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1 Homework problems added to syllabus:
Friday 9/7 Ch. 8, # 52, 56, 60 Monday 9/10 Ch. 8, # 62, 66

2 Buffer Solutions

3 Buffer Solutions Buffer solutions aid in maintaining a consistent pH range for a reaction.

4 The buffer acts as a sponge for
excess acid or base.

5 Buffer Solutions Changes in reaction pH can be caused by:

6 Buffer Solutions Changes in reaction pH can be caused by: Acidic or basic product

7 A + B HC + D

8 A + B HC + D HC(aq) + H2O H3O+(aq) + C-(aq)

9 A + B HC + D HC(aq) + H2O H3O+(aq) + C-(aq) [HC] [H3O+]

10 Buffer Solutions Changes in reaction pH can be caused by: Acidic or basic product Acidic or basic reactant

11 A + NH3(aq) + H2O(l) A NH3(aq) + NH4+(aq) + OH-(aq)

12 A + NH3(aq) + H2O(l) A NH3(aq) + NH4+(aq) + OH-(aq) [NH3]

13 A + NH3(aq) + H2O(l) A NH3(aq) + NH4+(aq) + OH-(aq) [NH3] [OH-]

14 A buffer consists of a weak acid and
its conjugate base or a weak base and its conjugate acid.

15 A buffer consists of a weak acid and
its conjugate base or a weak base and its conjugate acid. A conjugate base or conjugate acid does not necessarily have to come from solution of an acid or base.

16 Weak acid HA(aq) + H2O(aq) H3O+(aq) + A-(aq)

17 Weak acid HA(aq) + H2O(aq) H3O+(aq) + A-(aq) [H3O+][A-] Ka = [HA]

18 Weak acid HA(aq) + H2O(aq) H3O+(aq) + A-(aq) [H3O+][A-] Ka = [HA] [HA] [H3O+] = Ka [A-]

19 Weak acid HA(aq) + H2O(aq) H3O+(aq) + A-(aq) [HA] [H3O+] = Ka [A-] pH = -log10[H3O+]

20 Weak acid HA(aq) + H2O(aq) H3O+(aq) + A-(aq) [HA] [H3O+] = Ka [A-] pH = -log10[H3O+] [HA] pH  [A-]

21 Weak acid HA(aq) + H2O(aq) H3O+(aq) + A-(aq) [HA] [H3O+] = Ka [A-] If [HA] and [A-] are large (  1 M ), the ratio will change slowly if dilute (0.1 M or less) strong acid is added.

22 CH3COOH M NaCH3COO 0.5 M

23 CH3COOH M NaCH3COO 0.5 M CH3COOH(aq) + H2O(l) H3O+(aq) + CH3COO-(aq)

24 CH3COOH M NaCH3COO 0.5 M CH3COOH(aq) + H2O(l) H3O+(aq) + CH3COO-(aq) CH3COOH(aq) + H2O(l) + NaCH3COO (aq) Na+(aq) + H3O+(aq) + 2 CH3COO-(aq)

25 CH3COOH M NaCH3COO 0.5 M CH3COOH(aq) + H2O(l) + NaCH3COO (aq) Na+(aq) + H3O+(aq) + 2 CH3COO-(aq)

26 CH3COOH M Na CH3COO 0.5 M CH3COOH(aq) + H2O(l) + NaCH3COO (aq) Na+(aq) + H3O+(aq) + 2 CH3COO-(aq)

27 CH3COOH M NaCH3COO 0.5 M CH3COOH(aq) + H2O(l) + NaCH3COO (aq) Na+(aq) + H3O+(aq) + 2 CH3COO-(aq) [CH3COOH] [H3O+] [CH3COO-] Start 

28 CH3COOH M NaCH3COO 0.5 M CH3COOH(aq) + H2O(l) + NaCH3COO (aq) Na+(aq) + H3O+(aq) + 2 CH3COO-(aq) [CH3COOH] [H3O+] [CH3COO-] Start  Change y y y

29 CH3COOH M Na CH3COO 0.5 M CH3COOH(aq) + H2O(l) + NaCH3COO (aq) Na+(aq) + H3O+(aq) + 2 CH3COO-(aq) [CH3COOH] [H3O+] [CH3COO-] Start  Change y y y Equilibrium 1.0-y y y

