Chapter 6: Oxidation-Reduction Reactions Chemistry: The Molecular Nature of Matter, 6E Jespersen/Brady/Hyslop Oxidation-Reduction Reactions Electron transfer reactions Electrons transferred from one substance to another Originally only combustion of fuels or reactions of metal with oxygen Important class of chemical reactions that occur in all areas of chemistry & biology Also called redox reactions Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 2 Oxidation–Reduction Reactions Involves 2 processes: Oxidation = Loss of Electrons (LEO) Na Na+ + e Oxidation Half-Reaction Reduction = Gain of electrons (GER) Cl2 + 2e 2Cl Reduction Half-Reaction Net reaction: 2Na + Cl2 2Na+ + 2Cl Oxidation & reduction always occur together Can't have one without the other Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 3 Oxidation Reduction Reaction Oxidizing Agent Substance that accepts e's Accepts e's from another substance Substance that is reduced Cl2 + 2e 2Cl– Reducing Agent Substance that donates e's Releases e's to another substance Substance that is oxidized Na Na+ + e– Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 4 Redox Reactions Very common Batteries—car, flashlight, cell phone, computer Metabolism of food Combustion Chlorine Bleach Dilute NaOCl solution Cleans through redox reaction Oxidizing agent Destroys stains by oxidizing them Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 5 Redox Reactions Ex. Fireworks displays Net: 2Mg + O2 2MgO Oxidation: Mg Mg2+ + 2e Loses electrons = Oxidized Reducing agent Reduction: O2 + 4e 2O2 Gains electrons = Reduced Oxidizing agent Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 6 Your Turn! Which species functions as the oxidizing agent in the following oxidation-reduction reaction? Zn(s) + Pt2+(aq) Pt(s) + Zn2+(aq) A. Pt(s) B. Zn2+(aq) C. Pt2+(aq) D. Zn(s) E. None of these, as this is not a redox reaction. Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 7 Guidelines For Redox Reactions Oxidation & reduction always occur simultaneously Total number of electrons lost by one substance = total number of electrons gained by second substance For a redox reaction to occur, something must accept electrons that are lost by another substance Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 8 Oxidation Numbers Bookkeeping Method Way to keep track of electrons Not all redox reactions contain O2 & give ions Covalent molecules & ions often involved Ex. CH4, SO2, MnO4–, etc. Defined by set of rules How to divide up shared electrons in compounds with covalent bonds Change in oxidation number of element during reaction indicates redox reaction has occurred Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 9 Hierarchy of Rules for Assigning Oxidation Numbers 1. Oxidation numbers must add up to charge on molecule, formula unit or ion. 2. Atoms of free elements have oxidation numbers of zero. 3. Metals in Groups 1A, 2A, and Al have +1, +2, and +3 oxidation numbers, respectively. 4. H & F in compounds have +1 & –1 oxidation numbers, respectively. 5. Oxygen has –2 oxidation number. 6. Group 7A elements have –1 oxidation number. Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 10 Hierarchy of Rules for Assigning Oxidation Numbers 7. Group 6A elements have –2 oxidation number. 8. Group 5A elements have –3 oxidation number. 