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Acids & Bases CHAPTER 16 (& part of CHAPTER 17) Chemistry: The Molecular Nature of Matter, 6 th edition By Jesperson , Brady, & Hyslop. CHAPTER 16: Acids & Bases. Learning Objectives: Define Brønsted -Lowry Acid/Base Define Lewis Acid/Base Evaluate the strength of acids/bases
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Acids & Bases CHAPTER 16 (& part of CHAPTER 17) Chemistry: The Molecular Nature of Matter, 6th edition By Jesperson, Brady, & Hyslop
CHAPTER 16: Acids & Bases • Learning Objectives: • Define Brønsted-Lowry Acid/Base • Define Lewis Acid/Base • Evaluate the strength of acids/bases • Strong vs weak acids/bases • Periodic trends • Conjugate acids/bases • Identify likely compounds that will form acids and bases from the periodic table • Acidic metal ions • Acid/Base equilibrium: • pH, pOH • Ka, Kb, pKa, pKb • Kw of water Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
CHAPTER 16: Acids & Bases Lecture Road Map: Brønsted-Lowry Acids/Bases Trends in acid strength Lewis Acids & Bases Acidity of hydrated metal ions Acid/Base equilibrium Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
CHAPTER 16 Acids & Bases Brønsted-Lowry Acid/Base Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Arrhenius Acid/Base Definition Acid produces H3O+ in water Basegives OH– Acid-base neutralization • Acid and base combine to produce water and a salt. e.g. HCl(aq) + NaOH(aq) H2O + NaCl(aq) H3O+(aq) + Cl–(aq) + Na+(aq) + OH–(aq) 2H2O +Cl–(aq) + Na+(aq) • Many reactions resemble this without forming H3O+ or OH– in solution Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Arrhenius Acid/Base Definition Gas Phase Acid/Base chemistry not covered by Arrhenius definition e.g. NH3(g) + HCl(g) NH4Cl(s) Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Brønsted-Lowry Definition • Acid = proton donor • Base = proton acceptor • Allows for gas phase acid-base reactions e.g. HCl + H2O H3O+ + Cl– • HCl = acid • Donates H+ • Water = base • Accepts H+ Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Brønsted-Lowry Conjugate Acid-Base Pair • Species that differ by H+ e.g. HCl + H2O H3O+ + Cl– • HCl = acid • Water = base • H3O+ • Conjugate acid of H2O • Cl– • Conjugate base of HCl Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Brønsted-Lowry Example: Formic Acid • Formic acid (HCHO2) is a weak acid • Must consider equilibrium • HCHO2(aq) + H2O CHO2–(aq) + H3O+(aq) • Focus on forward reaction Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Brønsted-Lowry Example: Formic Acid Now consider reverse reaction: • Hydronium ion transfers H+ to CHO2– • Formate Ion is the Brønsted Base Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Group Problem • Identify the conjugate partner for each Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Group Problem Write a reaction that shows that HCO3– is a Brønstedacidwhen reacted with OH– Write a reaction that shows that HCO3– is a Brønstedbasewhen reacted with H3O+(aq) Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Group Problem In the following reaction, identify the acid/base conjugate pairs. (CH3)2NH + H2SO4 → (CH3)2NH+ + HSO4– A. (CH3)2NH / H2SO4 (CH3)2NH+ / HSO4– B. (CH3)2NH / (CH3)2NH+ H2SO4 / HSO4– C. H2SO4 / HSO4– (CH3)2NH+ / (CH3)2NH D. H2SO4 / (CH3)2NH (CH3)2NH+ / HSO4– Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Brønsted-Lowry Amphoteric Substances • Can act as either acid or base • Can be either molecules or ions e.g. Hydrogen carbonate ion: • Acid HCO3–(aq) + OH–(aq) CO32–(aq) + H2O • Base HCO3–(aq) + H3O+(aq) H2CO3(aq) + H2O [Amphiproticsubstances can donate or accept a proton. This is a subtle but important difference from the word amphoteric] Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Group Problem Which of the following can act as an amphoteric substance? A. CH3COOH B. HCl C. NO2– D. HPO42– Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