30 [CH3COOH] [H3O+] [CH3COO-]
Start  Change y y y Equilibrium 1.0-y y y [H3O+][CH3COO-] Ka = [CH3COOH]

31 [CH3COOH] [H3O+] [CH3COO-]
Start  Change y y y Equilibrium 1.0-y y y [H3O+][CH3COO-] (y)(0.5+y) Ka = = (1-y) [CH3COOH] Ka = 1.8 x 10-5

32 [CH3COOH] [H3O+] [CH3COO-]
Start  Change y y y Equilibrium 1.0-y y y (y)(0.5+y) 1.8 x 10-5 = (1-y) Assume y << 1

33 [CH3COOH] [H3O+] [CH3COO-]
Start  Change y y y Equilibrium 1.0-y y y (y)(0.5) 1.8 x 10-5 = (1) Assume y << 1

34 [CH3COOH] [H3O+] [CH3COO-]
Start  Change y y y Equilibrium 1.0-y y y y = 2( 1.8 x 10-5) = 3.6 x 10-5

35 [CH3COOH] [H3O+] [CH3COO-]
Start  Change y y y Equilibrium 1.0-y y y y = 2( 1.8 x 10-5) = 3.6 x 10-5 pH = -log10(3.6x10-5) = 4.44

36 [CH3COOH] [H3O+] [CH3COO-]
Start  Change y y y Equilibrium 1.0-y y y y = 2( 1.8 x 10-5) = 3.6 x 10-5 pH = -log10(3.6x10-5) = 4.44 buffer pH = 2.37 for 1 M CH3COOH

37 pH = -log10(3.6x10-5) = 4.44 buffer pH = 2.37 for 1 M CH3COOH [H3O+][CH3COO-] Ka = [CH3COOH] CH3COOH(aq) + H2O(l) H3O+(aq) + CH3COO-(aq)

38 pH = -log10(3.6x10-5) = 4.44 buffer pH = 2.37 for 1 M CH3COOH [H3O+][CH3COO-] Ka = [CH3COOH] [CH3COOH] [H3O+] = Ka [CH3COO-]

39 Prepare buffer solution of CH3COOH and
CH3COO- and include 0.1 M HCl.

40 Prepare buffer solution of CH3COOH and
CH3COO- and include 0.1 M HCl. HCl(aq) + H2O(aq) H3O+ + Cl-(aq)

41 Prepare buffer solution of CH3COOH and
CH3COO- and include 0.1 M HCl. HCl(aq) + H2O(aq) H3O+ + Cl-(aq) HCl is a strong acid % dissociation

42 Prepare buffer solution of CH3COOH and
CH3COO- and include 0.1 M HCl. HCl(aq) + H2O(aq) H3O+ + Cl-(aq) HCl is a strong acid % dissociation H3O+(aq)+ CH3COO-(aq) CH3COOH(aq) + H2O(l)

43 Prepare buffer solution of CH3COOH and
CH3COO- and include 0.1 M HCl. HCl(aq) + H2O(aq) H3O+ + Cl-(aq) HCl is a strong acid % dissociation H3O+(aq)+ CH3COO-(aq) CH3COOH(aq) + H2O(l) Ka of CH3COOH favors products

44 Assume all HCl reacts with CH3COO-
to form an extra 0.1 M CH3COOH and reduces CH3COO- by 0.1 M.

45 [CH3COOH] [H3O+] [CH3COO-]
Start  Change y y y Equilibrium 1.1-y y y [CH3COOH] [H3O+] = Ka [CH3COO-]

46 [CH3COOH] [H3O+] [CH3COO-]
Start  Change y y y Equilibrium 1.1-y y y [CH3COOH] [H3O+] = Ka [CH3COO-] (1.1-y) [H3O+] = Ka = (0.4+y)

47 [CH3COOH] [H3O+] [CH3COO-]
Start  Change y y y Equilibrium 1.1-y y y [CH3COOH] [H3O+] = Ka [CH3COO-] (1.1-y) 1.1 [H3O+] = Ka = Ka (0.4+y) 0.4

