Reactions in Aqueous Solution Chapter 4 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

2 A solution is a homogenous mixture of 2 or more substances The solute is(are) the substance(s) present in the smaller amount(s) The solvent is the substance present in the larger amount SolutionSolventSolute Soft drink (l) Air (g) Soft Solder (s) H2OH2O N2N2 Pb Sugar, CO 2 O 2, Ar, CH 4 Sn aqueous solutions of KMnO 4

3 An electrolyte is a substance that, when dissolved in water, results in a solution that can conduct electricity. A nonelectrolyte is a substance that, when dissolved, results in a solution that does not conduct electricity. nonelectrolyte weak electrolyte strong electrolyte

4 Strong Electrolyte – 100% dissociation NaCl (s) Na + (aq) + Cl - (aq) H2OH2O Weak Electrolyte – not completely dissociated CH 3 COOH CH 3 COO - (aq) + H + (aq) Conduct electricity in solution? Cations (+) and Anions (-)

5 Ionization of acetic acid CH 3 COOH CH 3 COO - (aq) + H + (aq) A reversible reaction. The reaction can occur in both directions. Acetic acid is a weak electrolyte because its ionization in water is incomplete.

6 Hydration is the process in which an ion is surrounded by water molecules arranged in a specific manner.   H2OH2O

7 Dissolution of a Solid in a Liquid

8 Nonelectrolyte does not conduct electricity? No cations (+) and anions (-) in solution C 6 H 12 O 6 (s) C 6 H 12 O 6 (aq) H2OH2O

9 Precipitation Reactions Acid–Base Reactions Oxidation–Reduction Reactions Types of Chemical Reactions

10 Precipitation Reactions Precipitate – insoluble solid that separates from solution molecular equation ionic equation net ionic equation Pb NO Na + + 2I - PbI 2 (s) + 2Na + + 2NO 3 - Na + and NO 3 - are spectator ions PbI 2 Pb(NO 3 ) 2 (aq) + 2NaI (aq) PbI 2 (s) + 2NaNO 3 (aq) precipitate Pb I - PbI 2 (s)

11 Precipitation of Lead Iodide PbI 2 Pb I - PbI 2 (s)

12 Solubility is the maximum amount of solute that will dissolve in a given quantity of solvent at a specific temperature.

Section 4.5 Precipitation Reactions Return to TOC Copyright © Cengage Learning. All rights reserved 13 1.Most nitrate (NO 3  ) salts are soluble. 2.Most alkali metal (group 1A) salts and NH 4 + are soluble. 3.Most Cl , Br , and I  salts are soluble (except Ag +, Pb 2+, Hg 2 2+ ). 4.Most sulfate salts are soluble (except BaSO 4, PbSO 4, Hg 2 SO 4, CaSO 4 ). 5.Most OH  are only slightly soluble (NaOH, KOH are soluble, Ba(OH) 2, Ca(OH) 2 are marginally soluble). 6.Most S 2 , CO 3 2 , CrO 4 2 , PO 4 3   salts are only slightly soluble, except for those containing the cations in Rule 2. Simple Rules for Solubility

Section 4.5 Precipitation Reactions Return to TOC Copyright © Cengage Learning. All rights reserved 14 Concept Check Which of the following ions form compounds with Pb 2+ that are generally soluble in water? a)S 2– b)Cl – c)NO 3 – d)SO 4 2– e)Na +

15 Examples of Insoluble Compounds CdS PbSNi(OH) 2 Al(OH) 3

16 Writing Net Ionic Equations 1.Write the balanced molecular equation. 2.Write the ionic equation showing the strong electrolytes completely dissociated into cations and anions. 3.Cancel the spectator ions on both sides of the ionic equation 4.Check that charges and number of atoms are balanced in the net ionic equation AgNO 3 (aq) + NaCl (aq) AgCl (s) + NaNO 3 (aq) Ag + + NO Na + + Cl - AgCl (s) + Na + + NO 3 - Ag + + Cl - AgCl (s) Write the net ionic equation for the reaction of silver nitrate with sodium chloride.

