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CHE 116: General Chemistry

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1 CHE 116: General Chemistry
CHAPTER SIXTEEN Copyright © Tyna L. Heise All Rights Reserved

2 Acids and Bases: Review
Properties of Acids sour taste change with litmus Properties of Bases bitter taste change with litmus

3 Acids and Bases: Review
scientists have recognized that all acids contain hydrogen, but not all hydrogen bearing compounds are acids Svante Arrhenius - linked acid behavior with the presence of an H+ and base behavior with the presence of an OH-

4 Bronsted-Lowry Acids and Bases
Arrhenius’ definition is useful, but restricts acid base reactions to aqueous conditions Johannes Bronsted and Thomas Lowry proposed a more general definition which involves the transfer of an H+ ion from one molecule to another

5 Bronsted-Lowry Acids and Bases
H+ ion is simply a proton with no surrounding valence electron. Small particle interacts strongly with the nonbonding pairs of water molecules to form hydrated hydrogen ions chemists use H+ and H3O+ interchangeably

6 Bronsted-Lowry Acids and Bases
Demonstrates the interconnections possible between hydrogenated water Fig 16.1

7 Bronsted-Lowry Acids and Bases
Definitions: Acid - any compound which transfers an H+ to another molecule Base - any compound which accepts a transfer of an H+ from another molecule * an acid and base always work together

8 Bronsted-Lowry Acids and Bases
Definitions: Amphoteric - some substances can be an acid or a base depending on reaction Conjugate Acid Base pairs - two compounds that differ only in the presence of an H+. The molecule with the extra H is the acid.

9 Bronsted-Lowry Acids and Bases
Fig 16.7, 16.8

10 Bronsted-Lowry Acids and Bases
Sample Exercise: Write the formula for the conjugate acid of each of the following: HSO3- F- PO43- CO

11 Bronsted-Lowry Acids and Bases
Sample Exercise: Write the formula for the conjugate acid of each of the following: HSO3- F- PO43- CO Given a base, bases accept H+, so add an H+ to each molecule.

12 Bronsted-Lowry Acids and Bases
Sample Exercise: Write the formula for the conjugate acid of each of the following: H2SO3 HSO3- F- PO43- CO Given a base, bases accept H+, so add an H+ to each molecule.

13 Bronsted-Lowry Acids and Bases
Sample Exercise: Write the formula for the conjugate acid of each of the following: H2SO3 HSO3- HF F- PO43- CO Given a base, bases accept H+, so add an H+ to each molecule.

14 Bronsted-Lowry Acids and Bases
Sample Exercise: Write the formula for the conjugate acid of each of the following: H2SO3 HSO3- HF F- HPO PO43- CO Given a base, bases accept H+, so add an H+ to each molecule.

15 Bronsted-Lowry Acids and Bases
Sample Exercise: Write the formula for the conjugate acid of each of the following: H2SO3 HSO3- HF F- HPO PO43- HCO+ CO Given a base, bases accept H+, so add an H+ to each molecule.

16 Bronsted-Lowry Acids and Bases
Sample Exercise: When lithium oxide, Li2O, is dissolved in water, the solution turns basic from the reaction of the oxide ion, O2-, with water. Write the reaction that occurs, and identify the conjugate acid base pairs.

17 Bronsted-Lowry Acids and Bases
Sample Exercise: When lithium oxide, Li2O, is dissolved in water, the solution turns basic from the reaction of the oxide ion, O2-, with water. Write the reaction that occurs, and identify the conjugate acid base pairs. O2- + H2O  OH- + OH-

18 Bronsted-Lowry Acids and Bases
Sample Exercise: When lithium oxide, Li2O, is dissolved in water, the solution turns basic from the reaction of the oxide ion, O2-, with water. Write the reaction that occurs, and identify the conjugate acid base pairs. O2- + H2O  OH- + OH-

19 Bronsted-Lowry Acids and Bases
Sample Exercise: When lithium oxide, Li2O, is dissolved in water, the solution turns basic from the reaction of the oxide ion, O2-, with water. Write the reaction that occurs, and identify the conjugate acid base pairs. O2- + H2O  OH- + OH- acid base base acid

20 Bronsted-Lowry Acids and Bases
Relative Strengths of Acids and Bases: the more readily a substance donates an H+, the less readily it’s conjugate base will accept one the more readily a substance accepts an H+, the less readily it’s conjugate acid will donate one the stronger one of the substances is, the weaker it’s conjugate