9. When there is a conflict between 2 of these rules or ambiguity in assigning an oxidation number, apply rule with lower oxidation number & ignore conflicting rule. Oxidation State Used interchangeably with oxidation number Indicates charge on monatomic ions Iron (III) means +3 oxidation state of Fe or Fe3+ Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 11 Ex. Assigning Oxidation Number 1. Li2O Li (2 atoms) × (+1) = +2 (Rule 3) O (1 atom) × (–2) = –2 (Rule 5) sum = 0 (Rule 1) +2 –2 = 0 so the charges are balanced to zero 2. CO2 C (1 atom) × (x) = x O (2 atoms) × (–2) = –4 sum = 0 x 4 = 0 or x = +4 (Rule 5) (Rule 1) C is in +4 oxidation state Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 12 Learning Check Assign oxidation numbers to all atoms: Ex. ClO4 O (4 atoms) × (–2) = –8 Cl (1 atom) × (–1) = –1 (molecular ion) sum ≠ –1 (violates Rule 1) Rule 5 for O comes before Rule 6 for halogens O (4 atoms) × (–2) = –8 Cl (1 atom) × (x) = x sum = –1 (Rule 1) –8 + x = –1 or x = 8 –1 So x = +7; Cl is oxidation state +7 Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 13 Learning Check Assign Oxidation States To All Atoms: MgCr2O7 Mg =+2; O = –2; and Cr = x (unknown) +2 + 2x + {7 × (–2)} = 0 2x – 12 = 0 x = +3 Cr is oxidation # of +3 KMnO4 K =+1; O = – 2; so Mn = x +1 + x + {4 × (–2)} = 0 x–7=0 x = +7 Mn is oxidation # of +7 Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 14 Your Turn! What is the oxidation number of each atom in H3PO4? A. H = –1; P = +5; O = –2 B. H = 0; P = +3; O = –2 C. H = +1; P = +7; O = –2 D. H = +1; P = +1; O = –1 E. H = +1; P = +5; O = –2 Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 15 Redefine Oxidation-Reduction in Terms of Oxidation Number A redox reaction occurs when there is a change in oxidation number. Oxidation Increase in oxidation number e loss Reduction Decrease in oxidation number e gain Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 16 Using Oxidation Numbers to Recognize Redox Reactions Sometimes literal electron transfer: decrease reduction increase oxidation +2 Cu 2+ 0 + Zn +2 Zn 2+ 0 + Cu Cu: oxidation number decreases by 2 reduction Zn: oxidation number increases by 2 oxidation Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 17 Using Oxidation Numbers to Recognize Redox Reactions Sometimes electron transferred in "formal" O: decrease reduction sense. C: increase -4 +1 0 oxidation CH4 + 2O2 +4 -2 +1 -2 CO2 + 2H2O O: oxidation number decreases by 2 reduction C: oxidation number increases by 8 oxidation Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 18 Ion Electron Method Way to balance redox equations Must balance both mass & charge Write skeleton equation Only ions & molecules involved in reaction Break into 2 half-reactions Oxidation Reduction Balance each half-reaction separately Recombine to get balanced net ionic equation Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 19 Balancing Redox Reactions Some Redox reactions are simple: Ex. 1 Cu2+(aq) + Zn(s) Cu(s) + Zn2+(aq) Break into half-reactions Zn(s) Zn2+(aq) + 2e oxidation LEO Reducing agent Cu2+(aq) + 2e Cu(s) reduction GER Oxidizing agent Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 20 Example 1 Zn(s) Zn2+(aq) + 2e Cu2+(aq) + 2e Cu(s) oxidation reduction Each half-reaction is balanced for atoms Same # atoms of each type on each side Each half-reaction is balanced for charge Same sum of charges on each side Add both equations algebraically, canceling e’s NEVER have e's in net ionic equation Cu2+(aq) + Zn(s) Cu(s) + Zn2+(aq) Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 21 Balancing Redox Equations in Aqueous Solutions Many redox reactions in aqueous solution involve H2O and H+ or OH Balancing the equation cannot be done by inspection. Need method to balance equation correctly Start with acidic solution then work to basic conditions Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 22 Redox in Aqueous Solution Ex. 2 Mix solutions of K2Cr2O7 & FeSO4 Dichromate ion, Cr2O72–, oxidizes Fe2+ to Fe3+ Cr2O72– is reduced to form Cr3+ Acidity of mixture decreases as H+ reacts with oxygen to form water Skeletal Eqn. Cr2O72– + Fe2+ Cr3+ + Fe3+ Ox. # Cr = +6 Jespersen/Brady/Hyslop Fe = +2 Cr = +3 Chemistry: The Molecular Nature of Matter, 6E Fe = +3 23 Ion-Electron Method – Acidic Solution 1. Divide equation into 2 half-reactions 2. Balance atoms other than H & O 3. Balance O by adding H2O to side that needs O 4. Balance H by adding H+ to side that needs H 5. Balance net charge by adding e– 6. Make e– gain equal e– loss; then add halfreactions 7. Cancel anything that is the same on both sides Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 24 Ion Electron Method Ex. 2 Balance in Acidic Solution Cr2O72– + Fe2+ Cr3+ + Fe3+ 1. Break into half-reactions Cr2O72 Cr3+ Fe2+ Fe3+ 2. Balance atoms other than H & O Cr2O72 2Cr3+ Put in 2 coefficient to balance Cr Fe2+ Fe3+ Fe already balanced Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 25 Ex. 2 Ion-Electron Method in Acid 3. Balance O by adding H2O to the side that needs O. Cr2O72 2Cr3+ + 7 H2O Right side has 7 O atoms Left side has none Add 7 H2O to left side Fe2+ Fe3+ No O to balance Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 26 Ex. 2 Ion-Electron Method in Acid 4. Balance H by adding H+ to side that needs H 14H+ + Cr2O72 2Cr3+ + 7H2O Left side has 14 H atoms Right side has none Add 14 H+ to right side Fe2+ Fe3+ No H to balance Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 27 Ex. 2 Ion-Electron Method in Acid 5. Balance net charge by adding electrons. 6e + 14H+ + Cr2O72 2Cr3+ + 7H2O Net Charge = 14(+1) (–2) = 12 Net Charge = 2(+3)+7(0) = 6 6 electrons must be added to reactant side Fe2+ Fe3+ + e 1 electron must be added to product side Now both half-reactions balanced for mass & charge Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 28 Ex. 2 Ion-Electron Method in Acid 6. Make e– gain equal e– loss; then add half- reactions 6e + 14H+ + Cr2O72– 2Cr3+ + 7H2O 6[ Fe2+ Fe3+ + e ] 3+ + 2Cr3+ 6e + 6Fe2+ 6Fe + 2 + 14H + Cr2O7 + 7H2O + 6e 7. Cancel anything that's the same on both sides 6Fe2+ + 14H+ + Cr2O72 Jespersen/Brady/Hyslop 6Fe3+ + 2Cr3+ + 7H2O Chemistry: The Molecular Nature of Matter, 6E 29 Ion-Electron in Basic Solution The simplest way to balance an equation in basic solution Use steps 1-7 above, then 8. Add the same number of OH– to both sides of the equation as there are H+. 9. Combine H+ & OH– to form H2O 10. Cancel any H2O that you can from both sides Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 30 Ex.2 Ion-Electron Method in Base Returning to our example of Cr2O72 & Fe2+ 8. Add to both sides of equation the same number of OH– as there are H+. 