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Chapter 15

Acids and Bases: A Second Look

Brady and Senese


5th Edition

1
Index
15.1 Brønsted-Lowry acids and bases exchange
protons
15.2 Strengths of Brønsted acids and bases follow
periodic trends
15.3 Lewis acids and bases involve coordinate
covalent bonds
15.4 Elements and their oxides demonstrate acid-
base properties
15.5 pH is a measure of the acidity of a solution
15.6 Strong acids and bases are fully dissociated in
solution
2
Brønsted Acid/Base Reactions Transfer H+
• Acid is a proton donor
• Base is a proton acceptor
• NaOH + HCl → NaCl + H2O
HCl is the acid – it donate a proton to the base
NaOH is the base – it accepts the proton from the acid
• In water:
H2O + HCl → H3O+ + Cl–
HCl is the acid – it donate a proton to the base
Water is the base – it accepts the proton from the acid

15.1 Brønsted-Lowry acids and bases exchange protons


3
Conjugate Acid-Base Pairs
• Products differ by one H+ from the reactants to
form conjugate
• Conjugate acid-base pairs differ by one H+.
conjugate pair

acid base
HCN(aq) + OH-(aq) → H2O(l) + CN-(aq)
base acid

conjugate pair

• Note that in the conjugate pairs, the acid has one


more H+ than its conjugate base
15.1 Brønsted-Lowry acids and bases exchange protons
4
Learning Check
Identify the conjugate partner for each

Conjugate Base Conjugate Acid

Cl- HCl
NH3 NH4+
C2H3O2- HC2H3O2
CN- HCN
F- HF

15.1 Brønsted-Lowry acids and bases exchange protons 5


Your Turn
How many of the following pairs are conjugate
pairs:
i. HCN/CN- ii. HCl/Cl- iii. H2S/S2-
A. 1
B. 2
C. 3
D. None of them are conjugate

15.1 Brønsted-Lowry acids and bases exchange protons 6


Amphoteric Substances
• Amphoteric (amphiprotic) substances are able to
act either as Brønsted acid or Brønsted base
• Anions containing H+ (except HSO4-) have the
ability to act as either.
• In water they have a preference, and are usually
basic
 In stronger bases, act as acids
 In stronger acids, act as bases
• Water is amphoteric

15.1 Brønsted-Lowry acids and bases exchange protons 7


Learning Check
• Write a reaction that shows that HCO3- is a
Brønsted acid when reacted with OH-(aq).
HCO3-(aq) + OH-(aq) ↔ H2O + CO32-(aq)

• Write a reaction that shows that HCO3- is a


Brønsted base when reacted with H3O+(aq).
HCO3-(aq) + H3O+(aq) ↔ H2CO3(aq) + H2O

15.1 Brønsted-Lowry acids and bases exchange protons 8


Your Turn
How many of the following are amphoteric?
HC2H3O2 , H2PO42-, HSO4-
A. 1
B. 2
C. 3
D. None of these

15.1 Brønsted-Lowry acids and bases exchange protons 9


Acid/Base Strengths in Aqueous Solution

• Hydronium ion (H3O+) is the strongest acid in an


aqueous solution: stronger acids react completely
with water to give H3O+
• Hydroxide ion (OH-) is the strongest possible base
in an aqueous solution: stronger bases react
completely with water to give OH-
• The reaction of all stronger acids and bases in
water to the same strength is termed leveling
• Acid-base reactions occur in favor of the weaker
acid and base

15.2 Strengths of Brønsted acids and bases follow periodic trends 10


Conjugate Pairs Have Reciprocal Strengths
• The stronger the acid,
the weaker its
conjugate base
• The stronger the base,
the weaker its
conjugate acid
• Strong acids are
ionized 100%: their
anions are
extraordinarily poor
bases - most are
neutral
15.2 Strengths of Brønsted acids and bases follow periodic trends 11
Identify the Preferred Direction of the Following

• H3O+(aq) + CO32-(aq) ↔ HCO-3(aq) + H2O

• NH4+(aq) + HCO3- (aq) ↔ NH3(aq) + H2CO3(aq)

• Cl-(aq) + HCN(aq) ↔ HCl(aq) + CN-(aq)

H2 O HCN NH4+ H2CO3 H 3 O+


Increasing Acid Strength

15.2 Strengths of Brønsted acids and bases follow periodic trends 12


Your Turn
Which reaction is not written as in the preferred
direction?