48 [CH3COOH] [H3O+] [CH3COO-]
Start  Change y y y Equilibrium 1.1-y y y [CH3COOH] [H3O+] = Ka [CH3COO-] 1.1 [H3O+] = Ka = (1.8 x 10-5)(2.75)= 0.4

49 [CH3COOH] [H3O+] [CH3COO-]
Start  Change y y y Equilibrium 1.1-y y y [CH3COOH] [H3O+] = Ka [CH3COO-] 1.1 [H3O+] = Ka = (1.8 x 10-5)(2.75)= 4.95 x 10-5 0.4

50 [CH3COOH] [H3O+] [CH3COO-]
Start  Change y y y Equilibrium 1.1-y y y [CH3COOH] [H3O+] = Ka [CH3COO-] [H3O+] = 4.95 x 10-5 pH = 4.31

51 pH 1.0 M CH3COOH pH 1.0 M CH3COOH/ 0.5 M CH3COO 0.5 M CH3COO-/ 0.1 M HCl

52 pH 1.0 M CH3COOH pH 1.0 M CH3COOH/ 0.5 M CH3COO 0.5 M CH3COO-/ 0.1 M HCl The pH decreases due to the increase in CH3COOH concentration.

53 pH 1.0 M CH3COOH pH 1.0 M CH3COOH/ 0.5 M CH3COO 0.5 M CH3COO-/ 0.1 M HCl pH 0.1 M HCl

54 The action of the buffer involves the
reaction of the strong acid with the conjugate base of a weak acid.

55 The action of the buffer involves the
reaction of the strong acid with the conjugate base of a weak acid. This generates a weak acid of roughly the equivalent of the added strong acid.

56 This increased amount of weak acid
decreases the pH of the solution, but it is a much smaller decrease than would have occurred with the addition of strong acid only.

57 CH3COOH(aq) + H2O(l) + NaCH3COO (aq)
Na+(aq) + H3O+(aq) + 2 CH3COO-(aq)

58 Prepare same buffer with 0.5 M HCl

59 [CH3COOH] [H3O+] [CH3COO-]
Start  Change y y y Equilibrium 1.5-y y y [CH3COOH] [H3O+] = Ka [CH3COO-]

60 [CH3COOH] [H3O+] [CH3COO-]
Start  Change y y y Equilibrium 1.5-y y y [CH3COOH] [H3O+] = Ka [CH3COO-] y2 = Ka[CH3COOH]

61 [CH3COOH] [H3O+] [CH3COO-]
Start  Change y y y Equilibrium 1.5-y y y [CH3COOH] [H3O+] = Ka [CH3COO-] y2 = Ka[CH3COOH] = (1.8 x 10-5)(1.5)

62 [CH3COOH] [H3O+] [CH3COO-]
Start  Change y y y Equilibrium 1.5-y y y [CH3COOH] [H3O+] = Ka [CH3COO-] y2 = Ka[CH3COOH] = (1.8 x 10-5)(1.5) = 2.7 x 10-5

63 [CH3COOH] [H3O+] [CH3COO-]
Start  Change y y y Equilibrium 1.5-y y y [CH3COOH] [H3O+] = Ka [CH3COO-] y2 = 2.7 x 10-5 y = 5.20 x 10-3

64 [CH3COOH] [H3O+] [CH3COO-]
Start  Change y y y Equilibrium 1.5-y y y [CH3COOH] [H3O+] = Ka [CH3COO-] y2 = 2.7 x 10-5 y = 5.20 x 10-3 pH = 2.28

65 pH 1.0 M CH3COOH pH 1.0 M CH3COOH/ 0.5 M CH3COO 0.5 M CH3COO-/ 0.1 M HCl pH buffer M HCl pH 0.1 M HCl

66 [CH3COOH] [H3O+] [CH3COO-]
Start  Change y y y Equilibrium 1.0-y y y [H3O+][CH3COO-] Ka = [CH3COOH] Add 0.51 M HCl

67 [CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.5-y y y [H3O+][CH3COO-] Ka = [CH3COOH] Add 0.51 M HCl

68 [CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.5-y y y (0.01+y)(y) [H3O+][CH3COO-] Ka = = [CH3COOH] (1.5-y)

69 [CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.5-y y y (0.01+y)(y) [H3O+][CH3COO-] Ka = = = (1.5-y) [CH3COOH] (0.01y+y2) = (1.5-y)

