Chapter 15

Chapter 15
Acids and Bases
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Education.
Acids
Have a sour taste. Vinegar owes its taste to acetic acid.
Citrus fruits contain citric acid.
React with certain metals to produce hydrogen gas.
React with carbonates and bicarbonates to produce

carbon dioxide gas.
Bases
Have a bitter taste.
Feel slippery. Many soaps contain bases.
© McGraw-Hill Education. 15-2

Brønsted Acids and Bases
A Brønsted acid is a proton donor

A Brønsted base is a proton acceptor
NH 3 (aq)  H 2 O(l )  NH 4 (aq)  OH  ( aq)

base acid  acid base
conjugate conjugate
base acid
acid base

Example 15.1 (1 of 2)
Strategy
Remember that a conjugate base always has one fewer H

atom and one more negative charge (or one fewer positive
charge) than the formula of the corresponding acid.
Solution
NH3 has one fewer H atom and one fewer positive charge
than NH 4 .F
has one fewer H atom and one more negative charge than
HF. Therefore, the conjugate acid-base pairs are
 1 NH 4 and NH 3 and  2  HF and F .
Identify the conjugate acid-base pairs in the reaction

between ammonia and hydrofluoric acid in aqueous
solution
NH 3 (aq )  HF(aq )  NH 4 ( aq)  F ( aq )

Acid-Base Properties of Water
H 2 O(l )  H  (aq)  OH  (aq)

autoionization of water
Jump to long description

conjugate
base acid
H 2 O  H 2 O  H O  OH 
3

acid conjugate
base

The Ion Product of Water

 H 

 
 OH 

H 2 O  l   H  aq   OH  aq  K c 
 
 H 2O   constant
 H2 O
K c  H 2 O   K w   H   OH  
The ion-product constant (Kw) is the product of

 
the molar concentrations of H and OH ions at a
particular temperature. Solution Is
At 25C  H    OH   neutral
K w   H    OH    1.0  1014  H    OH   acidic

 H    OH   basic

The concentration of OH ions in a certain
household ammonia cleaning solution is 0.0025 M.
Calculate the concentration of H  ions.

Strategy
We are given the concentration of the OH  ions and

asked to calculate [H  ]. The relationship between
[H  ] and [OH  ] in water or an aqueous solution is
given by the ion-product of water, Kw [Equation
(15.3)].

Solution
Rearranging Equation (15.3), we write
14
K 1.0 10
[H  ]  W

  4.0  10 12
M
[OH ] 0.0025
Check
 H    OH  
Because the solution is basic, as we would
expect from the earlier discussion of the reaction of
ammonia with water.
pH – A Measure of Acidity
pH  log  H  
Solution Is At 25C
neutral  H    OH    H    1.0  1.0 7 pH  7
acidic  H    OH    H    1.0  1.0 7 pH  7
basic  H    OH    H    1.0  1.0 7 pH  7
pH   H   

Other Important Relationships
Table 15.1 The
pHs of Some
Common Fluids.
pOH   log OH  
Sample pH Value  H    OH    K w  1.0  10 14
Gastric juice in the stomach 1.0-2.0
Lemon juice 2.4  log  H    log OH    14.00
Vinegar 3.0
Grapefruit juice 3.2 pH  pOH  14.00
Orange juice 3.5
Urine 4.8-7.5
Water exposed to air* 5.5
Saliva 6.4-6.9
Milk 6.5
Pure water 7.0
Blood 7.35-7.45
Tears 7.4
Milk of magnesia 10.6
Household ammonia 11.5
*Water exposed to air for a long pH Meter

period of time absorbs atmospheric
CO2 to form carbonic acid, H2CO3.

The concentration of H ions in a bottle of table wine
4
was 3.2  10 M right after the cork was removed.
Only half of the wine was consumed. The other half,
after it had been standing open to the air for a month,
was found to have a hydrogen ion concentration
3
equal to 1.0  10 M. Calculate the pH of the wine on
these two occasions.

Strategy
We are given the H  ion concentration and asked to

calculate the pH of the solution. What is the
definition of pH?

Solution

According to Equation (15.4), pH   log[H ].
 4
When the bottle was first opened, [H ]  3.2 10 M ,
Which we substitute in Equation (15.4)
pH  log[H  ]
 log(3.2  104 )  3.49
On the second occasion,[H  ]  1.0  10 3 M,so that
pH   log(1.0  103 )  3.00

Comment
The increase in hydrogen ion concentration (or

decrease in pH) is largely the result of the conversion
of some of the alcohol (ethanol) to acetic acid, a
reaction that takes place in the presence of molecular
oxygen.