6Fe2++ 14H+ 6Fe3+ + 2Cr3+ + 7H2O + 14 OH– + Cr2O72 + 14 OH– 9. Combine H+ and OH– to form H2O. 7 2+ 6Fe + 14H2O 6Fe3+ + 2Cr3+ + Cr2O72 + 7H2O + 14OH 10. Cancel any H2O that you can 6Fe2+ + 7H2O 6Fe3+ + 2Cr3+ + Cr2O72 + 14OH Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 31 Your Turn! Which of the following is a correctly balanced reduction half-reaction? A. Fe3+ + e– Fe° B. 2Fe + 6HNO3 2Fe(NO3)3 + 3H2 C. Mn2+ + 4H2O MnO4– + 8H+ + 5e– D. 2O2– O2 + 4e– E. Mg2+ + 2e– Mg° Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 32 Ex. 3 Ion-Electron Method Balance the following equation in basic solution: MnO4– + HSO3– Mn2+ + SO42 1. Break it into half-reactions MnO4– Mn2+ HSO3– SO42– 2. Balance atoms other than H & O MnO4 Mn2+ Balanced for Mn HSO3 SO42 Balanced for S Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 33 Ex. 3 Ion-Electron Method 3. Add H2O to balance O MnO4 Mn2+ + 4H2O H2O + HSO3 SO42 4. Add H+ to balance H + 8H + MnO4 Mn2+ + 4H2O H2O + HSO3 SO42+ 3H+ Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 34 Ex. 3 Ion-Electron Method 5. Balance net charge by adding e–. 5e– + 8H+ + MnO4 Mn2+ + 4H2O 8(+1) + (–1) = +7 +2 + 0 = +2 Add 5 e– to reactant side H2O + HSO3 SO42 + 3H+ + 2 e– 0 + (–1) = –1 –2 + 3(+1) = +1 Add 2 e– to product side Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 35 Ex. 3 Ion-Electron Method 6. Make e– gain equal e– loss 2[5e– + 8H+ + MnO4 Mn2+ + 4H2O ] 5[H2O + HSO3 SO42 + 3H+ + 2e– ] Must multiply Mn half-reaction by 2 Must multiply S half-reaction by 5 Now have 10 e– on each side Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 36 Ex. 3 Ion-Electron Method 6. Then add the two half-reactions 10e– + 16H+ + 2MnO4 2Mn2+ + 8H2O 5H2O + 5HSO3 5SO42 + 15H+ + 10e– 1 3 + 2+ + 16H + 2MnO4 2Mn + 8H2O + + 5H2O + 5HSO3 5SO42 + 15H+ + 10e 10e– 7. Cancel anything that is the same on both sides. H+ + 2MnO4 + 5HSO3 2Mn2+ + 3H2O + 5SO42 Balanced in acid. Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 37 Ex.3 Ion-Electron Method in Base 8. Add same number of OH– to both sides of equation as there are H+ H+ + 2MnO4 2Mn2+ + 3H2O – + 5SO42 + OH– + OH + 5HSO3 9. Combine H+ and OH– to form H2O H2O + 2MnO4 + 5HSO3 2 + 3H2O + 5SO42 + OH 10. Cancel any H2O that you can 2MnO4 + 5HSO3 2Mn2+ + 2H2O + OH + 5SO42 Jespersen/Brady/Hyslop 2Mn2+ Chemistry: The Molecular Nature of Matter, 6E 38 Your Turn! Balance each equation in Acid & Base using the Ion Electron Method. MnO4– + C2O42– MnO2 + CO32– Acid: 2MnO4– + 3C2O42– + 2H2O 2MnO2 + 4H+ + 6CO32– Base: 2MnO4– + 3C2O42– + 4OH– 2MnO2 + 2H2O + 6CO32– ClO– + VO3– ClO3– + V(OH)3 Acid: ClO– + 2H2O + 2VO3– + 2H+ ClO3–+ 2V(OH)3 Base: ClO– + 4H2O + 2VO3– ClO3–+ 2V(OH)3 + 2OH– Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 39 Acids as Oxidizing Agents Metals often react with acid Form metal ions & Molecular hydrogen gas Molecular Equation Zn(s) + 2HCl(aq) H2(g) + ZnCl2(aq) Net Ionic Equation Zn(s) + 2H+(aq) H2(g) + Zn2+(aq) Jespersen/Brady/Hyslop M oxidized H+ reduced H+ oxidizing reagent Zn reducing reagent Chemistry: The Molecular Nature of Matter, 6E 40 Oxidation of Metals by Acids Ease of oxidation process depends on metal Metals that react with HCl or H2SO4 Easily oxidized by H+ More active than hydrogen (H2) Ex. Mg, Zn, alkali