70 [CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.5-y y y (0.01+y)(y) [H3O+][CH3COO-] Ka = = = (1.5-y) [CH3COOH] y y x 10-5 = 0

71 [CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.5-y y y (0.01+y)(y) [H3O+][CH3COO-] Ka = = = (1.5-y) [CH3COOH] y y x 10-5 = 0 y = 9.93 x 10-3

72 [CH3COOH] [H3O+] [CH3COO-]
Start Change y y y Equilibrium 1.5-y y y (0.01+y)(y) [H3O+][CH3COO-] Ka = = = (1.5-y) [CH3COOH] y y x 10-5 = 0 y = 9.93 x 10-3 pH = 2.00

73 pH 1.0 M CH3COOH pH 1.0 M CH3COOH/ 0.5 M CH3COO 0.5 M CH3COO-/ 0.1 M HCl pH buffer M HCl pH buffer M HCl pH 0.01 M HCl

74

75 Additional conjugate base will create
a solution which can react with more acid before the pH decreases appreciably.

76 Additional conjugate base will create
a solution which can react with more acid before the pH decreases appreciably. This implies that the weak acid concentration should be raised as well.

77 Determining correct acid-conjugate
base combination and concentration for a desired buffer pH.

78 Determining correct acid-conjugate
base combination and concentration for a desired buffer pH. Ka > pH < 7

79 Determining correct acid-conjugate
base combination and concentration for a desired buffer pH. Ka > pH < 7 Ka < pH > 7

80 HA(aq) + H2O(aq) H3O+(aq) + A-(aq)
Ka = [HA]

81 HA(aq) + H2O(aq) H3O+(aq) + A-(aq)
Ka = [HA] [A- ]o,[HA]o = original concentrations

82 HA(aq) + H2O(aq) H3O+(aq) + A-(aq)
Ka = [HA] [A- ]o,[HA]o = original concentrations [HA]  [HA]o [A-]  [A-]o

83 HA(aq) + H2O(aq) H3O+(aq) + A-(aq)
[H3O+][A-]o Ka = [HA] [HA]o

84 HA(aq) + H2O(aq) H3O+(aq) + A-(aq)
[H3O+][A-]o Ka = [HA] [HA]o [HA]o [H3O+]  Ka [A-]o

85 HA(aq) + H2O(aq) H3O+(aq) + A-(aq)
[H3O+][A-]o Ka = [HA] [HA]o [HA]o [H3O+]  Ka [A-]o [HA]o [H3O+]  Ka -log10 = [A-]o

86 HA(aq) + H2O(aq) H3O+(aq) + A-(aq)
[HA]o [H3O+]  Ka [A-]o [HA]o -log10 [H3O+]  Ka = [A-]o [HA]o pH  pKa -log10 [A-]o

87 HA(aq) + H2O(aq) H3O+(aq) + A-(aq)
[HA]o pH  pKa -log10 [A-]o Henderson-Hasselbach equation

88 [CH3COOH] [H3O+] [CH3COO-]
Start  Change y y y Equilibrium 1.0-y y y [CH3COOH] [H3O+] = Ka [CH3COO-] Henderson-Hasselbach equation pH = -log10(3.6x10-5) = 4.44

89 [HA]o pH  pKa -log10 [A-]o To prepare a buffer of a given pH, start with an acid with pKa  pH.

90 [HA]o pH  pKa -log10 [A-]o To prepare a buffer of a given pH, start with an acid with pKa  pH. [HA]o  1 [A-]o

91 [HA]o pH  pKa -log10 [A-]o To prepare a buffer of a given pH, start with an acid with pKa  pH. [HA]o Log10(1) = 0  1 [A-]o

92 [HA]o pH  pKa -log10 [A-]o Design a buffer with a pH of 9.20

93 [NH4+]o pH  pKa -log10 [NH3]o Design a buffer with a pH of 9.20 pKa NH4+ = 9.25

94 [NH4+]o pH  pKa -log10 [NH3]o [NH4+] log10 = pKa - pH [NH3] Design a buffer with a pH of 9.20 pKa NH4+ = 9.25

