1. Acids and Bases Chapter 16 Acids and Bases John D. Bookstaver St. Charles Community College St. Peters, MO  2006, Prentice Hall, Inc. Chemistry, The Central Science, 10th edition Theodore L. Brown; H. Eugene LeMay, Jr.; and Bruce E. Bursten

2. Acids and Bases Some Definitions Arrhenius  Acid:Substance that, when dissolved in water, increases the concentration of hydrogen ions.  Base:Substance that, when dissolved in water, increases the concentration of hydroxide ions.

3. Acids and Bases Some Definitions Brønsted–Lowry  Acid:Proton donor  Base:Proton acceptor

4. Acids and Bases A Brønsted–Lowry acid… …must have a removable (acidic) proton. A Brønsted–Lowry base… …must have a pair of nonbonding electrons.

5. Acids and Bases If it can be either…...it is amphiprotic. HCO 3 − HSO 4 − H2OH2O

6. Acids and Bases 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.

7. Acids and Bases Conjugate Acids and Bases: From the Latin word conjugare, meaning “to join together.” Reactions between acids and bases always yield their conjugate bases and acids.

8. Acids and Bases 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.

9. Acids and Bases Acid and Base Strength Substances with negligible acidity do not dissociate in water.  Their conjugate bases are exceedingly strong.

10. Acids and Bases Acid and Base Strength In any acid-base reaction, the equilibrium will favor the reaction that moves the proton to the stronger base. HCl (aq) + H 2 O (l)  H 3 O + (aq) + Cl − (aq) H 2 O is a much stronger base than Cl −, so the equilibrium lies so far to the right K is not measured (K>>1).

11. Acids and Bases Acid and Base Strength Acetate is a stronger base than H 2 O, so the equilibrium favors the left side (K<1). C 2 H 3 O 2 (aq) + H 2 O (l) H 3 O + (aq) + C 2 H 3 O 2 − (aq)

12. Acids and Bases 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. H 2 O (l) + H 2 O (l) H 3 O + (aq) + OH − (aq)

13. Acids and Bases Ion-Product Constant The equilibrium expression for this process is K c = [H 3 O + ] [OH − ] This special equilibrium constant is referred to as the ion-product constant for water, K w. At 25°C, K w = 1.0  10 −14

14. Acids and Bases pH pH is defined as the negative base-10 logarithm of the hydronium ion concentration. pH = −log [H 3 O + ]

15. Acids and Bases pH In pure water, K w = [H 3 O + ] [OH − ] = 1.0  10 −14 Because in pure water [H 3 O + ] = [OH − ], [H 3 O + ] = (1.0  10 −14 ) 1/2 = 1.0  10 −7

16. Acids and Bases pH Therefore, in pure water, pH = −log (1.0  10 −7 ) = 7.00 An acid has a higher [H 3 O + ] than pure water, so its pH is <7 A base has a lower [H 3 O + ] than pure water, so its pH is >7.

17. Acids and Bases pH These are the pH values for several common substances.

18. Acids and Bases Other “p” Scales The “p” in pH tells us to take the negative log of the quantity (in this case, hydrogen ions). Some similar examples are  pOH −log [OH − ]  pK w −log K w

19. Acids and Bases Watch This! Because [H 3 O + ] [OH − ] = K w = 1.0  10 −14, we know that −log [H 3 O + ] + −log [OH − ] = −log K w = 14.00 or, in other words, pH + pOH = pK w = 14.00

20. Acids and Bases 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  An indicator

21. Acids and Bases How Do We Measure pH? For more accurate measurements, one uses a pH meter, which measures the voltage in the solution.

22. Acids and Bases Strong Acids You will recall that the seven strong acids are HCl, HBr, HI, HNO 3, H 2 SO 4, HClO 3, and HClO 4. These are, by definition, strong electrolytes and exist totally as ions in aqueous solution. For the monoprotic strong acids, [H 3 O + ] = [acid].

23. Acids and Bases Strong Bases Strong bases are the soluble hydroxides, which are the alkali metal and heavier alkaline earth metal hydroxides (Ca 2+, Sr 2+, and Ba 2+ ). Again, these substances dissociate completely in aqueous solution.

24. Acids and Bases Dissociation Constants For a generalized acid dissociation, the equilibrium expression would be This equilibrium constant is called the acid-dissociation constant, K a. [H 3 O + ] [A − ] [HA] K c = HA (aq) + H 2 O (l) A − (aq) + H 3 O + (aq)

25. Acids and Bases Dissociation Constants The greater the value of K a, the stronger the acid.

26. Acids and Bases Calculating K a from the pH The pH of a 0.10 M solution of formic acid, HCOOH, at 25°C is 2.38. Calculate K a for formic acid at this temperature. We know that [H 3 O + ] [COO − ] [HCOOH] K a =

27. Acids and Bases Calculating K a from the pH The pH of a 0.10 M solution of formic acid, HCOOH, at 25°C is 2.38. Calculate K a for formic acid at this temperature. To calculate K a, we need the equilibrium concentrations of all three things. We can find [H 3 O + ], which is the same as [HCOO − ], from the pH.

28. Acids and Bases Calculating K a from the pH pH = −log [H 3 O + ] 2.38 = −log [H 3 O + ] −2.38 = log [H 3 O + ] 10 −2.38 = 10 log [H 3 O + ] = [H 3 O + ] 4.2  10 −3 = [H 3 O + ] = [HCOO − ]

29. Acids and Bases Calculating K a from pH Now we can set up a table… [HCOOH], M[H 3 O + ], M[HCOO − ], M Initially0.1000 Change −4.2  10 -3 +4.2  10 -3 +4.2  10 −3 At Equilibrium 0.10 − 4.2  10 −3 = 0.0958 = 0.10 4.2  10 −3

30. Acids and Bases Calculating K a from pH [4.2  10 −3 ] [0.10] K a = = 1.8  10 −4