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18-1
Etching with acids
The inside surfaces of these light Acids are used to wash away
bulbs are etched with HF. oxides of silicon and metals during
the production of computer chips.
Neutralization occurs when the H+ ion from the acid and the OH- ion
from the base combine to form water.
18-3
Strong acids dissociate completely into ions in water.
[H3O+][A-]
Kc =
[H2O][HA] stronger acid, higher [H3O+],
larger Ka
[H3O+][A-]
Kc[H2O] = Ka = weaker acid, lower [H3O+],
[HA] smaller Ka
18-4
The extent of dissociation of strong acids
Figure 18.3
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
18-5
The extent of dissociation of weak acids
Figure 18.3 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
18-6
Reaction of zinc with a strong and a weak acid
1 M HCl(aq) 1 M CH3COOH(aq)
Figure 18.4
18-7
Acid strength
decreases down
the table (smaller
Ka values)
18-8
SAMPLE PROBLEM 18.1 Classifying acid and base strength from the
chemical formula
PLAN: Pay attention to the text definitions of acids and bases. Look at O for
acids and for the -COOH group; watch for amine groups and cations
in bases.
18-9
The auto-ionization of water and the pH scale
H2O(l) H2O(l)
[H3O+][OH-]
Kc =
[H2O]2
18-11
The relationship between [H3O+] and [OH-] and the
relative acidity of solutions
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Figure 18.5
18-12
SAMPLE PROBLEM 18.2 Calculating [H3O+] and [OH-] in an aqueous
solution
PLAN: Use the Kw at 25 oC and the [H3O+] to find the corresponding [OH-].
18-13
The pH values of
some familiar
aqueous solutions
pH = -log [H3O+]
Related Expressions
pK = -log K
Figure 18.6
18-14
A low pK corresponds to a high K.
18-15
Relationships
between
[H3O+], QuickTime™ and a
Photo - JPEG decompressor
pH, [OH-] and are needed to see this picture.
pOH
Figure 18.7
18-16
SAMPLE PROBLEM 18.3 Calculating [H3O+], pH, [OH-], and pOH
PLAN: HNO3 is a strong acid so [H3O+] = [HNO3]. Use Kw to find the [OH-]
and then convert to pH and pOH.
SOLUTION: For 2.0 M HNO3, [H3O+] = 2.0 M and -log [H3O+] = -0.30 = pH
[OH-] = Kw/ [H3O+] = 1.0 x 10-14/2.0 = 5.0 x 10-15 M; pOH =
14.30
For 0.3 M HNO3, [H3O+] = 0.30 M and -log [H3O+] = 0.52 = pH
[OH-] = Kw/ [H3O+] = 1.0 x 10-14/0.30 = 3.3 x 10-14 M; pOH = 13.48
18-17
Methods for measuring the pH of an aqueous solution
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Figure 18.8
18-18
The Brønsted-Lowry Definition of Acids and Bases
An acid is a proton donor, that is, any species that donates an H+ ion.
All Arrhenius acids are Brønsted-Lowry acids.
18-19
Proton transfer is the essential feature of a Brønsted-
Lowry acid-base reaction
lone pair
binds H+
+
+
HCl H 2O Cl- H 3 O+
(acid, H+ donor) (base, H+ acceptor)
lone pair
binds H+
+
+
Every acid has a conjugate base, and every base has a conjugate acid.
18-21
The conjugate base of the pair has one fewer H and one more
negative charge than the acid.
The conjugate acid of the pair has one more H and one less
negative charge than the base.