metals Mg(s) + 2H+(aq) Mg2+(aq) + H2(g) 2Na(s) + 2H+(aq) 2Na+(aq) + H2(g) Metals that don’t react with HCl or H2SO4 Not oxidized by H+ Less active than H2 Ex. Cu, Pt Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 41 Anion Determines Oxidizing Power Acids are divided into 2 classes: 1.Nonoxidizing Acids Anion is weaker oxidizing agent than H3O+ Only redox reaction is 2H+ + 2 e– H2 or 2H3O+ + 2 e– H2 + 2H2O HCl(aq), HBr(aq), HI(aq) H3PO4(aq) Cold, dilute H2SO4(aq) Most organic acids (e.g., HC2H3O2) Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 42 2. Oxidizing Acids Anion is stronger oxidizing agent than H3O+ Used to react metals that are less active than H2 No H2 gas formed HNO3(aq) Concentrated Dilute Very dilute, with strong reducing agent H2SO4(aq) Hot, conc’d, with strong reducing agent Hot, concentrated Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 43 Nitrate Ion as Oxidizing Agent A. Concentrated HNO3 Ex. NO3– more powerful oxidizing agent than H+ NO2 is product Partial reduction of N (+5 to +4) NO3–(aq) + 2H+(aq) + e– NO2(g) + H2O oxidation reduction 0 +5 +2 +4 Cu(s) + 2NO3–(aq) + 4H+(aq) Cu2+(aq) + 2NO2(g) + 2H2O Reducing Oxidizing agent agent Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 44 Nitrate Ion as Oxidizing Agent B. Dilute HNO3 NO3– is more powerful oxidizing agent than H+ NO is product Partial reduction of N (+5 to +2) NO3–(aq) + 4H+(aq) + 3e– NO(g) + 2H2O Used to react metals that are less active than H2 Ex. Reaction of copper with dilute nitric acid 3Cu(s) + 8HNO3(dil, aq) 3Cu(NO3)2(aq) + 2NO(g) + 4H2O Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 45 Reactions of Sulfuric Acid A. Hot, Concentrated H2SO4 Becomes potent oxidizer SO2 is product Partial reduction of S (+6 to +4) SO42– + 4H+ + 2e– SO2(g) + 2H2O Ex. Cu + 2H2SO4(hot, conc.) CuSO4 + SO2 + 2H2O B. Hot, conc’d, with strong reducing agent H2S is product Complete reduction of S (+6 to –2) SO42– + 10H+ + 8e– H2S(g) + 4H2O Ex. 4Zn + 5H2SO4(hot, conc.) 4ZnSO4 + H2S + 4H2O Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 46 Your Turn! Which of the following statements about oxidizing acids is false? A. H2SO4 can behave as either an oxidizing or nonoxidizing acid, depending on the solution conditions. B. Oxidizing acids can oxidize metals that are less active than hydrogen. C. The anions of oxidizing acids are reduced in their reactions with metals. D. Most strong acids are oxidizing acids. E. Oxidizing acids are acids whose anions are stronger oxidizing agents than H+. Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 47 Redox Reactions of Metals Acids reacting with metal Special case of more general phenomena Single Replacement Reaction Reaction where one element replaces another A + BC → AC + B 1.Metal A can replace metal B If A is more active metal, or 2.Nonmetal A can replace nonmetal C If A is more active than C Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 48 Single Replacement Reaction Left = Zn(s) + CuSO4(aq) Center = Cu2+(aq) reduced to Cu(s); Zn(s) oxidized to Zn2+(aq) Right = Cu(s) plated out on Zn bar Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 49 Single Replacement Reaction Zn2+ ions take place of Cu2+ ions in solution Cu atoms take place of Zn atoms in solid Cu2+ oxidizes Zn° to Zn2+ Zn° reduces Cu2+ to Cu° More active Zn° replaces less active Cu2+ Zn° is easier to oxidize! Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 50 Activity Series of Metals Cu less active, can't replace Zn2+ Can't reduce Zn2+ Cu(s) + Zn2+(aq) No reaction General phenomenon Element that is more easily oxidized will displace one that is less easily oxidized from its compounds Activity Series (Table 6.3) Metals at bottom more easily oxidized (more active) than those at top This means that given element will be displaced from its compounds by any metal below it in table Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 51 How Activity Series Generated 2H+(aq) + Sr(s) Sr2+(aq) + H2(g) H+ oxidizes Sro to Sr2+ Sro reduces H+ to H2 More active Sro replaces less active H+ Sro is easier to oxidize! H2 (g) + Sr2+(aq) NO REACTION! Why? H2 less active, can't replace Sr2+ Can't reduce Sr2+ Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 52 Learning Check: Metal Activity Using the following observations, rank these metals from most reactive to least reactive: Cu(s) + HCl(aq) → no reaction Zn(s) + 2HCl(aq) → ZnCl2(aq) + H2(g) Mg(s) + ZnCl2(aq) → MgCl2(aq) + Zn(s) Mg > Zn > H > Cu Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 53 Table 6.3 Activity Series of Some Metals Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 54 Reactivity Varies by Metal M at very bottom of Table Very strong reducing agents Very easily oxidized Na down to Cs Alkali & alkaline earth metals React with H2O as well as H+ 2Na(s) + 2H2O H2(g) + 2NaOH(aq) Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 55 Reactivity Varies by Metal Ag = no reaction (top of activity series) 2HCl(aq) + Ag(s) 2AgCl(aq) + H2(g) Zn= somewhat reactive (middle of activity series) 2HCl(aq) + Zn(s) ZnCl2(aq) + H2(g) Mg = very reactive (bottom of activity series) 2HCl(aq) + Mg(s) MgCl2(aq) + H2(g) Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 56 Using Activity Series to Predict Reactions If M is below H Can displace H from solutions containing H+ 2H+ H2(g) If M is above H Doesn't react with Nonoxidizing acids HCl, H3PO4, etc. In general Metal below replaces ion above Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 57 Uses of Activity Series Predictive tool for determining outcome of single replacement reactions Given M & M'n+ Look at chart & draw arrow from M to M'n+ Arrow that points up from bottom left to top right will occur Arrow that points down from top left to bottom right will NOT occur Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 58 Learning Check 2Au3+(aq) + 3Ca(s) 2Au(s) + 3Ca2+(aq) rxn occurs Au(s) + Ca2+(aq) NO reaction Sn(s) + Na+(aq) NO reaction Mn(s) + Co2+(aq) Co(s) + Mn2+(aq) rxn occurs Cu(s) + H+(aq) NO reaction Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 59 Your Turn! The activity series of metals is Au < Ag < Cu < Sn < Cd < Zn < Al < Mg < Na < Cs (least active) (most active) Based on this list, which element would undergo reduction most readily? A. Ag B. Al C. Cu D. Cd E. Zn Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 60 Oxygen as an Oxidizing Agent Oxygen Reacts With Many Substances Combustion Rapid reaction of substance with oxygen that gives off both heat and light Hydrocarbons are important fuels Products depend on how much O2 is available 1. Complete Combustion O2 plentiful