Dissolve Acidic/neutral sulfide basic sulfide sulfoacid salt Acidic/neutral sulfide base oxysalt+ sulfoacid salt As2S3+3Na2S→2 NasAs3 AS2S3+6OH'-AsO3 +AsS3+3H20 As2Ss+ 3Na2S-2Na3ASS4 4AS2S5+240H3AsO4+5AsS4 +12H,O 第11页 2006-02-22
第 11 页 2006-02-22 11 Bi2S3 – – Dissolve – – Acidic/neutral sulfide + basic sulfide → sulfoacid salt Acidic/neutral sulfide + base → oxysalt + sulfoacid salt As2S3 + 3Na2S →2Na3AsS3 As2S3+6OH- →AsO3 3-+AsS3 3-+3H2O As2S5 + 3Na2S →2Na3AsS4 4As2S5+24OH- →3AsO4 3-+5AsS4 3-+12H2O
Chapter Two Oxygen Family ( GroupⅥ) Central Contents 1. Know the general properties of group VI 2. Understand the structure of ozone and formation of i bond 3. Understand the structure and properties of H2O 4. Know well the properties of H2S, MSy 5. Understand the properties of the oxyacids of sulfur(H2S04, H2S2O3, H2S2O7, H2S2O8)and their 6. Know how to identify $, SO3, S203 and SO4 Section One General Properties Sulfur Selenium tellurium Polonium Element (O) (Te) (Po) Atomic number 8 16 34 52 84 Valence shell electron 32p4|3 configuration Atomic radius/pm 66 117 137 153 0,-2,0,+2 -2,0,+2 Oxidation number 1-2.0 +4+6 M6+ 221 lonic radius/pm M 56 67 First ionization energy 1314 1000 869 812 I,/kJ-mol- Electronic affinity 200.4 -190.2 -173.7 EAJkJ mor Electronegativity 3.5 2.5 2.4 2.0 第12页 2006-02-22
第 12 页 2006-02-22 12 Chapter Two Oxygen Family (Group Ⅵ) Central Contents: 1. Know the general properties of group Ⅵ 2. Understand the structure of ozone and formation of π bond 3. Understand the structure and properties of H2O2 4. Know well the properties of H2S, MxSy 5. Understand the properties of the oxyacids of sulfur (H2SO4, H2S2O3, H2S2O7, H2S2O8) and their salts 6. Know how to identify S2-, SO3 2-, S2O3 2- and SO4 2- Section One General Properties Element Oxygen (O) Sulfur (S) Selenium (Se) Tellurium (Te) Polonium (Po) Atomic number 8 16 34 52 84 Valence shell electron configuration 2s2 2p4 3s2 3p4 4s2 4p4 5s2 5p4 6s2 6p4 Atomic radius/pm 66 104 117 137 153 Oxidation number -1,-2,0 -2,0, +4,+6 -2,0,+2, +4,+6 -2,0,+2, +4,+6 - M6+ 140 184 198 221 - Ionic radius/pm M2- - 29 42 56 67 First ionization energy I1/kJ·mol-1 1314 1000 941 869 812 Electronic affinity EA1/kJ·mol-1 -141 -200.4 -195 -190.2 -173.7 Electronegativity 3.5 2.5 2.4 2.1 2.0
Oxidation number Type of compounds Examples Normal oxides, oxyacids, oxysalts Na2O, Cao, H2O Peroxides Na2O2, BaO, H2O2 -1/2 Hyperoxide KO 1/3 Ozonides KO For the following oxides, determine the type PbO2, BaO,, SnO,, Na2O, KO,, Na2O2 The properties of peroxides and hyperoxide 1. React with water or acid Na,O 2H,o=2NaoH +H,O Na2O2+H2SO4= Na2 SO4+ H2O 2KO2+2H20=2KOH H2O2+O2t 2KO2+H2so4=K2SO4+ H2O2+ O2t 2. React with carbon dioxide 2Na202+ 2CO2=2Na2CO3 +O21 2BaO2+ 2CO2=2BaCO3+ O2t 4KO2+ 2CO2=2K2CO3 3021 Section Two Oxygen, and hydrogen peroxide 1. Ozone: O3 1) Formation: bond 2) Structure 2. H2O2(hydrogen peroxide 1)Structure 2)Properties SPure hydrogen peroxide is a colorless liquid hydrogen peroxide molecules will associate if they exist in liquid state or solid state because of hydrogen bonds; hydrogen peroxide can dissolve in water in any proportion 第13页 2006-02-22
第 13 页 2006-02-22 13 Oxidation number Type of compounds Examples -2 Normal oxides, oxyacids, oxysalts Na2O, CaO, H2O -1 Peroxides Na2O2, BaO2, H2O2 -1/2 Hyperoxides KO2 -1/3 Ozonides KO3 0 O2, O3 For the following oxides, determine the type: PbO2, BaO2, SnO2, Na2O, KO2, Na2O2 The properties of peroxides and hyperoxides: 1. React with water or acid: Na2O2 + 2H2O = 2NaOH + H2O2 Na2O2 + H2SO4 = Na2SO4 + H2O2 2KO2 + 2H2O = 2KOH + H2O2 + O2↑ 2KO2 + H2SO4 = K2SO4 + H2O2 + O2↑ 2. React with carbon dioxide 2Na2O2 + 2CO2 = 2Na2CO3 + O2↑ 2BaO2 + 2CO2 = 2BaCO3 + O2↑ 4KO2 + 2CO2 = 2K2CO3 + 3O2↑ Section Two Oxygen, and hydrogen peroxide 1. Ozone :O3 1) Formation: bond 2) Structure 2. H2O2 (hydrogen peroxide): 1) Structure 2) Properties ○ 1Pure hydrogen peroxide is a colorless liquid; hydrogen peroxide molecules will associate if they exist in liquid state or solid state because of hydrogen bonds; hydrogen peroxide can dissolve in water in any proportion