18-22
Table 18.4 Conjugate Pairs in Some Acid-Base Reactions
conjugate pair
conjugate pair
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18-23
SAMPLE PROBLEM 18.4 Identifying conjugate acid-base pairs
18-24
Relative Acid-Base Strength and Reaction Direction
a b b a
H2S + NH3 HS- + NH4+ Kc > 1
a b b a
HF + H2O F - + H3 O + Kc < 1
18-25
Strengths of
conjugate acid-
base pairs
Figure 18.10
18-26
SAMPLE PROBLEM 18.5 Predicting the net direction of an acid-base
reaction
PROBLEM: Predict the net direction and whether Ka is greater or less than 1
for each of the following reactions (assume equal initial
concentrations of all species):
(a) H2PO4-(aq) + NH3(aq) HPO42-(aq) + NH4+(aq)
PLAN: Identify the conjugate acid-base pairs and then consult Figure 18.10
to determine the relative strength of each. The stronger the species,
the more preponderant will be its conjugate.
18-28
Find the Ka of a weak acid from the pH of its
SAMPLE PROBLEM 18.6
solution
Ka = [H3O+][PAc-]
[HPAc]
18-29
SAMPLE PROBLEM 18.6 (continued)
[H3O+] = 10-pH = 2.5 x 10-3 M, which is >> 10-7 ([H3O+] from water)
SOLUTION: [HPr]
initial 0.10 - 0 0
change -x - +x +x
equilibrium 0.10 - x - x x
[H3O+][Pr-] (x)2
Ka = 1.3 x 10-5 = =
[HPr] 0.10
5 = 1.1 x 10-3 M = [H3O+]
x (0.10)(1.3x10 )
Checking assumptions:
[HPr]diss: 1.1 x 10-3 M / 0.10 M x 100 = 1.1%
18-32
As the initial concentration of a weak acid decreases, the
percent dissociation of the acid increases!
[HA]dissociated
percent HA dissociation = x 100
[HA]initial
18-33
Polyprotic Acids that contain more
acids than one ionizable proton
18-34
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18-35
Why are the Ka values successively smaller as more H+ ions
dissociate from a polyprotic acid like phosphoric acid?
18-36
SAMPLE PROBLEM 18.8 Calculating equilibrium concentrations for a
polyprotic acid
[HAsc-][H3O +]
SOLUTION:
Ka1 =
H2Asc(aq) + H2O(l) HAsc-(aq) + H3O+(aq) [H2Asc]
= 1.0 x 10-5
[Asc2-][H3O +]
HAsc-(aq) + H2O(l) Asc2-(aq) + H3O+(aq) Ka2 =
[HAsc-]
= 5 x 10-12
18-37
SAMPLE PROBLEM 18.8 (continued)
initial 0.050 - 0 0
change -x - +x +x
equilibrium 0.050 - x - x x
change -x - +x +x
equilibrium 7.1 x 10-4 - x - x x
+
x = [(7.1 x 10-4)(5 x 10-12)]0.5 = 6 x 10-8 M = [H3O ]
18-38
We can ignore the hydronium ion generated by second ionization.
18-39
Weak Bases: Their Relationship to Weak Acids
[BH+][OH-]
Kc =
[B][H2O]
Base-dissociation constant, Kb
[BH+][OH-]
Kb =
[B]
18-40
Main Classes of Weak Bases: nitrogen-containing molecules (ammonia
and amines) and anions of weak acids.
