Acid/Base Equilibria Chapter 16

Models of Acids and Bases Arrhenius Concept: Acids produce H+ in solution, bases produce OH ion. Brønsted-Lowry: Acids are H+ donors, bases are proton acceptors. HCl + H2O  Cl + H3O+ acid base

© 2012 Pearson Education, Inc. A Brønsted–Lowry acid… …must have a removable (acidic) proton. A Brønsted–Lowry base… …must have a pair of nonbonding electrons. © 2012 Pearson Education, Inc.

What Happens When an Acid Dissolves in Water? Water acts as a Brønsted–Lowry base and abstracts a proton (H+) from the acid. As a result, the conjugate base of the acid and a hydronium ion are formed. © 2012 Pearson Education, Inc.

Conjugate Acid/Base Pairs HA(aq) + H2O(l)  H3O+(aq) + A(aq) conj conj conj conj acid 1 base 2 acid 2 base 1 conjugate base: everything that remains of the acid molecule after a proton is lost. conjugate acid: formed when the proton is transferred to the base.

Acid Dissociation Constant (Ka) HA(aq) + H2O(l)  H3O+(aq) + A(aq)

Acid Strength Strong Acid: Its equilibrium position lies far to the right. (HNO3) Yields a weak conjugate base. (NO3)

© 2012 Pearson Education, Inc. Acid and Base Strength Strong acids are completely dissociated in water. Their conjugate bases are quite weak. Weak acids only dissociate partially in water. Their conjugate bases are weak bases. © 2012 Pearson Education, Inc.

Strong Acid - Weak Acid

© 2012 Pearson Education, Inc. Strong Acids You will recall that the seven strong acids are HCl, HBr, HI, HNO3, H2SO4, HClO3, and HClO4. These are, by definition, strong electrolytes and exist totally as ions in aqueous solution. For the monoprotic strong acids, [H3O+] = [acid]. © 2012 Pearson Education, Inc.

© 2012 Pearson Education, Inc. Strong Acids HCl – Hydrochloric Acid HBr – Hydrobromic Acid HI – Hydroiodic Acid HNO3 - Nitric Acid H2SO4 – Sulfuric Acid HClO3 – Chloric Acid HClO4 – Perchloric Acid © 2012 Pearson Education, Inc.

Acid Strength (continued) Weak Acid: Its equilibrium lies far to the left. (CH3COOH) Yields a much stronger (it is relatively strong) conjugate base than water. (CH3COO)

Strong Acid Weak Acid

Water as an Acid and a Base Water is amphoteric (it can behave either as an acid or a base). H2O + H2O  H3O+ + OH conj conj acid 1 base 2 acid 2 base 1 Kw = 1  1014 at 25°C

Autoionization of Water As we have seen, water is amphoteric. In pure water, a few molecules act as bases and a few act as acids. This is referred to as autoionization. © 2012 Pearson Education, Inc.

© 2012 Pearson Education, Inc. Ion Product Constant The equilibrium expression for this process is Kc = [H3O+] [OH] This special equilibrium constant is referred to as the ion product constant for water, Kw. At 25C, Kw = 1.0  1014 © 2012 Pearson Education, Inc.

The pH Scale pH  log[H+] pH in water ranges from 0 to 14. Kw = 1.00  1014 = [H+] [OH] pKw = 14.00 = pH + pOH As pH rises, pOH falls (sum = 14.00).

© 2012 Pearson Education, Inc. How Do We Measure pH? For less accurate measurements, one can use Litmus paper “Red” paper turns blue above ~pH = 8 “Blue” paper turns red below ~pH = 5 Or an indicator. © 2012 Pearson Education, Inc.

© 2012 Pearson Education, Inc. How Do We Measure pH? For more accurate measurements, one uses a pH meter, which measures the voltage in the solution. © 2012 Pearson Education, Inc.

Solving Weak Acid Equilibrium Problems List major species in solution. Choose species that can produce H+ and write reactions. Based on K values, decide on dominant equilibrium. Write equilibrium expression for dominant equilibrium. List initial concentrations in dominant equilibrium.

Solving Weak Acid Equilibrium Problems (continued) Define change at equilibrium (as “x”). Write equilibrium concentrations in terms of x. Substitute equilibrium concentrations into equilibrium expression. Solve for x the “easy way.” Verify assumptions using 5% rule. Calculate [H+] and pH.

Percent Dissociation (Ionization)

Polyprotic Acids . . . can furnish more than one proton (H+) to the solution.

Acids and Bases

NaOH(s)  Na+(aq) + OH(aq) Bases “Strong” and “weak” are used in the same sense for bases as for acids. strong = complete dissociation (hydroxide ion supplied to solution) NaOH(s)  Na+(aq) + OH(aq)

Strong Bases

H3CNH2(aq) + H2O(l)  H3CNH3+(aq) + OH(aq) Bases (continued) weak = very little dissociation (or reaction with water) H3CNH2(aq) + H2O(l)  H3CNH3+(aq) + OH(aq)

Acid-Base Properties of Salts

Problem An unknown salt is either NaF, NaCl or NaOCL. When 0.050 moles of the salt is dissolved in 0.500 L of solution, the pH of the solution is 8.08. What is the identity of the salt? Show Calculations.

Problem Sorbic acid (C5H7COOH) is a weak monoprotic acid with Ka = 1.7 x10-5. Its salt (potassium sorbate) is added to cheese to inhibit the formation of mold. What is the pH of a solution containing 9.50 g of potassium sorbate in 2.00 L of solution?

Problem – 16.90 Trisodium phosphate (Na3PO4) is available in hardware stores as TSP and is used as a cleaning agent. The label on a box of TSP warns that the substance is very basic (caustic or alkaline). What is the pH of a solution containing 35.0 g of TSP in a liter of solution?

Structure and Acid-Base Properties Two factors for acidity in binary compounds: Bond Polarity (high is good) Bond Strength (low is good)

Oxides Acidic Oxides (Acid Anhydrides): OX bond is strong and covalent. SO2, NO2, CrO3 Basic Oxides (Basic Anhydrides): OX bond is ionic. K2O, CaO

Lewis Acids and Bases Lewis Acid: electron pair acceptor Lewis Base: electron pair donor

Problem 16.86 Predict whether aqueous solutions of the following are acidic, basic, or neutral: CrBr3 LiCl K3PO4 (CH3NH3)Cl KHSO4

END