Selected Reactions of Some Anions

Memorize or familiarize yourself with the solubility rules Use the centrifuge to your advantage Addition of acid and bases are usually used to remove ions identified from a previous test, familiarize yourself with these methods. A. Test for anions that produce volatile products with strong acid Reagent: 6.00M H2SO4 Analytes: S2-, S2O32-, CO32-, C2O42-, PO43-, CrO42- and CH3COOResults: Chemical Reaction Observation 2+ Colorless and odourless gas; effervescence CO3 + 2H CO2 (g) + H2O Burnt rubber-like smell gas with milky yellow ppt S2O32- + 2H+ S(s) + SO2 + H2O Colorless, foul-smelling gas; rotten egg smell S2- + 2H+ H2S (g) Vinegar-like smell CH3COO- + H+ CH3COOH 2CrO42- + 2H+ Cr2O72- + H2O Orange solution PO43- + 3H+ H3PO4 H3PO4 is a colorless and not volatile species; NVR NDS C2O42- + 2H+ H2C2O4 H2C2O4 is a colorless and not volatile species; NVR NDS NOTE: Milky yellow ppt appears to be pale yellow over time Test for Strong Reducing Anions Reagents: 6.00M HCl (to make medium acidic); freshly prepared K3Fe(CN)6 the one that gets reduced and 0.10M FeCl3 Analytes: S2-, S2O32-, C2O42-, CNS-, I- and BrResults: If strong reducing anion is present Reduction Half-Reaction: Fe(CN)62- + e- [Fe(CN)6]4Formation of Prussian blue: 3[Fe(CN)6]4- + 4FeCl3 Fe4[Fe(CN)6]3 + 12ClIf strong reducing anion is absent Brown ppt: [Fe(CN)6]4- + Fe3+ Fe[Fe(CN)6] Oxidation half reaction for strong reducing anions Chemical Reaction Observation Conclusion Prussian blue ppt. present Strong reducing anion S2- S(s) + 2ePrussian blue ppt. present Strong reducing anion 2S2O32- S4O62- + 2ePrussian blue ppt. present Strong reducing anion 2I- I2 + 2eC2O42-, CNS-, BrInsignificant (-) NOTE: Fe3+ may react with CNS-; Fe3+ + CNS- [FeCNS]2+, in this case centrifuge the solution to check if a prussian blue ppt is present from other anions NOTE: I2 is a brown solution when left through time Test for Strong Oxidizing Anions Reagents: saturated MnCl2 and 12.0M HCl (to make the medium acidic) Analytes: SO42-, CH2COO-, CO32-, PO43-, CrO42- and NO3Results: If strong oxidizing anion is present Oxidation half reaction: Mn2+ Mn3+ + eMn3+ then forms a brown chloro complex Reduction half-reactions for strong oxidizing anions Chemical Reaction Observation Conclusion 2CrO42-(yellow) + 2H+ Cr2O72-(orange) + H2O Brown solution Strong oxidizing anion Cr2O72- + 14H+ + 6e- 2Cr3+ + 7H2O NO3- + 2H+ + 2e- NO2- + H2O; Brown solution Strong oxidizing anion NO2- + 2H+ + e- NO + H2O

B.

C.

SO42-, CH3COO-, CO32-, PO43May not be observed in the laboratory D.

Insignificant

(-)

Test for anions that give insoluble Ca2+ and Ba2+ salts D1. Reaction with acidified CaCl2 Reagents: 3.00M HOAc and 0.10M CaCl2 Analytes: S2O32-, SO42-, CO32-, C2O42-, PO43- and CrO42Results: Chemical Reaction Observation White ppt. C2O42- + Ca2+ CaC2O4(s) Notes: *Addition of HOAc and warm bathing prior to the addition of CaCl2 were done to remove the anions that give volatile products, hence there are NVRs for these anions (see A). *solubility of Ca3(PO4)2 is enhanced by the addition of acid (recall Expt. 9) D2. Reaction with acidified BaCl2 Reagents: 3.00M HOAc and 0.10M BaCl2 Analytes: S2O32-, SO42-, CO32-, C2O42-, PO43- and CrO42Results: Chemical Reaction Observation 22+ Yellow ppt CrO4 + Ba BaCrO4 (s) 22+ White ppt SO4 + Ba BaSO4 (s) *Refer to notes on D1 for the rest of the anions tested. *A precipitate for S2O32- may be observed. *There is a difficulty in observing a precipitate because CrO42- becomes Cr2O72- in acidic medium. (Barium chlomate is insoluble while barium dichromate is soluble) D3. Test for anions that did not precipitate on D2 Reagents: solution from D2 + 6.00M NH3 Analytes: solutions containing S2O32-, Co32-, C2O42- and PO43Results: Chemical Reaction Ba3(PO4)2 (s) + 2H+ 3Ba2+ + 2HPO42- (with HOAc) 3Ba2+ + 2HPO42- + 2OH- Ba3(PO4)2 + 2H2O (with NH3) *Precipitates for SO32- and CO32- may be observed.