21 Bronsted-Lowry Acids and Bases
Relative Strengths of Acids and Bases: strong acids completely transfer their protons to water, leaving no undissociated molecules weak acids are those that only partly dissociate in aqueous solution and therefore exist in the solution as a mixture of acid molecules and component ions

22 Bronsted-Lowry Acids and Bases
Relative Strengths of Acids and Bases: negligible acids are those that have hydrogen but do not donate them at all, their conjugate bases would be extremely strong, reacting with water to complete their octet and leaving OH- behind. In every acid base reaction, the position of the equilibrium favors transfer of H+ from stronger side to weaker side

23 Bronsted-Lowry Acids and Bases
Fig. 16.4

24 Bronsted-Lowry Acids and Bases
Sample exercise: For each of the following reactions, use Fig to predict whether the equilibrium lies predominantly to the left or right: a) PO43-(aq)+H2O(l)HPO42-(aq)+OH-(aq) b) NH4+(aq)+OH-(aq)  NH3(aq)+H2O(l)

25 Bronsted-Lowry Acids and Bases
Sample exercise: For each of the following reactions, use Fig to predict whether the equilibrium lies predominantly to the left or right: a) PO43-(aq)+H2O(l)HPO42-(aq)+OH-(aq) 2 acids are: H2O and HPO42- 2 bases are: PO43- and OH-

26 Bronsted-Lowry Acids and Bases
Sample exercise: For each of the following reactions, use Fig to predict whether the equilibrium lies predominantly to the left or right: a) PO43-(aq)+H2O(l)HPO42-(aq)+OH-(aq) 2 acids are: H2O and HPO42- 2 bases are: PO43- and OH- red indicates strength

27 Bronsted-Lowry Acids and Bases
Sample exercise: For each of the following reactions, use Fig to predict whether the equilibrium lies predominantly to the left or right: a) PO43-(aq)+H2O(l)HPO42-(aq)+OH-(aq) 2 acids are: H2O and HPO42- 2 bases are: PO43- and OH- reverse reaction favored

28 Bronsted-Lowry Acids and Bases
Sample exercise: For each of the following reactions, use Fig to predict whether the equilibrium lies predominantly to the left or right: a) PO43-(aq)+H2O(l)HPO42-(aq)+OH-(aq) 2 acids are: H2O and HPO42- 2 bases are: PO43- and OH- shifts left

29 Bronsted-Lowry Acids and Bases
Sample exercise: For each of the following reactions, use Fig to predict whether the equilibrium lies predominantly to the left or right: b) NH4+(aq)+OH-(aq)  NH3(aq)+H2O(l)

30 Bronsted-Lowry Acids and Bases
Sample exercise: For each of the following reactions, use Fig to predict whether the equilibrium lies predominantly to the left or right: b) NH4+(aq)+OH-(aq)  NH3(aq)+H2O(l) 2 acids are: NH4+ and H2O 2 bases are: NH3 and OH-

31 Bronsted-Lowry Acids and Bases
Sample exercise: For each of the following reactions, use Fig to predict whether the equilibrium lies predominantly to the left or right: b) NH4+(aq)+OH-(aq)  NH3(aq)+H2O(l) 2 acids are: NH4+ and H2O 2 bases are: NH3 and OH- red indicates strength

32 Bronsted-Lowry Acids and Bases
Sample exercise: For each of the following reactions, use Fig to predict whether the equilibrium lies predominantly to the left or right: b) NH4+(aq)+OH-(aq)  NH3(aq)+H2O(l) 2 acids are: NH4+ and H2O 2 bases are: NH3 and OH- favors forward reaction

33 Bronsted-Lowry Acids and Bases
Sample exercise: For each of the following reactions, use Fig to predict whether the equilibrium lies predominantly to the left or right: b) NH4+(aq)+OH-(aq)  NH3(aq)+H2O(l) 2 acids are: NH4+ and H2O 2 bases are: NH3 and OH- shifts right

34 The Autoionization of Water
One of the most important properties of water is its ability to ac as either a Bronsted acid or Bronsted base, depending on circumstances. One water molecule can donate a proton to another water molecule Fig 16.10

35 The Autoionization of Water
The autoionization of water, although rapid and weak, does exist as an equilibrium, and therefore has an equilibrium constant expression: Keq = [H3O+][OH-] [H2O]2 * because water is a liquid, it can be excluded from the equation...

