GROUP II CATIONS As+3, As+5, Sb+3, Sb+5, Sn+2, Cu+2, Hg+2, Pb+2, Cd+2, Bi+3

Ksp values of Group II and Group III cations In systematic analysis of cations, 13 cations are precipitated as their sulfides. Among these cations, 8 of them have lower solubilities in water and they are called as Group II cations while the remaning 5 cations with higher solubility in water are called as Group III cations: Ksp values of Group II and Group III cations Group II Group III Sulfides Ksp HgS 3,0x10–53 ZnS 1,2x10–23 CuS 1,0x10–44 CoS 7,0x10–23 Bi2S3 1,6x10–72 NiS 1,4x10–24 Sb2S3 1x10–30 FeS 3,7x10–19 CdS 3,6x10–29 MnS 1,4x10–15 PbS 3,4x10–28   SnS 1,8x10–28 As2S3 4,4x10–27 When the concentrations of these cations are hold around 0,1 M - 0,01 M and the medium is acidified with 0.3 M acid, Group II cations with lower solubility will be precipitated upon addition of sulfides while Group III cations having higher solubility will stay in the solution. For this reason, adjustment of acidity is important in separation of these two groups.

The equilibrium for hydrogen sulfide: H2S ↔ 2 H+ + S–2 k= [H + ] 2 [ S −2 ] [ H 2 S] = 6,8 x 10–23 In this equilibrium, [H+] = 0.3 M since the acidity of the medium is adjusted to 0.3 M and [H2S]=0.1 M since the highest concentration of it is 0.1 M at 25oC considering the solubility: 0,3 2 [ S −2 ] 0,1 = 6,8 x 10–23 [S–2] = 7,5 x 10–23 Among Group III cations, NiS has the lowest solubility and in our courses the samples are prepared in 0.01 M: Q= [Ni+2] [S–2] = 0,01 x 7,5 x 10–23 = 7,5 x 10–25 7,5 x 10–25 < Ksp (1,4x10-24) Since Q is smaller than Ksp NiS does not precipitate. The other Group III cations have higher Ksp than NiS and all of them stay dissolved. On the other hand Q of Group II cations are higher than Ksp of them in this medium and it means all Group II cations will be precipitated.

Thioacetamide can be used as sulfide source Thioacetamide can be used as sulfide source. Hydrogen sulfide will be produced when thioacetamide solution is heated. For this reason, the test tube containing your sample will be heated in a water bath after addition of required amount of thioacetamide. Since the produced hydrogen sulfide will immediately react with cations in the sample, hazardous effects of hydrogen sulfide such as rotten egg smell will be reduced. In the analysis, the flow chart will be followed. Sulfides of Group II cations have different colors so you may have preliminary information at the beginning of the analysis: Bi2S3,HgS, CuS, PbS = Black As2S3, As2S5 = Yellow CdS = Pale yellow Sb2S3, Sb2S5 = Orange SnS= Deep brown Following you can find the specific reactions of Group II cations when they are alone.

Cu+2 1- The solutions of Cu salts have blue or bluish-green color. Looking the color of your sample you can predict the presence of Cu in your sample. 2- Reaction with K4[Fe(CN)6] (potassium ferrocyanide) : Red-brown precipitates are formed and they are soluble in diluted ammonia 2Cu+2 + [Fe(CN)6] –4 → Cu2[Fe(CN)6] ↓ 3- Reaction with KCN (potassium cyanide): Firstly greenish-yellow Cu(CN)2 ↓ precipitates are formed and upon excess adition of KCN, it will be dissolved by formation of K3[Cu(CN)4] (potassium cyanocuprate)

Cd+2 1- Reaction with H2S: colloidal and yellow colored CdS is formed and it is soluble in HNO3. Cd+2 +H2S → CdS ↓ (sarı) + 2H+ 3CdS + 8H+ + 2NO3– → 3Cd+2 + 3S + 2NO + 4H2O 2- Reaction with KCN: In the beginning, white colored Cd(CN)2 precipitates are formed and upon addition of excess KCN it is dissolved by formation of K2[Cd(CN)4] (potassium tetracyanocadmate(II)) complex. This complex can react with H2S to produce CdS CdSO4 + 2 KCN → Cd(CN)2 + K2 SO4 Cd(CN)2 + 2 KCN → K2[Cd(CN)4] K2[Cd(CN)4] + H2S → CdS ↓ + 2KCN +2HCN Yellow The last reaction is the difference between Cd+2 and Cu+2 , K3[Cu(CN)4] complex does not react with H2S while K2[Cd(CN)4] reacts.

Bi+3 ** Main oxidation states of bismuth are +3, –3, +5. Bi-3 behaves strong reducing agent while Bi+5 is strong oxidizing agent. 1- Reaction with Na2SnO2 (Sodium stannite ): Bismuth is reduced to black colored metallic Bi0 2Bi(OH)3 + 3Na2SnO2 → 2Bi0↓+ 3Na2SnO3 + 3H2O black 2- Reaction with KI: Bi+3 + KI→ BiI3 ↓ black precipitate BiI3 + KI ↔ [BiI4]– Soluble complex

Sn+2 (Tin) The hydrolysis of Sn+2 salts produce white precipitates of Sn(OH)Cl. 1- Luminescence test: The sample is directly used without any pretreatment. In a small beaker, add 5-10 mL of sample. Add one spatula of Zn granules and 4-5 mL of 6 HCl. Fill a test tube with cold tap water and immerse this test tube into the beaker. Then hold the test tube into the reducing zone of a flame. Blue shining (luminescence) indicates the presence of Sn+2 2- Reaction with H2S: Brown SnS precipitates. 3- Tin reduce Bi+3 to black Bi0 in basic medium. Add NaBiO3 (sodium bismuthate) prepared in basic medium.

As+3, As+5 (Arsenic) They both form strong covalent bonds with oxygen in water As+3 : AsO3–3, AsO2– (arsenite) As+5 : AsO4–3 (arsenate) 1-Reaction with AgNO3 yields red-brown colored Ag3AsO4 (silver arsenate). 3Ag+ + AsO4- → Ag3AsO4↓ red-brown

It can produce white colored SbOCl precipitates in water. Sb+3, Sb+5 (Antimony) It can produce white colored SbOCl precipitates in water. 1- Reaction with H2S: Orange Sb2S3 (antimony sulfide) precipitates 2Sb+3 + 3H2S → Sb2S3 ↓ + 6H+ orange 2- Reaction with NaOH: White colored SbOCl precipitates. SbCl3 + NaOH → SbOCl ↓ + HCl + NaCl white

ATTENTION!!! *While working with KCN (For Cu+2 and Cd+2 tests), the medium must be strictly checked with litmus paper for its basicity. If the solution is acidic, then highly toxic HCN gas is evolved. KCN + H+ → HCN (g)