1. Acids and Bases Chapter 14

2. Properties of Acids Acids: taste sour (citrus fruits & vinegar)taste sour (citrus fruits & vinegar) affect indicators (e.g. turn blue litmus red)affect indicators (e.g. turn blue litmus red) produce H + ions in aqueous solutionproduce H + ions in aqueous solution corrosive to metalscorrosive to metals pH < 7pH < 7

3. Classifying Acids Organic acids contain a carboxyl group or -COOH -- HC 2 H 3 O 2 & citric acid. Inorganic acids -- HCl, H 2 SO 4, HNO 3. Oxyacids -- acid proton attached to oxygen -- H 3 PO 4. Monoprotic -- HCl & HC 2 H 3 O 2 Diprotic -- H 2 SO 4 Triprotic -- H 3 PO 4

4. Properties of Bases Bases: taste bittertaste bitter feel slipperyfeel slippery affect indicators (e.g. turn red litmus blue)affect indicators (e.g. turn red litmus blue) produce OH - ions in aqueous solutionproduce OH - ions in aqueous solution pH > 7pH > 7 causticcaustic

5. 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 + H 2 O  Cl  + H 3 O + acid base acid base

6. Hydronium Ion Hydronium ion is a hydrated proton -- H + Hydronium ion is a hydrated proton -- H +. H 2 O. The H + ion is simply a proton. It has a very high charge density, so it strongly is attracted to the very electronegative oxygen of the polar water molecule.

7. Conjugate Acid/Base Pairs HA(aq) + H 2 O(l)  H 3 O + (aq) + A  (aq) conj conj conj conj 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. Which is the stronger base--H 2 O or A - ?

8. Acid Dissociation Constant (K a ) HA(aq) + H 2 O(l)  H 3 O + (aq) + A  (aq) K a values for common acids are found in Table 14.2 on page 663.

10. Bronsted-Lowry Model The Bronsted-Lowry Model is not limited to aqueous solutions like the Arrhenius Model. NH 3(g) + HCl (g) ----> NH 4 Cl (s) This is an acid-base reaction according to Bronsted-Lowry, but not according to Arrhenius!

11. Acid Strength -Its equilibrium position lies far to the right. (HNO 3 ) -Yields a weak conjugate base. (NO 3  ) Strong Acid:

12. Acid Strength (continued) -Its equilibrium lies far to the left. (CH 3 COOH) -Yields a much stronger (water is relatively strong) conjugate base than water. (CH 3 COO  ) Weak Acid:

13. A strong acid is nearly 100 % ionized, while a weak acid is only slightly ionized.

14. Diagram a represents a strong acid, while b represents a weak acid which remains mostly in the molecular form.

16. The relationship of acid strength and conjugate base strength for acid- base reactions.

17. Arranging Species According to Increasing Basic Strength H 2 O, F -, Cl -, NO 2 -, & CN - Use Table 14.2 on page 663. Cl - is weakest since it is conjugate base of strong acid and weaker than water. Use K a values to arrange the remaining bases. Cl - < H 2 O < F - < NO 2 - < CN -

18. Water as an Acid and a Base Water is amphoteric (it can behave either as an acid or a base). H 2 O + H 2 O  H 3 O + + OH  conj conj conj conj acid 1 base 2 acid 2 base 1 acid 1 base 2 acid 2 base 1 K w = 1  10  14 M 2 at 25°C

19. Ion product Constant, K w K w is called the ion-product constant or dissociation constant. neutral solution [H + ] = [OH - ] = 1.0 x 10 -7 M acidic solution [H + ] > [OH - ] [H + ] > 1.0 x 10 -7 M basic solution [H + ] 1.0 x 10 -7 M No matter what the concentration of H + or OH - in an aqueous solution, the product, K w, will remain the same.

20. [H + ] & [OH - ] Calculations Calculate the [H + ] for a 1.0 x 10 -5 M OH -. K w = [H + ][OH - ] [H + ] = K w /[OH - ] [H + ] = 1.0 x 10 -14 M 2 /1.0 x 10 -5 M [H + ] = [H + ] = 1.0 x 10 -9 M

21. [H + ] & [OH - ] Calculations Continued Calculate the [OH - ] for a 10.0 M H +. K w = [H + ][OH - ] [OH - ] = K w /[H + ] [OH -] = 1.0 x 10 -14 M 2 /10.0 M [OH - ] = [OH - ] = 1.0 x 10 -15 M

22. K w &  H At 60 o C, the value of K w is 1 x 10 -13 for the dissociation of water: 2 H 2 O (l) H 3 O + (aq) + OH - (aq) Is this reaction exothermic or endothermic? Endothermic -- K w increased with temperature.

23. The pH Scale pH =  log[H + ] pH in water usually ranges from 0 to 14. K w = 1.00  10  14 = [H + ] [OH  ] pK w = 14.00 = pH + pOH As pH rises, pOH falls (sum = 14.00).

24. pH & [H + ] OH - H3O+H3O+ H3O+H3O+ H3O+H3O+ 1x 10 -14 1 x 10 -7 1 x 10 0 1 x 10 -7 1 x 10 -14 pH = 0 pH = 7pH = 14

25. Logarithms -log 1.00 x 10 -7 = 7.000 7.000 characteristicmantissa The number of significant digits in 1.00 x 10 -7 is three, therefore, the log has three decimal places. The mantissa represents the log of 1.00 and the characteristic represents the exponent 7.

26. pH scale and pH values for common substances. A pH of 1 is 100 times more acidic than a pH of 3.