36 The Autoionization of Water
Keq[H2O]2 = [H3O+][OH-] Kw = [H3O+][OH-] = 1.0 x 10-14 * this equation is not only applicable to water, but to all aqueous solutions, and it is upon this fact that the pH scale was built.

37 The Autoionization of Water
Sample exercise: Indicate whether each of the following solutions is neutral, acidic, or basic: a) [H+] = 2 x 10-5 b) [OH-] = 3 x 10-9 c) [OH-] = 1 x 10-7

38 The Autoionization of Water
Sample exercise: Indicate whether each of the following solutions is neutral, acidic, or basic: a) [H+] = 2 x 10-5 then [OH-] must equal 1.0 x which is x10-5 [OH-] = 5.0 x 10-10

39 The Autoionization of Water
Sample exercise: Indicate whether each of the following solutions is neutral, acidic, or basic: a) [H+] = 2 x 10-5 then [OH-] must equal 1.0 x which is x10-5 [OH-] = 5.0 x 10-10 [H+] > [OH-] so acidic

40 The Autoionization of Water
Sample exercise: Indicate whether each of the following solutions is neutral, acidic, or basic: b) [OH-] = 3 x 10-9 then [H+] must equal 1.0 x which is x10-9 [H+] = 3.3 x 10-6

41 The Autoionization of Water
Sample exercise: Indicate whether each of the following solutions is neutral, acidic, or basic: b) [OH-] = 3 x 10-9 then [H+] must equal 1.0 x which is x10-9 [H+] = 3.3 x 10-6 [H+] > [OH-] so acidic

42 The Autoionization of Water
Sample exercise: Indicate whether each of the following solutions is neutral, acidic, or basic: c) [OH-] = 1 x 10-7 then [H+] must equal 1.0 x which is x10-7 [H+] = 1.0 x 10-7

43 The Autoionization of Water
Sample exercise: Indicate whether each of the following solutions is neutral, acidic, or basic: c) [OH-] = 1 x 10-7 then [H+] must equal 1.0 x which is x10-7 [H+] = 1.0 x 10-7 [H+] = [OH-] so neutral

44 The pH Scale For convenience, we can use a logarithmic version of concentration to turn the very small concentrations of [H+] and [OH-] into whole numbers. p(anything) = - log[anything] p(H) = -log[H+] p(OH) = - log[OH-] ** pH + pOH = 14

45 The pH Scale

46 The pH Scale Common household products and their relative pH’s.

47 The pH Scale Sample exercise: In a sample of lemon juice [H+] is 3.8 x 10-4 M. What is the pH?

48 The pH Scale Sample exercise: In a sample of lemon juice [H+] is 3.8 x 10-4 M. What is the pH? pH = -log[H+]

49 The pH Scale Sample exercise: In a sample of lemon juice [H+] is 3.8 x 10-4 M. What is the pH? pH = -log[H+] pH = -log[3.8 x 10-4]

50 The pH Scale Sample exercise: In a sample of lemon juice [H+] is 3.8 x 10-4 M. What is the pH? pH = -log[H+] pH = -log[3.8 x 10-4] pH = 3.42

51 The pH Scale Sample exercise: A commonly available window-cleaning solution has a [H+] is x 10-9 M. What is the pH?

52 The pH Scale Sample exercise: A commonly available window-cleaning solution has a [H+] is x 10-9 M. What is the pH? pH = -log[H+]

53 The pH Scale Sample exercise: A commonly available window-cleaning solution has a [H+] is x 10-9 M. What is the pH? pH = -log[H+] pH = -log[5.3 x 10-9]

54 The pH Scale Sample exercise: A commonly available window-cleaning solution has a [H+] is x 10-9 M. What is the pH? pH = -log[H+] pH = -log[5.3 x 10-9] pH = 8.28

55 The pH Scale Sample exercise: A solution formed by dissolving an antacid tablet has a pH of Calculate [H+].

56 The pH Scale Sample exercise: A solution formed by dissolving an antacid tablet has a pH of Calculate [H+]. pH = -log[H+]

57 The pH Scale Sample exercise: A solution formed by dissolving an antacid tablet has a pH of Calculate [H+]. pH = -log[H+] 9.18 = -log[H+]

58 The pH Scale Sample exercise: A solution formed by dissolving an antacid tablet has a pH of Calculate [H+]. pH = -log[H+] 9.18 = -log[H+] = [H+]