The pH of rainwater collected in a certain region of

the northeastern United States on a particular day

was 4.82. Calculate the H ion concentration of the
rainwater.

Strategy
Here we are given the pH of a solution and asked to

calculate  H   .
Because pH is defined as pH   log  H
 

 , we can solve for 
 
H 
by taking the antilog of the pH; that is,  H    10 pH ,

as shown in Equation (15.5).

Solution
From Equation (15.4)

pH  log  H    4.82
Therefore,
log  H     4.82
To calculate  H   , We need to take the antilog of  4.82
 H    104.82  1.5  105 M

Check
Because the pH is between 4 and 5, we can expect

 H   to be between 1  104 M and1  105 M.
Therefore, the answer is reasonable.

In a NaOH solution OH   is 2.9  104 M.
Calculate the pH of the solution.

Strategy
Solving this problem takes two steps. First, we need to calculate

pOH using Equation (15.7). Next, we use Equation (15.9) to
calculate the pH of the solution.
Solution
We use Equation (15.7):

pOH   log OH  
  log  2.9  104 
 3.54
Now we use Equation (15.9):
pH + pOH = 14.00
pH = 14.00 − pOH
= 14.00 − 3.54 = 10.46
Alternatively, we can use the ion-product constant of water,

K w  [H  ] [OH  ] to calculate [H  ],
and then we can calculate the pH from the  H  
Check
The answer shows that the solution is basic (pH > 7), which is
consistent with a NaOH solution.
Electrolytes (1 of 3)
Strong Electrolyte – 100% dissociation
NaCl( s ) 
H2O
 Na  (aq )  Cl ( aq)
Weak Electrolyte – not completely dissociated

CH 3COOH  CH 3COO  ( aq)  H  ( aq)
Strong Acids are strong electrolytes

HCl ( aq )  H 2O (l )  H 3O  ( aq)  Cl  ( aq)
HNO3 (aq)  H 2O (l )  H 3O  (aq)  NO 3 ( aq)
HClO 4 (aq)  H 2O (l )  H 3O  ( aq)  ClO 4 ( aq)
H 2SO 4 ( aq)  H 2O (l )  H 3O  ( aq)  HSO 4 ( aq)

Weak Acids are weak electrolytes
HF(aq )  H 2 O (l )  H 3O  (aq)  F (aq)
HNO 2 (aq)  H 2 O (l )  H 3O  ( aq)  NO 2 (aq)
HSO 4 (aq )  H 2 O (l )  H 3O  ( aq)  SO 42 (aq)
H 2 O (l )  H 2 O (l )  H 3O  ( aq)  OH  ( aq)
Strong Bases are strong electrolytes

NaOH ( s ) 
H 2O
 Na  (aq)  OH  (aq)
KOH ( s ) 
H 2O
 K  ( aq)  OH  ( aq)
Ba (OH) 2 ( s ) 
H 2O
 Ba 2+ (aq)  2OH  (aq)
Weak Bases are weak electrolytes
F ( aq)  H 2 O (l )  OH  ( aq)  HF( aq)

NO 2 (aq)  H 2 O (l )  OH  ( aq)  HNO 2 ( aq)
Conjugate acid-base pairs:

The conjugate base of a strong acid has no measurable
strength.
H 3O  is the strongest acid that can exist in aqueous
solution.

The OH ion is the strongest base that can exist in
aqueous solution.

Acids and Conjugate Bases

Strong vs. Weak Acids
Strong Acid (HCl) Weak Acid (HF)
Jump to long description Jump to long description

Calculate the pH of a
 a  1.0  103 M HCl solution
 b  0.020 M Ba  OH  2 solution

Strategy
Keep in mind that HCl is a strong acid and Ba(OH)2 is a

strong base. Thus, these species are completely ionized
and no HCl or Ba(OH)2 will be left in solution.
Solution
a) The ionization of HCl is
HCl ( aq)  H  ( aq)  Cl  ( aq)

 
The concentrations of all the species (HCl, H , and Cl )
before and after ionization can be represented as follows:
HCl (aq)  H  (aq)  Cl  (aq)
Initial (M) : 1.0 103 0.0 0.0
Change (M) : 1.0 103 1.0 103 1.0 103
Final (M) 0.0 1.0 103 1.0  103
A positive (+) change represents an increase and a negative