95 [NH4+]o pH  pKa -log10 [NH3]o [NH4+] log10 = = 0.05 [NH3] Design a buffer with a pH of 9.20 pKa NH4+ = 9.25

96 [NH4+]o pH  pKa -log10 [NH3]o [NH4+] log10 = = 0.05 [NH3] [NH4+] = [NH3]

97 [NH4+]o pH  pKa -log10 [NH3]o [NH4+] log10 = = 0.05 [NH3] [NH4+] = = 1.12 [NH3]

98 [NH4+]o pH  pKa -log10 [NH3]o [NH4+] = = 1.12 [NH3] [NH4Cl] = 1.12 M [NH3] = 1.0 M

99 [NH4+]o pH  pKa -log10 [NH3]o [NH4+] = = 1.12 [NH3] [NH4Cl] = 1.12 M [NH4Cl] = M [NH3] = 1.0 M [NH3] = 0.10 M

100 Buffers in biological systems

101 Buffers in biological systems
Human blood pH

102 Buffers in biological systems
Human blood pH Buffer system Carbonic acid - hydrogen carbonate

103 Buffer system Carbonic acid - hydrogen carbonate H3O+(aq) + HCO3-(aq) H2CO3(aq) + H2O(l) CO2(g) + H2O(l)

104 H3O+(aq) + HCO3-(aq) H2CO3(aq) + H2O(l)
CO2(g) + H2O(l) pKa1 H2CO3 = 6.1 Human blood pH

105 H3O+(aq) + HCO3-(aq) H2CO3(aq) + H2O(l)
CO2(g) + H2O(l) pKa1 H2CO3 = 6.1 Human blood pH [HCO3-] Must significantly differ from 1 [H2CO3]

106 [HCO3-] calculate [H2CO3]

107 [HCO3-] calculate [H2CO3] [A-]o pH  pKa +log10 [HA]o Henderson-Hasselbach equation

108 [HCO3-] calculate [H2CO3] [A-]o pH  pKa +log10 [HA]o [A-]o log10 = pH - pKa [HA]o

109 pH = 7.4 [HCO3-] calculate [H2CO3] pKa = 6.1 [A-]o log10 = pH - pKa [HA]o

110 pH = 7.4 [HCO3-] calculate [H2CO3] pKa = 6.1 [A-]o log10 = pH - pKa [HA]o [A-]o log10 = = 1.3 [HA]o

111 pH = 7.4 [HCO3-] calculate [H2CO3] pKa = 6.1 [A-]o log10 = pH - pKa [HA]o [A-]o log10 = = 1.3 [HA]o 101.3 = 19.95

112 pH = 7.4 [HCO3-] calculate [H2CO3] pKa = 6.1 [A-]o log10 = pKb - pH [HA]o [A-]o log10 = = 0.4 [HA]o [A-]o  20 [HA]o

113 pH = 7.4 [HCO3-] calculate [H2CO3] pKa = 6.1 [A-]o log10 = pKb - pH [HA]o [A-]o log10 = = 0.4 [HA]o [HCO3-] = M [A-]o  20 [H2CO3] = M [HA]o

114 [HCO3-] = M [H2CO3] = M High acid capacity Low base capacity

115 H3O+(aq) + HCO3-(aq) H2CO3(aq) + H2O(l)
CO2(g) + H2O(l) pH < acidosis

116 H3O+(aq) + HCO3-(aq) H2CO3(aq) + H2O(l)
CO2(g) + H2O(l) pH < acidosis Failure to eliminate CO2

117 H3O+(aq) + HCO3-(aq) H2CO3(aq) + H2O(l)
CO2(g) + H2O(l) pH < acidosis Failure to eliminate CO2 Heavy exercise

118 H3O+(aq) + HCO3-(aq) H2CO3(aq) + H2O(l)
CO2(g) + H2O(l) pH > alkalosis

119 H3O+(aq) + HCO3-(aq) H2CO3(aq) + H2O(l)
CO2(g) + H2O(l) pH > alkalosis Eliminating too much CO2 - hyperventilation

120 H3O+(aq) + HCO3-(aq) H2CO3(aq) + H2O(l)
CO2(g) + H2O(l) pH > alkalosis Eliminating too much CO2 - hyperventilation Vomiting - removes acid from stomach


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