59 The pH Scale Sample exercise: A solution formed by dissolving an antacid tablet has a pH of Calculate [H+]. pH = -log[H+] 9.18 = -log[H+] = [H+] 6.61 x = [H+]

60 The pH Scale Measuring pH: a pH can be measured quickly and accurately using a pH meter. A pair of electrodes connected to a meter capable of measuring small voltages a voltage which varies with pH is generated when the electrodes are placed in a solution calibrated to give pH

61 The pH Scale Measuring pH: a pH can be measured quickly and accurately using a pH meter. Electrodes come in a variety of shapes and sizes a set of electrodes exists that can be placed inside a human cell acid base indicators can be used, but are much less precise

62 The pH Scale Fig 16.7

63 Strong Acids and Bases Strong acids and bases are strong electrolytes, existing in aqueous solution entirely as ions. Strong Acids HCl HBr HI monoprotic HNO HClO HClO H2SO4 diprotic

64 Strong Acids and Bases Strong acids and bases are strong electrolytes, existing in aqueous solution entirely as ions. Calculating the pH of a solution made up entirely of ions means the [H+] is proportional to [acid]

65 Strong Acids and Bases An aqueous solution of HNO3 has a pH of What is the concentration of the acid?

66 Strong Acids and Bases An aqueous solution of HNO3 has a pH of What is the concentration of the acid? pH = -log[H+]

67 Strong Acids and Bases An aqueous solution of HNO3 has a pH of What is the concentration of the acid? pH = -log[H+] = -log[H+]

68 Strong Acids and Bases An aqueous solution of HNO3 has a pH of What is the concentration of the acid? pH = -log[H+] = -log[H+] = [H+] 2.2 x 10-3 = [H+]

69 Strong Acids and Bases An aqueous solution of HNO3 has a pH of What is the concentration of the acid? pH = -log[H+] = -log[H+] = [H+] x 10-3 = [H+] x 10-3 M H mole HNO mole H+

70 Strong Acids and Bases An aqueous solution of HNO3 has a pH of What is the concentration of the acid? pH = -log[H+] = -log[H+] = [H+] x 10-3 = [H+] x 10-3 M H mole HNO mole H x 10-3 HNO3

71 Strong Acids and Bases The most soluble common bases are the ionic hydroxides of the alkali and alkaline earth metals. Due to the complete dissociation of the base into its ion components makes the pH calculation equally straightforward

72 Strong Acids and Bases Sample exercise: What is the concentration of a solution of KOH for which the pH is 11.89?

73 Strong Acids and Bases Sample exercise: What is the concentration of a solution of KOH for which the pH is 11.89? pH = -log[H+]

74 Strong Acids and Bases Sample exercise: What is the concentration of a solution of KOH for which the pH is 11.89? pH = -log[H+] = -log[H+]

75 Strong Acids and Bases Sample exercise: What is the concentration of a solution of KOH for which the pH is 11.89? pH = -log[H+] = -log[H+] = [H+]

76 Strong Acids and Bases Sample exercise: What is the concentration of a solution of KOH for which the pH is 11.89? pH = -log[H+] = -log[H+] = [H+] x = [H+]

77 Strong Acids and Bases Sample exercise: What is the concentration of a solution of KOH for which the pH is 11.89? pH = -log[H+] = -log[H+] = [H+] x = [H+] x = [OH-] x 10-12

78 Strong Acids and Bases Sample exercise: What is the concentration of a solution of KOH for which the pH is 11.89? pH = -log[H+] = -log[H+] = [H+] x = [H+] x = [OH-] = 7.8 x x 10-12

79 Strong Acids and Bases Sample exercise: What is the concentration of a solution of KOH for which the pH is 11.89? 1.0 x = [OH-] = 7.8 x x x 10-3 M OH mol KOH mol OH-

80 Strong Acids and Bases Sample exercise: What is the concentration of a solution of KOH for which the pH is 11.89? 1.0 x = [OH-] = 7.8 x x x 10-3 M OH mol KOH mol OH x 10-3 M KOH

81 Weak Acids Most acids are weak acids and only partially dissociate in aqueous solution. The extent to which a weak acid dissociates can be expressed using an equilibrium constant for the ionization reaction HX + H2O  H3O+ + X- Ka = [H3O+][X-] [HX] *the larger the Ka the stronger the acid

82 Weak Acids Calculating Ka from pH: a much more complicated calculation is required for the determinations of weak acids, in many cases, due to the extremely small magnitude of the values, some simpler approximations can be made.