Section 4.6 Describing Reactions in Solution Return to TOC Copyright © Cengage Learning. All rights reserved 17 Concept Check Write the correct formula equation, complete ionic equation, and net ionic equation for the reaction between cobalt(II) chloride and sodium hydroxide. Formula Equation: CoCl 2 (aq) + 2NaOH(aq)  Co(OH) 2 (s) + 2NaCl(aq) Complete Ionic Equation: Co 2+ (aq) + 2Cl  (aq) + 2Na + (aq) + 2OH  (aq)  Co(OH) 2 (s) + 2Na + (aq) + 2Cl  (aq) Net Ionic Equation: Co 2+ (aq) + 2OH  (aq)  Co(OH) 2 (s)

18 Chemistry In Action: CO 2 (aq) CO 2 (g) Ca 2+ (aq) + 2HCO 3 (aq) CaCO 3 (s) + CO 2 (aq) + H 2 O (l) - An Undesirable Precipitation Reaction

19 Properties of Acids Have a sour taste. Vinegar owes its taste to acetic acid. Citrus fruits contain citric acid. React with certain metals to produce hydrogen gas. React with carbonates and bicarbonates to produce carbon dioxide gas Cause color changes in plant dyes. 2HCl (aq) + Mg (s) MgCl 2 (aq) + H 2 (g) 2HCl (aq) + CaCO 3 (s) CaCl 2 (aq) + CO 2 (g) + H 2 O (l) Aqueous acid solutions conduct electricity.

20 Have a bitter taste. Feel slippery. Many soaps contain bases. Properties of Bases Cause color changes in plant dyes. Aqueous base solutions conduct electricity. Examples:

21 Arrhenius acid is a substance that produces H + (H 3 O + ) in water Arrhenius base is a substance that produces OH - in water

22 Hydronium ion, hydrated proton, H 3 O +

23 A Brønsted acid is a proton donor A Brønsted base is a proton acceptor acidbaseacidbase A Brønsted acid must contain at least one ionizable proton!

24 Monoprotic acids HCl H + + Cl - HNO 3 H + + NO 3 - CH 3 COOH H + + CH 3 COO - Strong electrolyte, strong acid Weak electrolyte, weak acid Diprotic acids H 2 SO 4 H + + HSO 4 - HSO 4 - H + + SO 4 2- Strong electrolyte, strong acid Weak electrolyte, weak acid Triprotic acids H 3 PO 4 H + + H 2 PO 4 - H 2 PO 4 - H + + HPO 4 2- HPO 4 2- H + + PO 4 3- Weak electrolyte, weak acid

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26 Identify each of the following species as a Brønsted acid, base, or both. (a) HI, (b) CH 3 COO -, (c) H 2 PO 4 - HI (aq) H + (aq) + I - (aq)Brønsted acid CH 3 COO - (aq) + H + (aq) CH 3 COOH (aq)Brønsted base H 2 PO 4 - (aq) H + (aq) + HPO 4 2- (aq) H 2 PO 4 - (aq) + H + (aq) H 3 PO 4 (aq) Brønsted acid Brønsted base

27 Neutralization Reaction acid + base salt + water HCl (aq) + NaOH (aq) NaCl (aq) + H 2 O (l ) H + + Cl - + Na + + OH - Na + + Cl - + H 2 O (l ) H + + OH - H 2 O (l )

28 Neutralization Reaction Involving a Weak Electrolyte weak acid + base salt + water HCN (aq) + NaOH (aq) NaCN (aq) + H 2 O HCN + Na + + OH - Na + + CN - + H 2 O HCN + OH - CN - + H 2 O

29 Neutralization Reaction Producing a Gas acid + base salt + water + CO 2 2HCl (aq) + Na 2 CO 3 (aq) 2NaCl (aq) + H 2 O +CO 2 2H + + 2Cl - + 2Na + + CO Na + + 2Cl - + H 2 O + CO 2 2H + + CO 3 2- H 2 O + CO 2

