCland Hg:Ch. Treat with 10 drops of @F amnoni ts choroughly, and cents (8) A blackening of the residue indieates the presenas of the mercurous ion. Contrifugate ‘Residue may contain mercury. (7) Wash ‘with10 drops of water and discard wash- ing Dissolve precipitate in 2 drops of firma presence of LEAD ION, | tic tate lead,. @uour 1 cations 187 the greup is precipitated with dilute HCI as insoluble chlorides, and the ‘perulting: wasbed with cold water to remove other cation & proups. Secohdly, lead chloride is removed from the precipitate by leaching with hot water. The third step involves the separation of AgCl from Hg:Ch with ammonia water. Details of these procedures are given tn the scheme‘ anslysia for Group I cations. ie ia) ; % Norse ox ram Axacram or Gnour I Cartons 1, Themlution to beanalysed may contain a white precipitate, Buch « precipitate ‘ndioa tn athe tha prevnce ofthe ehiorides of Group I eatin, or the oxychlorides of antimony and blemuth. The oxychlorides of antimony and bismuth have precipi- am to prot od soy be diferentNVR To the ebTorides of Group T by ‘their solubility! in concentrated HG. (Remove ¥ drops of the solution containing soms of tbs precipliate and'add I drop of concentrated HCl. The axychlorides of F antimony and biamuth will dissolve, whereas the chlorides of Group I cations will not.) ‘This reaction is reversible, and the preeence of the oxychloride precipitate in dependent ‘spon » low eonsentration of hydronium fons, BIQCL + 2H,0* = BI + Ct + 3H.0 pectin 2. A aligeremess.cf H.C not only causes a more:complete precipitation of the iblorides of Gionip I-due to common-ion effect, but thin excess also preventa the BIOG aid BLOCL ss Indicated in the above equation. However, a large concentration of HIG or chloride ions ia to be avoided, since the chloride ion in high tion ingrameen the solubilities of the precipitated chlorides through the forma- a AgCl + 20h = AgCle- oe I PbCh + 20> = PRA, end sles may sienlve syoeiae durin the washing process; conse- tamale ry so_that the solubility of lead chloride & 11 the eragnonional solution 4 lettin contact with the precipitate of Fa as apprecabla length of tne, the soluble silver eomplex ion maestros 2g + 2dg(NH,).* = Hew + 2Ag + ANE sredponcaratin of Ay may.not so the una tnt for the sliver fon, b of the solution with tus paper. The solution must ba noid ‘even tough silver ious be present, 20 aa sen Preent,the, Jet fom the ammonia treatment musk bn black or greatly di of colloidal mereury. rr + Bg + NES +>