83 Weak Acids Sample exercise: Niacin, one of the B vitamins, has the following molecular structure: C O H O N A M solution of niacin has a pH of 3.26 a) What % of the acid is ionized in this solution? b) What is the acid-dissociation constant?

84 Weak Acids Sample exercise: A M solution of niacin has a pH of 3.26 a) What % of the acid is ionized in this solution? pH = -log[H+] = -log[H+] e-3.26 = [H+] x 10-4 = [H+]

85 Weak Acids Sample exercise: A M solution of niacin has a pH of 3.26 a) What % of the acid is ionized in this solution? C6H4NOOH  C6H4NOO- + H+ initial change x x x 10-4 equil x x 10-4

86 Weak Acids Sample exercise: A M solution of niacin has a pH of 3.26 a) What % of the acid is ionized in this solution? % = part/total x 100 = 5.5 x 10-4/ x 100 = 2.8%

87 Weak Acids Sample exercise: A M solution of niacin has a pH of 3.26 b) What is the acid-dissociation constant? C6H4NOOH  C6H4NOO- + H+ Ka = [C6H4NOO- ][H+] [C6H4NOOH] = (5.5 x 10-4 )(5.5 x 10-4 ) = 1.55 x10-5

88 Weak Acids Using Ka to calculate pH:
Using the value of Ka and knowing the initial concentration of the weak acid, we can calculate the concentration of H+(aq). Example: Calculate the pH of a 0.30 M solution of acetic acid. HC2H3O2(aq)  H+(aq) + C2H3O2-(aq)

89 Weak Acids Example: Calculate the pH of a 0.30 M solution of acetic acid. HC2H3O2(aq)  H+(aq) + C2H3O2-(aq) From Table 16.2, Ka = 1.8 x 10-5 Ka = 1.8 x 10-5 = [H+][C2H3O2-] [HC2H3O2] set up data table of concentrations involved...

90 Weak Acids Ka = 1.8 x 10-5 = [H+][C2H3O2-] [HC2H3O2]
set up data table of concentrations involved… [HC2H3O2] [H+] [C2H3O2-] Initial M Change x x x Equilibrium x x x

91 Weak Acids Input concentrations in formula
Ka = 1.8 x 10-5 = [x][x] [0.30 -x] This will lead to a quadratic equation, but we can simplify the problem a bit. All weak acids dissociate so little that we can assume the initial concentration of the acid remains essentially the same, that means we can rewrite the formula to read...

92 Weak Acids Ka = 1.8 x 10-5 = [x][x] [0.30] 1.8 x 10-5 (0.30) = x2
= [H+] pH = -log [H+] = -log[0.0023] = 2.64

93 Weak Acids Sample Exercise: The Ka for niacin is x What is the pH of a M solution of niacin?

94 Weak Acids Sample Exercise: The Ka for niacin is x What is the pH of a M solution of niacin? C6H4NOOH  C6H4NOO- + H+ Ka = 1.5 x10-5 = [C6H4NOO-][H+] [C6H4NOOH]

95 Weak Acids Sample Exercise: The Ka for niacin is x What is the pH of a M solution of niacin? C6H4NOOH C6H4NOO- H+ initial change x x x equilibrium x x x

96 Weak Acids Sample Exercise: The Ka for niacin is x What is the pH of a M solution of niacin? C6H4NOOH  C6H4NOO- + H+ Ka = 1.5 x10-5 = [x][x] [0.010]

97 Weak Acids Sample Exercise: The Ka for niacin is x What is the pH of a M solution of niacin? 1.5 x10-5 [0.010] = x2 1.5 x10-5 [0.010] = x 3.87 x 10-4 = x

98 Weak Acids Sample Exercise: The Ka for niacin is x What is the pH of a M solution of niacin? 3.87 x 10-4 = x 3.87 x 10-4 = [H+] pH = -log[H+] pH = -log[3.87 x 10-4] pH = 3.41

99 Weak Acids The results seen in the two previous examples are typical of weak acids. The lower number of ions produced during the partial dissociation causes less electrical conductivity and a slower reaction rate with metals. Percent ionization is a good way to discover the actual conductivity, however...