30 Oxidation-Reduction Reactions (electron transfer reactions) 2Mg 2Mg e - O 2 + 4e - 2O 2- Oxidation half-reaction (lose e - ) Reduction half-reaction (gain e - ) 2Mg + O 2 + 4e - 2Mg O e - 2Mg + O 2 2MgO

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32 Zn (s) + CuSO 4 (aq) ZnSO 4 (aq) + Cu (s) Zn is oxidizedZn Zn e - Cu 2+ is reducedCu e - Cu Zn is the reducing agent Cu 2+ is the oxidizing agent Copper wire reacts with silver nitrate to form silver metal. What is the oxidizing agent in the reaction? Cu (s) + 2AgNO 3 (aq) Cu(NO 3 ) 2 (aq) + 2Ag (s) Cu Cu e - Ag + + 1e - AgAg + is reducedAg + is the oxidizing agent

33 Oxidation number The charge the atom would have in a molecule (or an ionic compound) if electrons were completely transferred. 1.Free elements (uncombined state) have an oxidation number of zero. Na, Be, K, Pb, H 2, O 2, P 4 = 0 2.In monatomic ions, the oxidation number is equal to the charge on the ion. Li +, Li = +1; Fe 3+, Fe = +3; O 2-, O = -2 3.The oxidation number of oxygen is usually –2. In H 2 O 2 and O 2 2- it is –1. 4.4

34 4.The oxidation number of hydrogen is +1 except when it is bonded to metals in binary compounds. In these cases, its oxidation number is –1. 6. The sum of the oxidation numbers of all the atoms in a molecule or ion is equal to the charge on the molecule or ion. 5.Group IA metals are +1, IIA metals are +2 and fluorine is always –1. HCO 3 - O = – 2H = +1 3x( – 2) ? = – 1 C = +4 What are the oxidation numbers of all the elements in HCO 3 - ? 7. Oxidation numbers do not have to be integers. Oxidation number of oxygen in the superoxide ion, O 2 -, is –½.

35 The Oxidation Numbers of Elements in their Compounds

36 NaIO 3 Na = +1O = -2 3x(-2) ? = 0 I = +5 IF 7 F = -1 7x(-1) + ? = 0 I = +7 K 2 Cr 2 O 7 O = -2K = +1 7x(-2) + 2x(+1) + 2x(?) = 0 Cr = +6 What are the oxidation numbers of all the elements in each of these compounds? NaIO 3 IF 7 K 2 Cr 2 O 7

37 Types of Oxidation-Reduction Reactions Combination Reaction A + B C 2Al + 3Br 2 2AlBr 3 Decomposition Reaction 2KClO 3 2KCl + 3O 2 C A + B

38 Types of Oxidation-Reduction Reactions Combustion Reaction A + O 2 B S + O 2 SO Mg + O 2 2MgO

39 Displacement Reaction A + BC AC + B Sr + 2H 2 O Sr(OH) 2 + H 2 TiCl 4 + 2Mg Ti + 2MgCl 2 Cl 2 + 2KBr 2KCl + Br 2 Hydrogen Displacement Metal Displacement Halogen Displacement Types of Oxidation-Reduction Reactions

40 The Activity Series for Metals M + BC MC + B Hydrogen Displacement Reaction M is metal BC is acid or H 2 O B is H 2 Ca + 2H 2 O Ca(OH) 2 + H 2 Pb + 2H 2 O Pb(OH) 2 + H 2

41 The Activity Series for Halogens Halogen Displacement Reaction Cl 2 + 2KBr 2KCl + Br F 2 > Cl 2 > Br 2 > I 2 I 2 + 2KBr 2KI + Br 2

42 The same element is simultaneously oxidized and reduced. Example: Disproportionation Reaction Cl 2 + 2OH - ClO - + Cl - + H 2 O Types of Oxidation-Reduction Reactions 0 +1 oxidized reduced

43 Ca 2+ + CO 3 2- CaCO 3 NH 3 + H + NH 4 + Zn + 2HCl ZnCl 2 + H 2 Ca + F 2 CaF 2 Precipitation Acid-Base Redox (H 2 Displacement) Redox (Combination) Classify each of the following reactions.

