Self-Ionization of Water. Even pure water conducts some electricity. This is due to the fact that water self-ionizes:

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1 1 Self-Ionization of Water Even pure water conducts some electricity. This is due to the fact that water self-ionizes: Self ionization of water movie The equilibrium constant for this process is called the ion product of water (K w ) At 25 C, K w = [H 3 O + ][OH ] = 1.0 x M 2 Equilibrium concentrations of pure water: [H 3 O + ] = [OH ] = 1.0 x 10 7 M The equilibrium constant K w is very important because it applies to all aqueous solutions acids, bases, salts, and nonelectrolytes not just to pure water. ph and poh ph is a measure of the strength of an acid; low ph = stronger acid ph = log[h 3 O + ] and [H 3 O + ] = 10 ph poh is a measure of the strength of a base; low poh = stronger base poh = log[oh ] and [OH ] = 10 poh Negative ph is also possible! The ph scale extends over 14 1

2 Ionization Constant Relationships pk w = log K w at 25 ºC, pk w = K w = [H + ][OH ] = M 2 pk w = ph + poh = For conjugate acid-base pairs: A student determines the ph of milk of magnesia, a suspension of solid magnesium hydroxide in its saturated aqueous solution, and obtains a value of What is the molarity of Mg(OH) 2 in its saturated aqueous solution? The suspended, undissolved Mg(OH) 2 (s) does not affect the measurement. 4 Is the solution 1.0 x 10 8 M HCl acidic, basic, or neutral? 2

3 5 Ordinary vinegar is approximately 1 M CH 3 COOH and it has a ph of about 2.4. Calculate the expected ph of 1.00 M CH 3 COOH(aq), and show that the calculated and measured ph values are in good agreement. 6 3

4 7 Polyprotic Acids A polyprotic acid has more than one ionizable H atom per molecule. Sulfuric acid, H 2 SO 4 Diprotic Carbonic acid, H 2 CO 3 Diprotic Phosphoric acid, H 3 PO 4 Triprotic The protons of a polyprotic acid dissociate in steps, each step having a different value of K a. Values of K a decrease successively for a given polyprotic acid: K a1 = M K a1 > K a2 > K a3, etc. K a2 = M Why? K a3 = M H 2 SO 4 H 3 PO 4 8 Calculate the following concentrations in an aqueous solution that is 5.0 M H 3 PO 4 : (a) [H 3 O + ] (b) [H 2 PO 4 ] (c) [HPO 4 2 ] (d) [PO 4 3 ] What is the approximate ph of 0.71 M H 2 SO 4? 4

5 9 Ions as Acids and Bases A carbonate ion accepts a proton from water, leaving behind an OH and making the solution basic. When Na 2 CO 3 dissolves, it completely dissociates into ions: Na 2 CO 3 2Na + + CO 3 2 Carbonate ion reacts to produce OH : CO H 2 O HCO 3 + OH This reaction raises [OH ] above 10 7 M, and [H 3 O + ] decreases accordingly. ph > 7 We say that CO 3 2 underwent hydrolysis. Ions as Acids and Bases 10 Salts of strong acids and strong bases form neutral solutions: NaCl, KNO 3 Why? Salts of strong acids and weak bases form acidic solutions: NH 4 NO 3 Why? Salts of weak acids and strong bases form basic solutions: KNO 2, NaClO Why? Salts of weak acids and weak bases form solutions that may be acidic, neutral, or basic; it depends on the relative strengths of the cations and the anions: NH 4 NO 2, CH 3 COONH 4. Why? 5

6 Ions as Acids and Bases 11 What conclusion can you draw about the equilibrium constants for the hydrolysis reactions in CH 3 COONH 4 (aq)? Neutral Basic Acidic Neutral NaCl(aq) CH 3 COONa(aq) NH 4 Cl(aq) CH 3 COONH 4 (aq) * with bromthymol blue as indicator The Common Ion Effect 12 Consider a solution of acetic acid. If we add acetate ion as a second solute (i.e., sodium acetate), the ph of the solution increases: LeChâtelier s principle: What happens to [H 3 O + ] when the equilibrium shifts to the left? 6

7 The Common Ion Effect 13 The common ion effect is the suppression of the ionization of a weak acid or a weak base by the presence of a common ion from a strong electrolyte. 1. Acetic acid solution at equilibrium: a few H 3 O + ions and a few CH 3 COO ions 2. When acetate ion is added, and equilibrium reestablished: more acetate ions, but fewer H 3 O + ions a) Calculate the ph of an aqueous solution that is both 1.00 M CH 3 COOH and 1.00 M CH 3 COONa. 14 b) Compare the ph of a solution of only 1.00 M CH 3 COOH. 7

8 15 Summary of Concepts Water undergoes limited self-ionization producing H 3 O + and OH. ph = log[h 3 O + ] poh = log[oh ] pk w = logk w The ph in both pure water and in neutral solutions is 7. Acidic solutions: ph < 7; basic solutions: ph > 7. In aqueous solutions at 25 o C, ph + poh = Hydrolysis reactions cause certain salt solutions to be either acidic or basic A strong electrolyte that produces an ion common to the ionization equilibrium of a weak acid (or a weak base) suppresses the ionization of the weak acid (base) 8

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