100 Weak Acids As the concentration of a weak acid increases, the % ionized decreases.

101 Weak Acids As the concentration of a weak acid increases, the % ionized decreases.

102 Weak Acids Sample Exercise: Calculate the % of niacin molecules ionized in a) the previous exercise b) a 1.0 x 10-3 M solution

103 Weak Acids Sample Exercise: Calculate the % of niacin molecules ionized in a) the previous exercise Our approximation was good so % = part x total = x 10-4 x 100 = 3.9%

104 Weak Acids Sample Exercise: Calculate the % of niacin molecules ionized in b) a 1.0 x 10-3 M solution Ka = 1.5 x10-5 = [x][x] [1.0 x 10-3] 1.5 x10-5 (1.0 x 10-3) = x2 1.2 x 10-4

105 Weak Acids Sample Exercise: Calculate the % of niacin molecules ionized in b) a 1.0 x 10-3 M solution Ka = 1.5 x10-5 = [x][x] [1.0 x 10-3] but, 1.2 x x x10-5 (1.0 x 10-3) = x x 10-3 1.2 x is greater than 5% so use quadratic...

106 Weak Acids Sample Exercise: Calculate the % of niacin molecules ionized in b) a 1.0 x 10-3 M solution Ka = 1.5 x10-5 = [x][x] [1.0 x x] -1.5 x 10-5(1.0 x10-3) x 10-5x + x2 = 0

107 Weak Acids Sample Exercise: Calculate the % of niacin molecules ionized in b) a 1.0 x 10-3 M solution -1.5 x 10-5(1.0 x10-3) x 10-5x + x2 = 0 x = -b ± b2 - 4ac a x =

108 Weak Acids Sample Exercise: Calculate the % of niacin molecules ionized in b) a 1.0 x 10-3 M solution -1.5 x 10-5(1.0 x10-3) x 10-5x + x2 = 0 x = -b ± b2 - 4ac a x = 1.1 x or -1.3 x 10-4

109 Weak Acids Sample Exercise: Calculate the % of niacin molecules ionized in b) a 1.0 x 10-3 M solution x = 1.1 x 10-4 1.1 x 10-4 x x 10-3

110 Weak Acids Sample Exercise: Calculate the % of niacin molecules ionized in b) a 1.0 x 10-3 M solution x = 1.1 x 10-4 1.1 x 10-4 x 100 = 11% x 10-3

111 Weak Acids Polyprotic Acids: many acids have more than one ionizable H atom H2SO3(aq)  H+(aq) + HSO3-(aq) Ka1 HSO3-(aq)  H+(aq) + SO3-2(aq) Ka2 The Ka are labeled according to which proton is dissociating it is always easier to remove the first proton than the second

112 Weak Acids

113 Weak Acids If Ka values differ by 103 or more, only use Ka1 to determine calculations.

114 Weak Acids Sample Exercise: Calculate the pH and concentration of oxalate ion, [C2O42-] in a M solution of oxalic acid.

115 Weak Acids Sample Exercise: Calculate the pH and concentration of oxalate ion, [C2O42-] in a M solution of oxalic acid. H2C2O4  HC2O4- + H+ Ka = 5.9 x 10-2 = [HC2O4- ][H+] [H2C2O4]

116 Weak Acids Sample Exercise: Calculate the pH and concentration of oxalate ion, [C2O42-] in a M solution of oxalic acid. H2C2O4  HC2O4- + H+ strong acid so 100% dissociation 0.020 M H+

117 Weak Acids Sample Exercise: Calculate the pH and concentration of oxalate ion, [C2O42-] in a M solution of oxalic acid. HC2O4-  C2O4-2 + H+ I D x x x E x x x

118 Weak Acids Sample Exercise: Calculate the pH and concentration of oxalate ion, [C2O42-] in a M solution of oxalic acid. Ka = 6.4 x 10-5 = [ x ][x] [ x] use your assumption

119 Weak Acids Sample Exercise: Calculate the pH and concentration of oxalate ion, [C2O42-] in a M solution of oxalic acid. Ka = 6.4 x 10-5 = [0.020 ][x] [0.020] 6.4 x 10-5 = x = [C2O42-]

120 Weak Acids Sample Exercise: Calculate the pH and concentration of oxalate ion, [C2O42-] in a M solution of oxalic acid. [H+] = 0.020

121 Weak Acids Sample Exercise: Calculate the pH and concentration of oxalate ion, [C2O42-] in a M solution of oxalic acid. pH = -log[H+] pH = - log[0.020] pH = 1.70

