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1 ed. Brad Collins Aqueous Chemistry Chapter 5 Some images copyright The McGraw-Hill Companies, Inc.

2 A solution is a homogenous mixture of 2 or more substances at the molecular level The solute(s) is(are) the substance(s) present in the smaller amount(s) The solvent is the substance present in the larger amount Solution Solvent Solute Soft drink (l) Air (g) Soft Solder (s) H 2 O N 2 Pb Sugar, CO 2 O 2, Ar, CH 4 Sn 5.1

3 Hydration is the process in which an ion is surrounded by water molecules arranged in a specific manner. δ δ + H 2 Ionic compounds dissolve by dissociation: The process of breaking up into ions. 5.1

4 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. nonelectrolyt weak strong 5.1

5 Conduct electricity in solution? Cations (+) and Anions (-) Strong Electrolyte 100% dissociation NaCl (s) H 2 O Na + (aq) + Cl - (aq) Weak Electrolyte not completely dissociated CH 3 COOH CH 3 COO - (aq) + H + (aq) 5.1

6 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. 5.1

7 A nonelectrolyte does not conduct electricity because: No cations (+) or anions (-) in solution C 6 H 12 O 6 (s) H 2 O C 6 H 12 O 6 (aq) 5.1

8 Solubility Solubility is the degree to which a compound dissolves in a solvent. Several ways to categorize: Saturated, unsaturated, supersaturated Saturated: Solvent contains as much solute as it can hold Unsaturated: Solvent contains less solute than a saturated solution Supersaturated: Solvent contains more solute than a saturated solution. 5.2

9 Solubility Trends In order of priority: Group 1A compounds, ammonium salts, and all acids are soluble. Nitrates, acetates, chlorates, and perchlorates are soluble Silver, lead, mercury(i) and copper(i) compounds are insoluble Chlorides, bromides, and iodides are soluble Sulfates are soluble (except barium and calcium sulfate) Compounds with a 2 or 3 anion are insoluble Hydroxides are insoluble (except Group 1A, calcium and barium hydroxides) 5.2

10 5.2

11 Practice: Solubility Classify the following compounds as soluble or insoluble, and cite the solubility rule involved: Sodium chloride Silver nitrate Silver chloride Iron(II) chloride Magnesium sulfate Calcium sulfide Barium hydroxide 5.2

12 Precipitation Reactions Precipitate insoluble solid that separates from solution precipitate Pb(NO 3 ) 2 (aq) + 2NaI (aq) PbI 2 (s) + 2NaNO 3 (aq) molecular equation Pb NO Na + + 2I - PbI 2 (s) + 2Na + + 2NO 3 - ionic equation Pb I - PbI 2 (s) PbI 2 (s) net ionic equation Na + and NO 3 - are spectator ions 5.2

13 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 Write the net ionic equation for the reaction of silver nitrate with sodium chloride. AgNO 3 (aq) + NaCl (aq) AgCl (s) + NaNO 3 (aq) Ag + + NO Na + + Cl - AgCl (s) + Na + + NO 3 - Ag + + Cl - AgCl (s) 5.2

14 Practice: Writing Ionic Equations Write the molecular and ionic equations for the following chemical reaction: Aluminum nitrate + sodium hydroxide 5.2

15 Properties of Acids Have a sour taste. Vinegar owes its taste to acetic acid. Citrus fruits contain citric acid. Cause color changes in plant dyes. React with certain metals to produce hydrogen gas. 2HCl (aq) + Mg (s) MgCl 2 (aq) + H 2 (g) React with carbonates and bicarbonates to produce carbon dioxide gas 2HCl (aq) + CaCO 3 (s) CaCl 2 (aq) + CO 2 (g) + H 2 O (l) Aqueous acid solutions conduct electricity. 5.3

16 Arrhenius acid is a substance that produces H + (H 3 O + ) in water Arrhenius base is a substance that produces OH - in water 5.3

17 Hydronium ion, hydrated proton, H 3 O + 5.3

18 Monoprotic acids HCl H + + Cl - HNO 3 H + + NO 3 - CH 3 COOH H + + CH 3 COO - Strong electrolyte, strong acid 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 2-4 HPO 2-4 H + + PO 3-4 Weak electrolyte, weak acid Weak electrolyte, weak acid Weak electrolyte, weak acid 5.3

19 Bases Have a bitter taste. Feel slippery. Many soaps contain bases. Cause color changes in plant dyes. Aqueous base solutions conduct electricity. 5.3

20 A Brønsted acid is a proton donor A Brønsted base is a proton acceptor base acid acid base A Brønsted acid must contain at least one ionizable proton! 5.3

21 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 + H 2 O H 3 O + (aq) + I - (aq) Brønsted acid CH 3 COO - (aq) + H 2 O CH 3 COOH + OH - Brønsted base H 2 PO 4 - (aq) + H 2 O H 3 O + (aq) + HPO 4 2- (aq) Brønsted acid H 2 PO 4 - (aq) + H 2 O H 3 PO 4 (aq) + OH (aq) Brønsted base 5.3

22 Acid-Base (Neutralization) Reaction acid + base salt + water HCl (aq) + NaOH (aq) H + + Cl - + Na + + OH - H + + OH - NaCl (aq) + H 2 O Na + + Cl - + H 2 O H 2 O 5.3