CHAPTER 16 Acids & Bases Trends in Acid/Base Strength Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Acid/Base Trends Strengths of Acids & Bases Strength of Acid • Measure of its ability to transfer H+ • Strongacids • React completely with water e.g.HCl and HNO3 • Weak acids • Less than completely ionized e.g.CH3COOH and CHOOH Strength of Baseclassified in similar fashion: • Strong bases • React completely with water e.g.Oxide ion (O2–) and OH– • Weak bases • Undergo incomplete reactions e.g.NH3 and NRH2 (NH2CH3, methylamine) Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Acid/Base Trends Strength in Water • Strongest acid= hydronium ion, H3O+ • If more powerful H+ donor added to H2O • Reacts with H2O to produce H3O+ Similarly, • Strongest baseis hydroxide ion (OH–) • More powerful H+ acceptors • React with H2O to produce OH– Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Acid/Base Trends Acid/Base Equilibrium • Acetic acid (HC2H3O2) is weak acid • Ionizes only slightly in water HC2H3O2(aq) + H2O H3O+(aq) + C2H3O2–(aq) weaker acidweaker basestronger acidstronger base • Hydronium ion • Better H+ donor than acetic acid • Stronger acid • Acetate ion • Better H+ acceptor than water • Stronger base • Position of equilibrium favors weakeracid and base Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Group Problem In the reaction: HCl + H2O → H3O+ + Cl– which species is the weakest base ? A. HCl B. H2O C. H3O+ D. Cl– Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Group Problem Group Problem Identify the preferred direction of the following reactions: H3O+(aq)+ CO32–(aq) HCO3–(aq)+ H2O Cl–(aq)+ HCN(aq)HCl(aq)+ CN–(aq) Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Acid/Base Trends General Trends • Stronger acids and bases tend to react with each other to produce their weaker conjugates • Stronger Brønsted acid has weaker conjugate base • Weaker Brønsted acid has stronger conjugate base • Can be applied to binary acids (acids made from hydrogen and one other element) Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Acid/Base Trends Binary Acid Trends Binary Acids = HnX X = Cl, Br, P, As, S, Se, etc. • Acid strength increases from left to right within same period (across row) • Acid strength increases as electronegativity of Xincreases e.g.HCl is stronger acid than H2S which is stronger acid than PH3 • or PH3 < H2S < HCl Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Acid/Base Trends Binary Acid Trends Binary Acids = HnX X = Cl, Br, P, As, S, Se, etc. 2. Acid strength increase from top to bottom within group • Acid strength increases as size of Xand bond length increases e.g. HCl is weaker acid than HBr which is weaker acid than HI • or HCl < HBr < HI Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Group Problem Which is stronger? • H2S or H2O • CH4 or NH3 • HF or HI
Acid/Base Trends Oxoacid Trends Oxoacids (HnX Om) • Acids of H, O, and one other element • HClO, HIO4, H2SO3, H2SO4, etc. • Acids with same number of oxygen atoms and differing X • Acid strength increasesfrom bottom to top within group • HIO4 < HBrO4 < HClO4 • Acid strength increases from left to right within period as the electronegativity of the central atom increases H3PO4 < H2SO4 < HClO4 Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Acid/Base Trends Definition Oxoacids (HnXOm) • For same X • Acid strength increases with number of oxygen atoms • H2SO3 < H2SO4 • More oxygens, remove more electron density from central atom, weakening O—H bond make H more acidic Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Group Problem Which is the stronger acid in each pair? • H2SO4 or H3PO4 • HNO3 or H3PO3 • H2SO4 or H2SO3 • HNO3 or HNO2 Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Group Problem Which corresponds to the correct order of acidity from weakest to strongest acid ? A. HBrO3, HBrO, HBrO2 B. HBrO, HBrO2, HBrO3 C. HBrO, HBrO3, HBrO2 D. HBrO3, HBrO2, HBrO
Acid/Base Trends Basicity • Acid strength can be analyzed in terms of basicity of anion formed during ionization • Basicity • Willingness of anion to accept H+ from H3O+ • Consider HClO3 and HClO4: Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Acid/Base Trends Basicity • Loneoxygens carry most of the negative charge • ClO4– has 4 O atoms, so each has –¼ charge • ClO3– has 3 O atoms, so each has –1/3 charge • ClO4–weaker base than ClO3– • Thus conjugate acid, HClO4, is stronger acid • HClO4 stronger acid as more fully ionized Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Group Problem