A. HC2H3O2 + H2AsO4- ↔ H3AsO4 + C2H3O2-


B. H3AsO4 + H2AsO3- ↔ H2AsO4- + H3AsO3
C. HC2H3O2 + H2AsO3- ↔ C2H3O2- + H3AsO3
D. All are preferred as written
H2O H3AsO3 HC2H3O2 H3AsO4 H3O+
Increasing Acid Strength

15.2 Strengths of Brønsted acids and bases follow periodic trends 13


Periodic Trends of Binary Acids (HnX)
• As we read left to right in a period, increasing
electronegativity of X makes the H–X bond more
polar
• Acid strength increases with increasing polarity
• As we read top to bottom in a group, the acid
strength increases due to increasing bond length of
the HX bond due to increased radius of the anion, X

15.2 Strengths of Brønsted acids and bases follow periodic trends 14


Learning Check
Which is a stronger acid?
δ- δ-
• H2S or H2O
δ+ δ+

δ-
• CH4 or NH3
δ+

δ+ δ+
• HF or HI
δ-
δ-

15.2 Strengths of Brønsted acids and bases follow periodic trends 15


Oxoacids A(O)m(OH)n
• Increase in strength as the
electronegativity of the central
atom, A, increases
• Increase in strength as the δ+
δ
number of oxygen atoms on -
δ+
(hence the oxidation state of)
the central atom, A, increases δ
-
• Electrical induction through
the central atom weakens
strength of the bond to H

15.2 Strengths of Brønsted acids and bases follow periodic trends 16


Learning Check
Which is a stronger acid?
• H2SO4 or H3PO4 H2SO4
• HNO3 or H3PO4 HNO3
• H2SO4 or H2SO3 H2SO4
• HNO3 or HNO2 HNO3

15.2 Strengths of Brønsted acids and bases follow periodic trends 17


Anions of Oxoacids are Basic
• Oxygen atoms are electron withdrawing, thus the
charge on an anion is located on the lone oxygens
• The more oxygen atoms there are that share the same
charge, the less basic is the anion
• The weaker the base behavior of the anion, the
greater the strength of the conjugate acid
- - 2O
3O
share
share
the (-)
the (-)
charge
charge

15.2 Strengths of Brønsted acids and bases follow periodic trends 18


Your Turn
Which statement about acid strength is false:
A. Binary acids get stronger as the anion gets larger
B. Oxoacids get stronger as the central atom
increases in size
C. Oxoacids acidic strength increases with
increasing oxidation state
D. None of these are false

15.2 Strengths of Brønsted acids and bases follow periodic trends 19


Lewis Acid/Base Reactions
• Lewis acids accept an electron pair to form
coordinate covalent bonds
• Lewis bases donate lone pairs of electron to form
coordinate covalent bonds
• Neutralization is the formation of a coordinate
covalent bond between the donor and acceptor

15.3 Lewis acids and bases involve coordinate covalent bonds 20


Lewis Acids and Bases
• Lewis acids
 Molecules and ions with incomplete valence shells
 Molecules and ions with multiple bonds that can
be shifted to accept electrons
 Molecules or ions with central atoms that can
accommodate additional electrons
• Lewis bases
 Molecules and ions that have complete valence
shells with unshared electrons

15.3 Lewis acids and bases involve coordinate covalent bonds 21


Learning Check
Identify the Lewis acid and base in the following:

• NH3 + H+ ↔ NH4+

• F- + BF3 ↔ BF4-
-
-
: :

: :

15.3 Lewis acids and bases involve coordinate covalent bonds 22


Your Turn
This is an example of a Lewis acid-base reaction.
A. True
B. False
C. Not enough information is available

15.3 Lewis acids and bases involve coordinate covalent bonds 23


Elements and Their Oxides: Acids and Bases
• Nonmetal oxides are usually acidic anhydrides:
 SO3(g), N2O5(g), and CO2(g)
• Metal oxides react with water to form hydroxide
ions are basic anhydrides
 Na2O and CaO
• Other metal oxides which are insoluble in water,
can react with acids
 Fe2O3(s) + 6H+ → 2Fe3+(aq) + 3H2O

15.4 Elements and their oxides demonstrate acid-base properties 24


Hydrated Metal Ions Can Act as Weak Acids
• Electron deficiency of metal cations causes them
to induce electrons towards it from the water of
hydration
• M(H2O)mn+ + H2O ↔ M(H2O)m-1OH(n-1)+ + H3O+
• The higher the charge density, the more acidic the
metal.
• Acidity increases left to right in a period.
• Acidity decreases top to bottom in a group.
ionic charge
charge density 
ionic volume
15.4 Elements and their oxides demonstrate acid-base properties 25
Oxides Can be Acidic
• The higher the oxidation state of the metal,
the greater the acidity
 Example Al2O3 acts as an acid in the presence
of OH-
 CrO3 is strongly acidic in water
• Non-metal oxides are acidic anhydrides
 SO2 + H2O → H2SO3