27. pH Calculations What is the pOH, [H + ], & [OH - ] for human blood with a pH of 7.41? pH + pOH = 14.00 pOH = 14.00 - pH pOH = 14.00 - 7.41 pOH = 6.59

28. pH Calculations Continued What is the pOH, [H + ], & [OH - ] for human blood with a pH of 7.41? pH = - log [H + ] [H + ] = antilog (-pH) [H + ] = antilog (-7.41) [H + ] = 3.9 x 10 -8 M Note: The number of significant figures in the antilog is equal to the number of decimal places in the pH.

29. pH Calculations Continued What is the pOH, [H + ], & [OH - ] for human blood with a pH of 7.41? pOH = - log [OH - ] [OH - ] = antilog (-pOH) [OH - ] = antilog (-6.59) [OH - ] = 2.6 x 10 -7 M Note: The number of significant figures in the antilog is equal to the number of decimal places in the pOH.

30. pH of Strong Acid Solutions Calculate the pH of a 0.10 M HNO 3 solution. Major species are: H +, NO 3 -, and H 2 O Sources of H + are from HNO 3 and H 2 O -- amount from water is insignificant.  [H + ] = 0.10 M pH = - log [H + ] pH = - log [0.10] pH = - log [0.10] pH = 1.00 pH = 1.00 Note: The number of significant figures in the [H + ] is the same as the decimal places in the pH.

31. pH & Significant Figures log log # Significant Figures -------> # decimal places <------- inv log pH = - log [H + ][H + ] = inv log (-pH) [H + ] = 1.0 x 10 -5 MpH = 5.00

32. 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.

33. 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.” x can be neglected when concentration is 2 powers of 10 (100x) greater than K a or K b. -Verify assumptions using 5% rule. -Calculate [H + ] and pH.

34. pH of Weak Acid Solutions Calculate the pH of a 0.100 M HOCl solution. Major species: HOCl and HOH K a HOCl = 3.5 x 10 -8 & K a HOH = 1.0 x 10 -14  HOCl will be only significant source of [H + ]. K a = 3.5 x 10 -8 = [H + ][OCl - ]/[HOCl]

35. pH of Weak Acid Solutions Continued ICE ICE [HOCl] [OCl - ] [H + ] [HOCl] [OCl - ] [H + ] Initial (mol/L) 0.100 0 0 Change (mol/L) - x + x + x Equil. (mol/L) 0.100 - x 0 + x 0 + x

36. pH of Weak Acid Solutions Continued K a = 3.5 x 10 -8 = [H + ][OCl - ]/[HOCl] 3.5 x 10 -8 = [x][x]/[0.100 - x] K a is more than 100 x smaller than concentration, x can be neglected in the denominator. K a = 3.5 x 10 -8 = [x][x]/[0.100] x 2 = 3.5 x 10 -9 x = 5.9 x 10 -5 M

37. pH of Weak Acid Solutions Continued Approximation check: % dissociation = (x/[HA] o ) (100%) % dissociation = (x/[HOCl] o ) (100%) % dissociation = (5.9 x 10 -5 /0.100)(100%) % dissociation = 0.059 % This is much less than 5 % and therefore the approximation was valid.

38. Percent Dissociation (Ionization) The percent dissociation calculation is exactly the same as the one to check the 5 % approximation. See Sample Exercise 14.10 on pages 678 and 679.

39. % Dissociation Calculations In a 0.100 M lactic acid solution (HC 3 H 5 O 3 ), lactic acid is 3.7 % dissociated. Calculate the K a for this acid. Major species: HC 3 H 5 O 3 & HOH HC 3 H 5 O 3(aq) H + (aq) + C 3 H 5 O 3 - (aq) K a = [H + ][C 3 H 5 O 3 - ]/ [HC 3 H 5 O 3 ]

40. % Dissociation Calculations Continued ICE ICE [HC 3 H 5 O 3 ] [C 3 H 5 O 3 - ] [H + ] [HC 3 H 5 O 3 ] [C 3 H 5 O 3 - ] [H + ] Initial (M) 0.10 0 0 Change (M) - 3.7 x 10 -3 + 3.7 x 10 -3 + 3.7 x 10 -3 Equil. (M) 0.10 + 3.7 x 10 -3 + 3.7 x 10 -3

41. % Dissociation Calculations Continued K a = [H + ][C 3 H 5 O 3 - ]/ [HC 3 H 5 O 3 ] K a = [3.7 x 10 -3 ] 2 / [0.10] K a = 1.4 x 10 -4

42. The effect of dilution on the % dissociation and [H + ] of a weak acid solution.

43. Bases Bases are often called alkalis because they often contain alkali or alkaline earth metals. “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)

44. Bases (continued) weak = very little dissociation (or reaction with water) H 3 CNH 2 (aq) + H 2 O(l)  H 3 CNH 3 + (aq) + OH  (aq) See Table 14.3 on page 685 for K b values of common bases. K b calculations are identical to K a calculations.

45. Polyprotic Acids... can furnish more than one proton (H + ) to the solution. See Table 14.4 on page 689 for Ka values for common polyprotic acids. Know Sample Exercises 14.15 & 14.16 on pages 689-692.

46. Acid-Base Properties of Salts

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

48. The effect of the number of attached oxygen on the H-O bond in a series of chlorine oxyacids.

49. Oxides Acidic Oxides (Acid Anhydrides): -O  X bond is strong and covalent. SO 2, NO 2, CrO 3 Basic Oxides (Basic Anhydrides): -O  X bond is ionic. K 2 O, CaO

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