Ammonia:
Amines:
RNH2, R2NH and R3N: all have a lone pair of electrons that
can bind a proton donated by an acid
18-41
Abstraction of a proton from water by methylamine
lone pair
binds H+
CH3NH2 H2O
methylamine
OH-
CH3NH3+
Figure 18.11
methylammonium ion
18-42 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Base strength
decreases
down
the table
(smaller
Kb values)
18-43
SAMPLE PROBLEM 18.9 Determining pH from Kb and initial [B]
SOLUTION:
concentration (CH3)2NH(aq) + H2O(l) (CH3)2NH2+(aq) + OH-(aq)
initial 1.50 - 0 0
change -x - +x +x
equilibrium 1.50 - x - x x
18-44
SAMPLE PROBLEM 18.9 (continued)
[(CH3)2NH2+][OH-]
Kb = 5.9 x 10-4 =
[(CH3)2NH]
(x) (x)
5.9 x 10-4 = x = 3.0 x 10-2 M = [OH-]
1.5 M
18-45
Anions of Weak Acids as Weak
Bases
A-(aq) + H2O(l) HA(aq) + OH-(aq)
18-46
SAMPLE PROBLEM 18.10 Determining the pH of a solution of A-
SOLUTION:
concentration Ac-(aq) + H2O(l) HAc(aq) + OH-(aq)
initial 0.25 - 0 0
change -x - +x +x
equilibrium 0.25 - x - x x
18-47
SAMPLE PROBLEM 18.10 (continued)
18-48
Molecular Properties and Acid Strength
18-49
The effect of atomic and molecular properties on
non-metal hydride acidity
electronegativity
6A(16) 7A(17) increases, acidity
increases
bond strength decreases,
H 2O HF
acidity increases
H 2S HCl
H2Se HBr
H2Te HI
Figure 18.12
18-50 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
The relative strengths of oxoacids
H O I > H O Br > H O Cl
H O Cl << H O Cl O
number of O atoms increases, O
acidity increases
Figure 18.13 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
18-51
Acidity of Hydrated Metal Ions
Aqueous solutions of certain metal ions are acidic because the hydrated
metal ion transfers an H+ ion to water.
Generalized Reactions
18-52
The acidic behavior of the hydrated Al3+ ion
H 2O H 3 O+
Al(H2O)63+ Al(H2O)5OH2+
Figure 18.14
18-53 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
high charge
QuickTime™ and a
Photo - JPEG decompressor
are needed to see this picture.
and small size
enhance acidity
18-54
Acid-Base Properties of Salt Solutions
A. Salts That Yield Neutral Solutions: the anion of a strong acid and
the cation of a strong base (the ions do not react with water)
The anion of a strong acid is a much weaker base than water (HNO3).
The cation of a strong base only becomes hydrated (NaOH).
18-55
B. Salts That Yield Acidic Solutions: (1) the anion of a strong acid
and the cation of a weak base (the cation acts as a weak acid); (2) small,
highly charged metal ions; (3) cations of strong bases and anions of
polyprotic acids with another ionizable proton.
18-56
C. Salts That Yield Basic Solutions: the anion of a weak acid and the
cation of a strong base (the anion acts as a weak base)
18-57
18-58
SAMPLE PROBLEM 18.11 Predicting the relative acidity of salt solutions
18-59
Salts of Weakly Acidic Cations and Weakly Basic Anions
example: NH4HS
18-60
SAMPLE PROBLEM 18.12 Predicting the relative acidity of salt solutions
from Ka and Kb of the ions
SOLUTION:
Zn(H2O)62+(aq) + H2O(l) Zn(H2O)5OH+(aq) + H3O+(aq)
Ka Zn(H2O)62+ = 1 x 10-9
18-61
The Leveling Effect
Any acid stronger than H3O+ donates its proton to H2O, and
any base stronger than OH- accepts a proton from H2O; thus,
water exerts a leveling effect (levels the strengths of all strong
acids and bases).
18-62
Three Definitions of Acids and Bases
18-63
The Lewis Acid-Base Definition
F The adduct
H F
H contains a
B + N new covalent
B N bond.
F HH F
F F HH
M(H2O)42+(aq)
M2 +
H2O(l) adduct
18-64
Lewis Acids with Electron-Deficient Atoms
Lewis acids
ROR’ + AlCl3 R-O-R’ contain (or can
adduct
base acid generate) a
AlCl3 vacant orbital.
18-65
Figure
18.15
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18-66
SAMPLE PROBLEM 18.13 Identifying Lewis acids and bases
PROBLEM: Identify the Lewis acids and Lewis bases in the following reactions:
SOLUTION: acceptor
(a) H+ + OH- H2O
donor
donor
(b) Cl- + BCl3 BCl4-
acceptor
acceptor
18-67