122 Weak Bases Many substances behave as weak bases in water. Such substances react with water, removing protons from water, leaving the OH- ion behind. NH3 + H2O  NH4+ + OH- Kb = [NH4+][OH-] [NH3] * Kb is the base dissociation constant utilizing the [OH-]

123 Weak Bases * Kb is the base dissociation constant utilizing the [OH-]
bases must contain one or more lone pair to bond with the H+ from water. as before, the larger the Kb the stronger the base stronger base have low pOH, but high pH

124 Weak Bases Sample exercise: Which of the following compounds should produce the highest pH as a 0.05 M solution? A) pyridine B) methylamine C) nitrous acid

125 Weak Bases Sample exercise: Which of the following compounds should produce the highest pH as a 0.05 M solution? A) pyridine Kb = 1.7 x 10-9 B) methylamine Kb = 4.4 x 10-4 C) nitrous acid Kb = 2.2 x 10-11

126 Weak Bases Sample exercise: Which of the following compounds should produce the highest pH as a 0.05 M solution? A) pyridine Kb = 1.7 x 10-9 Kb = 1.7 x 10-9 = [x][x] [0.05] x = [OH-] = 9.2 x 10-6 pOH = 5.0 so pH = 9.0

127 Weak Bases Sample exercise: Which of the following compounds should produce the highest pH as a 0.05 M solution? B) methylamine Kb = 4.4 x 10-4 Kb = 4.4 x 10-4 = [x][x] [0.05] x = [OH-] = 4.6 x 10-3 pOH = 2.32 so pH = 11.68

128 Weak Bases Sample exercise: Which of the following compounds should produce the highest pH as a 0.05 M solution? C) nitrous acid Kb = 2.2 x 10-11 Kb = 2.2 x = [x][x] [0.05] x = [OH-] = 1.0 x 10-6 pOH = 5.97 so pH = 8.02

129 Weak Bases Sample exercise: Which of the following compounds should produce the highest pH as a 0.05 M solution? A) pyridine pH = 9.0 B) methylamine pH = 11.68 C) nitrous acid pH = 8.02

130 Weak Bases Identifying a Weak Base
Neutral substances that have an atom with a nonbonding pair of electrons that can serve as a proton acceptor. Most of these are nitrogen atoms Anions of weak acids

131 Weak Bases Sample exercise: A solution of NH3 in water has a pH of What is the molarity of the solution?

132 Weak Bases Sample exercise: A solution of NH3 in water has a pH of What is the molarity of the solution? pH = so pOH = 3.50

133 Weak Bases Sample exercise: A solution of NH3 in water has a pH of What is the molarity of the solution? pOH = 3.50 NH3 + H20  NH4+ + OH- [OH-] = 3.16 x 10-4

134 Weak Bases Sample exercise: A solution of NH3 in water has a pH of What is the molarity of the solution? NH H20  NH OH- x x x x 10-4 x x x x 10-4

135 Weak Bases Sample exercise: A solution of NH3 in water has a pH of What is the molarity of the solution? NH H20  NH OH- Kb = 1.8 x 10-5 = [3.16 x 10-4][3.16 x 10-4] [x x 10-4]

136 Weak Bases Sample exercise: A solution of NH3 in water has a pH of What is the molarity of the solution? NH H20  NH OH- Kb = 1.8 x 10-5 = [3.16 x 10-4][3.16 x 10-4] [x x 10-4] x = M

137 Relationship Between Ka and Kb
When two reactions are added to give a third reaction, the equilibrium constant for the third reaction is equal to the product of the equilibrium constants for the two added reactants. NH4+(aq)  NH3(aq) + H+(aq) NH3(aq) + H2O(l)  NH4+(aq) + OH-(aq) H2O(l)  H+(aq) + OH-(aq)

138 Relationship Between Ka and Kb
NH4+(aq)  NH3(aq) + H+(aq) NH3(aq) + H2O(l)  NH4+(aq) + OH-(aq) H2O(l)  H+(aq) + OH-(aq) Ka x Kb = Kw pKa + pKb = pKw = 14

139 Relationship Between Ka and Kb
Sample exercise: Which of the following anions has the largest base-dissociation constant? A) NO2- B) PO43- C) N3-

140 Relationship Between Ka and Kb
Sample exercise: Which of the following anions has the largest base-dissociation constant? A) NO2- Ka = 4.5 x 10-4 Ka x Kb = 1.0 x 10-14 Kb = 1.0 x = 2.2 x 10-11 4.5 x 10-4