44 Chemistry in Action: Breath Analyzer 3CH 3 COOH + 2Cr 2 (SO 4 ) 3 + 2K 2 SO H 2 O 3CH 3 CH 2 OH + 2K 2 Cr 2 O 7 + 8H 2 SO

45 Solution Stoichiometry The concentration of a solution is the amount of solute present in a given quantity of solvent or solution. M = molarity = moles of solute liters of solution What mass of KI is required to make 500. mL of a 2.80 M KI solution? volume of KI solutionmoles KIgrams KI M KI 500. mL= 232 g KI 166 g KI 1 mol KI x 2.80 mol KI 1 L soln x 1 L 1000 mL x

46 Preparing a Solution of Known Concentration

47 Dilution is the procedure for preparing a less concentrated solution from a more concentrated solution. Dilution Add Solvent Moles of solute before dilution (i) Moles of solute after dilution (f) = MiViMiVi MfVfMfVf =

48 How would you prepare 60.0 mL of M HNO 3 from a stock solution of 4.00 M HNO 3 ? M i V i = M f V f M i = 4.00 M M f = MV f = L V i = ? L V i = MfVfMfVf MiMi = M x L 4.00 M = L = 3.00 mL Dilute 3.00 mL of acid with water to a total volume of 60.0 mL.

49 Gravimetric Analysis 1.Dissolve unknown substance in water 2.React unknown with known substance to form a precipitate 3.Filter and dry precipitate 4.Weigh precipitate 5.Use chemical formula and mass of precipitate to determine amount of unknown ion

50 Titrations In a titration a solution of accurately known concentration is added gradually added to another solution of unknown concentration until the chemical reaction between the two solutions is complete. Equivalence point – the point at which the reaction is complete Indicator – substance that changes color at (or near) the equivalence point Slowly add base to unknown acid UNTIL the indicator changes color

51 Titrations can be used in the analysis of Acid-base reactions Redox reactions H 2 SO 4 + 2NaOH 2H 2 O + Na 2 SO 4 5Fe 2+ + MnO H + Mn Fe H 2 O

52 What volume of a M NaOH solution is required to titrate mL of a 4.50 M H 2 SO 4 solution? WRITE THE CHEMICAL EQUATION! volume acidmoles redmoles basevolume base H 2 SO 4 + 2NaOH 2H 2 O + Na 2 SO mol H 2 SO mL soln x 2 mol NaOH 1 mol H 2 SO 4 x 1000 ml soln mol NaOH x mL = 158 mL M acid rxn coef. M base

53 WRITE THE CHEMICAL EQUATION! volume redmoles redmoles oxidM oxid mol KMnO 4 1 L x 5 mol Fe 2+ 1 mol KMnO 4 x L Fe 2+ x L = M M red rxn coef. V oxid 5Fe 2+ + MnO H + Mn Fe H 2 O mL of M KMnO 4 solution is needed to oxidize mL of an acidic FeSO 4 solution. What is the molarity of the iron solution? mL = L25.00 mL = L

54 Chemistry in Action: Metals from the Sea CaCO 3 (s) CaO (s) + CO 2 (g) Mg(OH) 2 (s) + 2HCl (aq) MgCl 2 (aq) + 2H 2 O (l) CaO (s) + H 2 O (l) Ca 2+ (aq) + 2OH (aq) - Mg 2+ (aq) + 2OH (aq) Mg(OH) 2 (s) - Mg e - Mg 2Cl - Cl 2 + 2e - MgCl 2 (aq) Mg (s) + Cl 2 (g)