Observation Colorless solution formation of white ppt.

FOR D4 BaCl2: The yellow colored precipitate would normally overpower the color of the white ppt, when yellow ppt appears and you cant see if there are white ppt use the Ag+ method: Add Ag+ to form AgCr2O4 then remove ppt youll get the remaining ions then precipitate it with BaCl2 E. Test for anions using silver E1. Reaction with acidified AgNO3 Reagents: 3.00M HNO3 and 0.10M AgNO3 Analytes: All anions Results: Chemical Reaction Ag+ + Cl- AgCl(s) Ag+ + I- AgI (s) + Ag + CNS- AgCNS (s)

Ksp 1.8 E-10 1.5 E-16 1.0 E-12

Observation White ppt. Yellow ppt. White ppt

3.3 E-13 Yellow ppt Ag+ + Br- AgBr (s) *Anions that give positive result in A have NVRs in this test *Solubility of silver salts of anions with basic properties is enhanced in an acidic medium (e.g. Ag3PO4 + H+ 3Ag+ + HPO42-) hence their silver precipitates are not observed Color is almost unnoticeable use a confirmatory test for this part E2. Solubility of the precipitates formed in E1 with NH3 Reagents: 3.00 M NH3 Analytes: washed precipitates from E1 Results: Chemical Reaction Keq Observation K * Ksp = f[Ag(NH3)2]+ AgCl AgCl (s) + 2NH3(aq) [Ag(NH3)2]+ + ClWhite ppt. colorless solution 2.86 x 10-3 *Among the silver salts formed in E1, AgCl has the largest Ksp value hence formation of [Ag(NH3)2]+ complex is favored. * Kf[Ag(NH3)2]+ = 1.59 E7 *Krxn with AgI = 2.4E-9; Krxn with AgCNS = 1.59E-5; Krxn with AgBr = 5.56 E-6 E3. Reprecipitation of the precipitate that dissolves in E2 Chemical Reaction [Ag(NH3)2]+(aq) + Cl-(aq) + 2H+ AgCl(s) + 2NH4+(aq) E4. Reaction with neutral AgNO3 Reagents: 0.10M AgNO3 Analytes: all anions Results: Chemical Reaction Cl- + Ag+ AgCl S2- + 2Ag+ Ag2S S2O32- + 2Ag+ Ag2S2O3 CO32- + 2Ag+ Ag2CO3 CrO42- + 2Ag+ Ag2CrO4 C2O42- + 2Ag+ Ag2C2O4 PO43- + 3Ag+ Ag3PO4 CNS- + Ag+ AgCNS Br- + Ag+ AgBr *Salts of the rest of the anions are soluble in water Observation Colorless soln white ppt

Observation White ppt Black ppt White ppt White ppt Red ppt. White ppt. Yellow ppt. White ppt. White ppt.

ATQ 1. List of the anions which belong to each group (Refer to the attached table: summary of results for anions) 2. Explain in the function of a. HOAc in procedures D1 and D2: To remove anions that give positive results in A and those that give Ca2+ salts which are soluble in dilute acid (these are anions that have basic properties). b. NH3 in procedure D3 To neutralize the acidic medium (due to the added 3.0M HOAc in D1), thereby allowing the formation of precipitates of Ca2+ salts that are soluble in dilute acid. c. HNO3 in procedure E1 To remove anions that give positive results in A and those that give Ag+ salts which are soluble in acid (these are anions that have basic properties). d. HNO3 in procedure E3 To neutralize the basic medium hence reformation of AgCl(s) from the ammonium complex becomes possible (see equation in E3).