141 Relationship Between Ka and Kb
Sample exercise: Which of the following anions has the largest base-dissociation constant? B) PO43- Ka = 4.2 x 10-13 Ka x Kb = 1.0 x 10-14 Kb = 1.0 x = 2.4 x 10-2 4.2 x 10-13

142 Relationship Between Ka and Kb
Sample exercise: Which of the following anions has the largest base-dissociation constant? C) N3- Ka = 1.9 x 10-5 Ka x Kb = 1.0 x 10-14 Kb = 1.0 x = 5.2 x 10-10 1.9 x 10-5

143 Relationship Between Ka and Kb
Sample exercise: Which of the following anions has the largest base-dissociation constant? A) NO2- Kb = 2.2 x 10-11 B) PO43- Kb = 2.4 x 10-2 C) N3- Kb = 5.2 x 10-10

144 Relationship Between Ka and Kb
Sample exercise: The base quinoline has a pKa of What is the base dissociation constant for quinoline?

145 Relationship Between Ka and Kb
Sample exercise: The base quinoline has a pKa of What is the base dissociation constant for quinoline? pKa + pKb = 14 x = 14 x = 9.1

146 Relationship Between Ka and Kb
Sample exercise: The base quinoline has a pKa of What is the base dissociation constant for quinoline? pKb = 9.1 pKb = -log[Kb] 9.1 = -log[Kb] [Kb] = 7.9 x 10-10

147 Acid Base Properties of Salt Soln’s
Salt solutions have the potential to be acidic or basic. Hydrolysis of a salt acid base properties are due to the behavior of their cations and anions perform the necessary double replacement reaction and examine the products using your strength rules

148 Acid Base Properties of Salt Soln’s
If a strong acid and strong base are produced, the resultant solution will be neutral. If a strong acid and weak base are produced, the resultant solution will be acidic. If a strong base and a weak acid are produced, the resultant solution will be basic.

149 Acid Base Properties of Salt Soln’s
If a weak acid and weak base are produced, the resultant solution will be dependent on the Ka values.

150 Acid Base Properties of Salt Soln’s
Sample exercise: In each of following, which salt will form the more acidic solution. A) NaNO3, Fe(NO3)3 NaNO3 + H2O  NaOH + HNO3 SB SA

151 Acid Base Properties of Salt Soln’s
Sample exercise: In each of following, which salt will form the more acidic solution. A) NaNO3, Fe(NO3)3 Fe(NO3)3 + 3H2O  Fe(OH)3 + 3HNO3 WB SA

152 Acid Base Properties of Salt Soln’s
Sample exercise: In each of following, which salt will form the more acidic solution. A) NaNO3, Fe(NO3)3 Fe(NO3)3 + 3H2O  Fe(OH)3 + 3HNO3 WB SA

153 Acid Base Properties of Salt Soln’s
Sample exercise: In each of following, which salt will form the more acidic solution. B) KBr, KBrO

154 Acid Base Properties of Salt Soln’s
Sample exercise: In each of following, which salt will form the more acidic solution. B) KBr, KBrO KBr + H2O  KOH + HBr SB SA

155 Acid Base Properties of Salt Soln’s
Sample exercise: In each of following, which salt will form the more acidic solution. B) KBr, KBrO KBrO + H2O  KOH + HBrO SB WA

156 Acid Base Properties of Salt Soln’s
Sample exercise: In each of following, which salt will form the more acidic solution. B) KBr, KBrO

157 Acid-Base Behavior & Chem Structure
How does the chemical structure determine which of the behaviors will be exhibited? Acidic a molecule containing H will transfer a proton only if the H-X bond is polarized like H -- X the stronger the bond the weaker the acid and vice versa

158 Acid-Base Behavior & Chem Structure
How does the chemical structure determine which of the behaviors will be exhibited? Acidic oxyacids exist when the H is attached to an oxygen bonded to a central atom if the OH’s attached are equal in number to the O’s present, acid strength increases with electronegativity

159 Acid-Base Behavior & Chem Structure
How does the chemical structure determine which of the behaviors will be exhibited? Acidic oxyacids exist when the H is attached to an oxygen bonded to a central atom the more O’s present compared to the OH’s, the more polarized the OH bond becomes and the stronger the acid is

160 Acid-Base Behavior & Chem Structure
How does the chemical structure determine which of the behaviors will be exhibited? Acidic carboxylic acids exist when the functional group COOH is present the strength also increases as the number of electronegative atoms in the molecule increase


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