CO2 & H2O products Ex. CH4(g) + 2 O2(g) CO2(g) + 2 H2O 2 C8H18(g) + 25 O2(g) 16 CO2(g) + 18 H2O Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 61 Oxidation of Organic Compounds 2. Incomplete Combustion Not enough O2 a. Limited O2 supply CO is carbon product 2CH4(g) + 3O2(g) 2CO(g) + 4H2O b. Very limited O2 C(s) is carbon product CH4(g) + O2(g) C(s) + 2H2O Gives tiny black particles Soot—lamp black Component of air pollution Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 62 Oxidation of Organic Compounds 3. Combustion of Organics containing O Still produce CO2 & H2O Need less added O2 C12H22O11(s) + 12 O2(g) 12 CO2(g) + 11 H2O 4. Combustion of Organics containing S Produce SO2 as product 2C4H9SH + 15O2(g) 8CO2(g) + 10H2O + 2SO2(g) SO2 turns into acid rain when mixed with water SO2 oxidized to SO3 SO3 reacts with H2O to form H2SO4 Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 63 B. Reaction of Metals with O2 Corrosion Direct reaction of metals with O2 Many metals corrode or tarnish when exposed to O2 Ex. 2Mg(s) + O2(g) 2MgO(s) 4Al(s) + 3O2(g) 2Al2O3(s) 4Fe(s) + 3O2(g) 2Fe2O3(s) 4Ag(s) + O2(g) 2Ag2O(s) Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 64 C. Reaction of Nonmetals with O2 Many nonmetals react directly with O2 to form nonmetal oxides Sulfur reacts with O2 Forms SO2 S(s) + O2(g) 2SO2(g) Nitrogen reacts with O2 Forms various oxides NO, NO2, N2O, N2O3, N2O4, and N2O5 Dinitrogen oxide, N2O Laughing gas used by dentists Propellant in canned whipped cream Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 65 Learning Check: Complete Following Reactions Aluminum metal and oxygen gas forms aluminum oxide solid 4Al(s) + 3O2(g) → 2Al2O3(s) Solid sulfur (S8) burns in oxygen gas to make gaseous sulfur trioxide S8(s) + 12O2(g) → 8SO3(g) Copper metal is heated in oxygen to form black copper(II) oxide solid 2Cu(s) + O2(g) → 2CuO(s) Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 66 Your Turn! Which of the following reactions is not a redox reaction? A. Na2S(aq) + MnCl2(aq) 2NaCl(aq) + MnS(s) B. CH4(g) + O2(g) C(s) + 2H2O C. 2Zn(s) + O2(g) 2ZnO(s) D. Cu(s) + 4H+(aq) + 2NO3–(aq) Cu2+(aq) + 2NO2(g) + 2H2O E. Sr(s) + 2H+(aq) Sr2+(aq) + H2(g) Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 67 Stoichiometry in Redox Reactions Like any other stoichiometry problem Balance redox reaction Use stoichiometric coefficients to relate mole of 1 substance to moles of another Types of problems Start with mass or volume of one reactant & find mass or volume of product Perform titrations Have limiting reactant calculations Calculate % yields Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 68 Stoichiometry in Redox Reactions Ex. How many grams of Na2SO3 (126.1 g/mol) are needed to completely react with 12.4 g of K2Cr2O7 (294.2 g/mol)? 1st need balanced redox equation 8H+(aq) + Cr2O72(aq) + 3SO32(aq) 3SO42(aq) + 2Cr3+(aq) + 4H2O Then do calculations 1. g K2Cr2O7 moles K2Cr2O7 moles Cr2O72(aq) 2. moles Cr2O72(aq) moles 3SO42(aq) 3. moles SO32(aq) moles Na2SO3 g Na2SO3 Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 69 Stoichiometry Example (cont) grams K2Cr2O7 moles K2Cr2O7 moles Cr2O72 (aq) 1 mol K 2 Cr2 O 7 1mol Cr2 O 27 12.4 g K 2 Cr2 O 7 294.2 g K 2 Cr2 O 7 1 mol K 2 Cr2 O 7 0.0421mol Cr2O27 moles Cr2O72 (aq) moles 3SO32 (aq) 0.0421mol