3 Instability: 2H,,=2H20+0 EAO20695H2O2176H2O EB°O20076HO2+0867OH left Disproportionation reaction Factors that affect decomposition of H2O2 Light or heat A Acid or base(In basic medium, the disproportionation reaction will be fast A Impurity: some ions of heavy metals: Mn2, Fe, Crt, Cu2* or their compounds will accelerate decomposition 3 Oxidizing /reducing properties A Oxidizing properties 2O2+2I+2H=l2+2H2O PbS+4 H202=PbSO4+4H2O 2Cr(OH)4+3H2O2 +20H=2CrO4+8H2O 2 Reducing properties 2MnO4+5H2O2+6H=2Mn+5021+8H2O Cl+ H202=2HCI+O 5H2O2+2HIO3=12+502↑+6H2O 5H2O2+12=2HIO3+4H2O Section Three Sulfur and main compounds of sulfur Oxidation number Type of compounds Example Sulfides, sulfoacid and the salts Na2S, AS2S3, Na2SnS3 Polysulfide Na2s? Simple substanc 第14页 2006-02-22
第 14 页 2006-02-22 14 ○ 2 Instability: 2H2O2=2H2O+O2 EA θ O2 0.695 H2O2 1.76 H2O EB θ O2 -0.076 HO2 - +0.867 OHEθ right>Eθ left →Disproportionation reaction Factors that affect decomposition of H2O2: △1 Light or heat △2 Acid or base (In basic medium, the disproportionation reaction will be fast) △3 Impurity: some ions of heavy metals: Mn2+, Fe3+, Cr3+, Cu2+ or their compounds will accelerate decomposition ○ 3 Oxidizing /reducing properties △1 Oxidizing properties H2O2 + 2I- + 2H+ = I2 + 2H2O PbS + 4 H2O2 = PbSO4 + 4H2O 2Cr(OH)4 - +3H2O2 +2OH- =2CrO4 2-+8H2O △2 Reducing properties 2MnO4 - +5H2O2+6H+ =2Mn2++5O2↑+8H2O Cl2 + H2O2 = 2HCl + O2 5H2O2 + 2HIO3 = I2 + 5O2↑ + 6H2O 5H2O2 + I2 = 2HIO3 + 4H2O ○ 4 Weak acid Section Three Sulfur and main compounds of sulfur Oxidation number Type of compounds Examples -2 Sulfides, sulfoacids and the salts Na2S, As2S3, Na2SnS3 -1 Polysulfide Na2S2 0 Simple substance S8
+2 Thiosulfuric acid Na2S,O +2.5 Tetrathionic acid NasAo Sulfurous acid Na2SO3, SO2 Disulfuric acid. sulfuric acid SO3, Na2S2O7 +6 Persulfuric acid H,S,O8 1. Hydrogen sulfide 1)Colorless gas, stinky poisonous gas CH3CSNH2+2H20=CH3 Coo +NH4 +H2St CH3CSNH220H=CH3 CO0+NH4 +S 2)Weak acid 3)Reducing properties 2H2S+O2=2S↓+2H2O 2H2S+3O2=2SO2↑+2H2O 2Fe3+H2S=2Fe+S↓+2H H2S+I2=2HI+S↓ H2S+Cl+ 4H20= H2SO4+ 8HCI 5H2S+8MnO4+24H=8Mn++ 5H2SO4+12 H2O 2. Sulfides 1) Solubil Acid salt: dissolve Normal salt s2:s2-+HO→HS+OH 3 A1 S3, Cr2S3 Complete hydrolysis) Al2S3+6H2O=2AlOH)3↓+3H2S↑ Cr2S3+6H2O=2Cr(OH)3↓+3H2S↑ Dissolve Insoluble. but dissolve in following solutions hydrolysis 第15页 2006-02-22
第 15 页 2006-02-22 15 +2 Thiosulfuric acid Na2S2O3 +2.5 Tetrathionic acid Na2S4O6 +4 Sulfurous acid Na2SO3, SO2 +6 Disulfuric acid, sulfuric acid SO3, Na2S2O7 +6 Persulfuric acid H2S2O8 1. Hydrogen sulfide 1) Colorless gas, stinky poisonous gas CH3CSNH2+2H2O=CH3COO- +NH4 + +H2S↑ CH3CSNH2+2OH- =CH3COO- +NH4 + +S2- 2) Weak acid 3) Reducing properties 2H2S + O2 = 2S↓ + 2H2O 2H2S + 3O2 = 2SO2↑ + 2H2O 2Fe3+ + H2S = 2Fe2+ + S↓ + 2H+ H2S + I2 = 2HI + S↓ H2S + Cl2 + 4H2O = H2SO4 + 8HCl 5H2S+8MnO4 - +24H+ =8Mn2++ 5H2SO4+12 H2O 2. Sulfides 1) Solubility: ○ 1 Acid salt: dissolve ○ 2 Normal salt 2) Hydrolysis: ○ 1 S2-: S2- + H2O ↔ HS- + OH- ○ 2 Al2S3, Cr2S3 (Complete hydrolysis) Al2S3 + 6H2O = 2Al(OH)3↓ + 3H2S↑ Cr2S3 + 6H2O = 2Cr(OH)3↓ + 3H2S↑ Dissolve Insoluble, but dissolve in following solutions Hydrolysis