23 Gas-Forming Reactions Reactions that produce carbonic acid Carbonic acid decomposes in water to form more water and carbon dioxide Reactions that produce sulfurous acid Aqueous sulfurous acid decomposes to form water and sulfur dioxide gas Reactions that produce hydrogen sulfide, H2S(g) Reactions between metals and acids Metal + Acid Salt + hydrogen gas Not all metals react with all acids to produce hydrogen gas Cu(s) + 4HNO3(aq) Cu(NO3)2(aq) + 2NO2(g) + H2O(l) 5.4

24 Oxidation-Reduction Reactions (electron transfer reactions) 2Mg (s) + O 2 (g) 2MgO (s) 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 5.5

25 5.5

26 Oxidation number rules - Part 1 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 = Group IA metals are +1, IIA metals are +2 and fluorine is always The oxidation number of hydrogen is +1 except when it is bonded to metals in binary compounds (e.g. LiH). In these cases, its oxidation number is

27 5. The oxidation number of oxygen is 2 except in H 2 O 2 and O 2 2- where it is Group 7A halogens (except fluorine) are -1 in binary compounds. When bonded with oxygen, other halides have + oxidation numbers 7. 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. Oxidation numbers of all the elements in HCO 3 -? HCO 3 - O = -2 H = +1 3x(-2) + 1 +? = -1 C =

28 Figure 4.10 The oxidation numbers of elements in their compounds 5.5

29 Oxidation numbers of all the elements in the following? IF 7 F = -1 7x(-1) +? = 0 I = +7 NaIO 3 Na = +1 O = -2 3x(-2) + 1 +? = 0 I = +5 K 2 Cr 2 O 7 O = -2 K = +1 7x(-2) + 2x(+1) + 2x(?) = 0 Cr =

30 Types of Oxidation-Reduction Reactions Combination Reaction A + B C S + O 2 SO 2 Decomposition Reaction C A + B KClO 3 2KCl + 3O 2 5.5

31 Types of Oxidation-Reduction Reactions Displacement Reaction A + BC Sr + 2H 2 O Sr(OH) 2 + H TiCl 4 + 2Mg Ti + 2MgCl Cl 2 + 2KBr 2KCl + Br 2 AC + B Hydrogen Displacement Metal Displacement Halogen Displacement 5.5

32 The Activity Series for Metals Hydrogen Displacement Reaction M + BC AC + B 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 Figure

33 Halogen Displacement The ability of one halogen to replace another in a displacement reaction. Order: F 2 > Cl 2 > Br 2 > I 2 Example: Cl 2 (g) + 2 KBr (aq) Cl 2 (g) + 2 NaI (aq) Br 2 (g) + 2 KI (aq) 2KCl (aq) + Br 2 (l) 2NaCl (aq) + I 2 (s) 2KBr (aq) + I 2 (s) 5.5

34 Types of Oxidation-Reduction Reactions Disproportionation Reaction Element is simultaneously oxidized and reduced Cl 2 + 2OH - ClO - + Cl - + H 2 O Chlorine Chemistry 5.5

35 Classify the following reactions. Ca 2+ + CO 3 2- CaCO 3 NH 3 + H + NH 4 + Zn + 2HCl ZnCl 2 + H 2 Precipitation Acid-Base Redox (H 2 Displacement) Ca + F 2 CaF 2 Redox (Combination) 4.4

36 Zn (s) + CuSO 4 (aq) ZnSO 4 (aq) + Cu (s) Zn Zn e - Zn is oxidized Zn is the reducing agent Cu e - Cu Cu 2+ is reduced 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 - Ag Ag + is reduced Ag + is the oxidizing agent 4.4

37 Chemistry in Action: Breath Analyzer +6 3CH 3 CH 2 OH + 2K 2 Cr 2 O 7 + 8H 2 SO CH 3 COOH + 2Cr 2 (SO 4 ) 3 + 2K 2 SO H 2 O 4.4

38 Molarity 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? M KI M KI volume KI moles KI grams KI 1 L 2.80 mol KI 166 g KI 500. ml x x x = 232 g KI 1000 ml 1 L soln 1 mol KI 5.6

39 5.6

40 Practice: Solution Concentration What is the molarity of an 85.0-mL ethanol (C 2 H 5 OH) solution, which contains 1.77g of ethanol? 5.6

41 Titrations In a titration a solution of accurately known concentration (titrant) is added gradually added to another solution of unknown concentration (titrand) until the chemical reaction between the two solutions is complete. Equivalence point the point at which the reaction is complete moles titrant (V A *M A ) = moles titrand (V B *M B ) Indicator substance that changes color at (or near) the equivalence point Example: Slowly add base to unknown acid UNTIL the indicator changes color 5.6

42 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! M H 2 SO 4 + 2NaOH 2H 2 O + Na 2 SO 4 volume acid moles acid moles base volume base acid rx coef. M bas 4.50 mol H 2 SO 4 2 mol NaOH 1000 ml soln ml x x x = 158 ml 1000 ml soln 1 mol H 2 SO mol NaOH 5.6

43 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) M i V i = M f V f 5.6

44 How would you prepare 60.0 ml of 0.2 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 f = V f = 0.06 L V i =? L V i = M fv f M i = x = L = 3 ml 3 ml of acid + 57 ml of water = 60 ml of solution 5.6

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