Cr2 O 27 3 mol SO 23 1 mol Cr2 O 27 0.126 mol SO23 moles SO32 (aq) moles Na2SO3 g Na2SO3 0.126 mol SO23 1 mol Na2SO3 1 mol SO23 126.1 g Na2SO3 1 mol Na2SO3 15.9 g Na2SO3 Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 70 Redox Titrations Equivalence point reached when # of moles of oxidizing & reducing agents have been mixed in the correct stoichiometric ratio No simple indicators to detect endpoints 3 very useful oxidizing agents that change color 1. KMnO4: Deep purple of MnO4 fades to almost colorless Mn2+ (very pale pink) 2. K2Cr2O7: Bright yellow orange of Cr2O72 changes to pale blue green of Cr3+ 3. IO3 : When reduced to I2(s) in presence of I, forms I3 which forms dark blue complex with starch Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 71 Redox Titration Example I reacts with IO3 in acidic solution to form I2(s). If 12.34 mL of 0.5678M I is needed to titrate 25.00 mL of a solution containing IO3, what is the M of the solution? 1. Write Unbalanced Equation 1 +5 0 I (aq) + IO3 (aq) I2(s) I (aq) is oxidized to I2 IO3(aq) is reduced to I2 Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 72 Redox Titration Example (cont) 2. Balance Equation Note: we are in acidic solution 5 [2I(aq) 2IO3(aq) + 12H+(aq) + 10e 10I(aq) + 2IO3(aq) + 12H+(aq) 2 2 2 I2(s) + 2e ] I2(s) + 6H2O 6I2(s) + 6H2O 2 2 Not done as not lowest whole number coefficients 5I(aq) + IO3(aq) + 6H+(aq) 3I2(s) + 3H2O Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 73 3. Now for the Calculations Calculate mmol of I– titrated 12.34 mL I 0.5678mmol I 7.007mmol I 1 mL I Convert to mmol of IO3– present 1 mmol IO 3 1.401mmol IO3 7.007 mmol I 5 mmol I Convert to M of IO3– solution 1.401mmol IO 3 25.00 mL IO 3 Jespersen/Brady/Hyslop = 0.0561 M IO3– Chemistry: The Molecular Nature of Matter, 6E 74 Ore Analysis A 0.3000 g sample of tin ore was dissolved in acid solution converting all the tin to tin(II). In a titration, 8.08 mL of 0.0500 M KMnO4 was required to oxidize the tin(II) to tin(IV). What was the percentage tin in the original sample? 3Sn2+(aq) + 2MnO4(aq) + 8H+(aq) 3Sn4+(aq) + 2MnO2(s) + 4H2O M of KMnO4 V = mol KMnO4 mol KMnO4 mol Sn/mol KMnO4 = mol Sn2+ mol Sn2+ MM = g Sn2+ in sample %Sn = g Sn/g sample 100 % Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 75 Tin Ore Analysis Continued M of KMnO4 V = mmol KMnO4 0.0500 M KMnO4 8.08 mL = 0.404 mmol KMnO4 mmol KMnO4 mmol MnO4 mmol Sn2+ 1 mmol MnO 4 3 mmol Sn2 0.404 mmol KMnO 4 × × 1 mmol KMnO 4 2 mmol MnO 4 = 0.606 mmol Sn2+ Mol Sn2+ g/mol = g Sn in original sample 0.606 mmol Sn2 1 mmol Sn 1 mmol Sn2 = 0.07194 g Sn 118.7 mg Sn 1g 1 mmol Sn 1000 mg %Sn = g Sn/ g sample 100 % 0.07194 g Sn 100 = 23.97% Sn 0.3000 g ore Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 76 Your Turn! The amount of hydrogen peroxide (H2O2, MM = 34.01 g/mol) in hair bleach was determined by titration with a standard KMnO4 (MM = 158.0 g/mol) solution: 2MnO4–(aq) + 5H2O2(aq) + 6H+(aq) 5O2(g) + 2Mn2+(aq) + 8H2O If 43.2 mL of 0.105 M MnO4– was needed to reach the endpoint, how many grams of H2O2 are in the sample of hair bleach? A. 0.771 g B. 0.386 g C. 0.0771 g D. 386 g E. 154 g 0.105M MnO 4 Jespersen/Brady/Hyslop 5 mol H2 O2 34.01 g H2 O2 43.2 mL 1000 mL/1 L 2 mol MnO 4 1 mol H2 O2 = 0.386 g H2O2 Chemistry: The Molecular Nature of Matter, 6E 77