Acid/Base Trends Organic Acid Trends • Organic acid —COOH • Presence of electronegative atoms (halide, nitrogen or other oxygen) near —COOH group • Withdraws electron density from O—H bond • Makes organic acid, stronger acids e.g.CH3CO2H < CH2ClCO2H < CHCl2CO2H < CCl3CO2H Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Group Problem Which of the following is the strongest organic acid? A B C D E
CHAPTER 16 Acids & Bases Lewis Acid/Base Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Lewis Acid/Base Definition • Broadest definition of species that can be classified as either acid or base • Definitions based on electron pairs • Lewis acid • Any ionic or molecular species that can acceptpair of electrons • Formation of coordinate covalent bond • Lewis base • Any ionic or molecular species that can donatepair of electrons • Formation of coordinate covalent bond Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Lewis Acid/Base Lewis Neutralization • Formation of coordinate covalent bond between electron pair donor and electron pair acceptor • NH3BF3 = addition compound • Made by joining two smaller molecules Addition Compound Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Lewis Acid/Base Lewis Acid-Base Reaction Electrons in coordinate covalent bond come from O in hydroxide ion Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Lewis Acid/Base Lewis Acids • Molecules or ions with incomplete valence shells e.g. BF3 or H+ • Molecules or ions with complete valence shells, but with multiple bonds that can be shifted to make room for more electrons e.g. CO2 • Molecules or ions that have central atoms that can expand their octets • Capable of holding additional electrons • Usually, atoms of elements in Period 3 and below e.g. SO2 Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Lewis Acid/Base Lewis Acid Example: SO2 O2– Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Lewis Acid/Base Lewis Bases • Molecules or ions that have unshared electron pairs and that have complete shells • e.g. O2– or NH3 Lewis Definition is Most General • All Brønsted acids and bases are Lewis acids and bases • All Arrhenius acids and bases are Brønsted acids and bases Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Lewis Acid/Base Proton (H+) Transfer H2O—H+ + NH3 H2O + H+—NH3 Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Group Problem Identify the Lewis acid and base in the following: • NH3 + H+NH4+ • F– + BF3BF4– • SeO3 + O2– SeO42–
Group Problem Which of the following species can act as a Lewis base ? A. Cl– B. Fe2+ C. NO2– D. O2–
CHAPTER 16 Acids & Bases Acidity of Oxides & Hydrates Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Acidic Metal Ions Acid-Base Properties of Elements & their Oxides Nonmetal oxides • React with H2O to form acids • Upper right hand corner of periodic table • Acidic Anhydrides • Neutralize bases • Aqueous solutions redto litmus • SO3(g) + H2O H2SO4(aq) • N2O5(g) + H2O 2HNO3(aq) • CO2(g) + H2O H2CO3(aq) Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Acidic Metal Ions Acid-Base Properties of Elements & their Oxides Metal oxides • React with H2O to form hydroxide (Base) • Group 1A and 2A metals (left hand side of periodic table) • BasicAnydrides • Neutralize acids • Aqueous solutions blue to litmus • Na2O(s) + H2O 2NaOH(aq) • CaO(s) + H2O Ca(OH)2(aq) Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Acidic Metal Ions Metal Oxides • Solids at room temperature • Many insoluble in H2O • Why? • Too tightly bound in crystal • Can't remove H+ from H2O • Do dissolve in solution of strong acid • Now H+ free, can bind to O2– and remove from crystal Fe2O3(s) + 6H+(aq) 2Fe3+(aq) + 3H2O Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E
Group Problem What is the acid formed by P2O3 when it reacts with water ? A. H2PO4 B. H2PO2 C. H3PO4 D. H3PO3
Acidic Metal Ions Metal Ions in Solution • Exist with sphere of water molecules with their negative poles directed toward Mn+ • Mn+(aq) + mH2O M(H2O)mn+(aq) Lewis AcidLewis Basehydrated metal ion = addition compound • n= charge on metal ion = 1, 2, or 3 depending on metal atom • For now assume m = 1 (monohydrate) Jesperson, Brady, Hyslop. Chemistry: The Molecular Nature of Matter, 6E