15.4 Elements and their oxides demonstrate acid-base properties 26


Auto-ionization of Water (Kw)
• Water ionizes to a very small extent (Kw = 10-14 at
room temperature) according to the following
reaction:
 H2O(l) + H2O(l) ↔ H3O+(aq) + OH-(aq)
• Since water is present in all aqueous solutions, the
Kw equilibrium exists in all aqueous solutions.
 Kw = [H3O+ ][OH-]
 Kw = 10-14 at 25 °C
• When [H3O+] = [OH-], the solution is neutral.

15.5 pH is a measure of the acidity of a solution 27


pH and Kw

• pH is defined for aqueous solutions only, and is


temperature dependent, because Kw is
• pH = -log[H3O+]
• It derives from the auto ionization of water.
Kw = [H3O][OH-]
log Kw = log[H3O+] + log[OH-]
-log Kw = -log[H3O+] - log[OH-]
pKw = pH + pOH
• pH > 7 is basic; pH = 7 is neutral; pH < 7 is acidic

15.5 pH is a measure of the acidity of a solution 28


Indicators Help Us Estimate pH

15.5 pH is a measure of the acidity of a solution 29


Learning Check
Complete the following with the missing data

[OH-] [H3O+] pH

3.2 × 10-3 M 3.1×10-12 M 11.51


4.3 × 10-10 M 2.3 × 10-5 M 4.63
1.5 × 10-2 M 6.7 × 10-13 M 12.17
3.92 × 10-9 M 2.55 × 10-6 M 5.593

15.5 pH is a measure of the acidity of a solution 30


Using pH
• pH = -log[H3O+]
• To find [H3O+]:
 -pH = log[H3O+]
 10-pH = [H3O+]
• When the pH of a solution is 12.24,
 10-12.24 = [H3O+]
 5.7 × 10-13 M
 Note that the number of significant figures in the log
value is equal to the number of digits to the right of the
decimal place.

15.5 pH is a measure of the acidity of a solution 31


Learning Check
• Complete the following with the missing data

pH pOH [H3O+]

2.33 11.67 4.7 × 10-3


12.11 1.89 7.8 × 10-13

15.5 pH is a measure of the acidity of a solution 32


Your Turn!
What is the pH of a solution that has a [OH-] = 1.2 ×
10-3 M?
A. 2.92
B. 11.08
C. 1.20
D. None of the above

15.5 pH is a measure of the acidity of a solution 33


Strong Acids Ionize 100% in Water
• As the substances are placed into water, they form
H3O+.
• The H3O+ formed by the acid suppresses water’s
ionization (if [acid] > 10-7 M)
• The pH can be calculated from the concentration
of H3O+ produced by the strong acid
• The reaction of strong acids occurs irreversibly, so
we show the reaction with a → instead of using a
double arrow

15.6 Strong acids and bases are fully dissociated in solution 34


Learning Check
What is the pH of 0.1 M HCl?

HCl(aq) + H2O(l) → H3O+(aq) + Cl-(aq)


I 0.1 N/A 0 0
C -0.1 -0.1 0.1 0.1
E 0 N/A 0.1 0.1

pH = -log (0.1) = 1

15.6 Strong acids and bases are fully dissociated in solution 35


Strong Bases Dissociate 100% In Water
• They are strong electrolytes that form OH- when
dissolved
• pOH can be calculated from the [OH-] from the
solution
• Water’s contribution is negligible if the base is
sufficiently concentrated [OH-] > 10-7 M

15.6 Strong acids and bases are fully dissociated in solution 36


Learning Check
What is the pH of 0.5 M Ca(OH)2?

Ca(OH)2(aq) → Ca2+(aq) + 2OH-(aq)


I 0.5 0 0
C -0.5 + 0.5 + 0.5 × 2
E 0 0.5 1.0

pOH = -log (1.0) = 0


pH = 14

15.6 Strong acids and bases are fully dissociated in solution 37


Your Turn
What is the pH of a 0.50 M solution of NaOH?
A. 0.50
B. 0.30
C. 13.70
D. None of these

15.6 Strong acids and bases are fully dissociated in solution 38

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