(−) change indicates a decrease in concentration. Thus,
[H  ]  1.0  103 M
pH   log(1.0 103 )
 3.00
 b  Ba  OH  2 is a strong base; each Ba  OH  2 unit produces two
OH  ions :
Ba  OH  2  aq   Ba 2  aq   2OH   aq 
The changes in the concentrations of all the

species can be represented as follows:
Ba  OH  2  aq   Ba 2  aq   2OH   aq 
Initial (M): 0.020 0.00 0.00
Change (M): −0.020 +0.020 +2(0.020)
Final (M): 0.00 0.020 0.040

Thus,
OH    0.040 M
pOH   log 0.040  1.40
Therefore, from Equation (15.8),
pH = 14.00 − pOH
= 14.00 − 1.40
=12.60
Check
Note that in both (a) and (b) we have neglected the contribution of the
autoionization of water to
 H   and OH   because 1.0  10 7 M is so small compared with

1.0  103 M and 0.040 M.
Predict the direction of the following reaction in

aqueous solution:
HNO 2  aq   CN   aq   HCN  aq   NO 2  aq 

Strategy
The problem is to determine whether, at equilibrium, the

reaction will be shifted to the right, favoring HCN and NO 2 ,
or to the left, favoring HNO 2 and CN  . Which of the two is a
stronger acid and hence a stronger proton donor: HNO2 or
HCN? Which of the two is a stronger base and hence a
 
stronger proton acceptor: CN or NO 2 ?
Remember that the stronger the acid, the weaker its
conjugate base.

Solution
In Table 15.2 we see that HNO2 is a stronger acid

 
than HCN. Thus, CN is a stronger base than NO 2.
The net reaction will proceed from left to right as
written because HNO2 is a better proton donor

than HCN (and CN is a better proton acceptor

than NO 2 ).

Weak Acids (HA) and Acid Ionization
Constants
HA  aq   H 2 O  l   H 3O   aq   A   aq 
HA  aq   H   aq   A   aq 
 H    A  
Ka 
 HA 
Ka is the acid ionization constant
Ka  weak acid strength 

Ionization Constants of Some Weak Acids
(1 of 2)
Jump to Long Description

(2 of 2)
Solving weak acid ionization problems:
1. Identify the major species that can affect the pH.
In most cases, you can ignore the autoionization of water.
 
Ignore [OH ] because it is determined by [H ].
2. Use ICE to express the equilibrium concentrations in
terms of single unknown x.
3. Write Ka in terms of equilibrium concentrations. Solve for
x by the approximation method. If approximation is not
valid, solve for x exactly.
4. Calculate concentrations of all species and/or pH of the
solution.

Calculate the pH of a 0.036 M nitrous acid (HNO2)

solution:
HNO 2  aq   H   aq   NO 2  aq 

Strategy
Recall that a weak acid only partially ionizes in water. We are given
the initial concentration of a weak acid and asked to calculate the pH
of the solution at equilibrium. It is helpful to make a sketch to keep
track of the pertinent species.
As in Example 15.6, we ignore the ionization of H2O so the major source


of H 
ions is the acid. The concentration of OH ions is very small as we
would expect from an acidic solution so it is present as a minor species.
Step 3: From Table 15.3 we write
 H    NO 2 
Ka 
 HNO2 
4 x2
4.5  10 
0.036  x
Applying the approximation 0.036 − x ≈ 0.036,

we obtain
4 x2 x2
4.5  10  
0.36  x 0.036
x 2  1.62  10 5
x
 4.0  103 M
Solution
We follow the procedure already outlined.
Step 1: The species that can affect the pH of the solution are
HNO 2 , H  , and the conjugate base NO 2 .Weignore
water's contribution to  H   .
Step 2: Letting x be the equilibrium concentration of H  and

NO2 ions in mol L, we summarize :
HNO 2  aq   H   aq   NO 2  aq 
Initial (M): 0.036 0.00 0.00
Change (M): −x +x +x
Equilibrium (M): 0.036 − x X x

To test the approximation,
4.0  103 M
 100%  11%
0.036 M
Because this is greater than 5%, our approximation is not

valid and we must solve the quadratic equation, as follows:
x 2  4.5  104 x  1.62  105  0

4
 4.5  10   4.5  10 4 2
 4  1   1.62  105 
x
2  1
 3.8  103 M or  4.3  103 M

The second solution is physically impossible, because the
concentration of ions produced as a result of ionization cannot be
negative. Therefore, the solution is given by the positive root,
3
x
.  3.8  10 M.
Step 4: At equilibrium
 H    3.8  103 M
pH   log  3.8  103 
Check  2.42
Note that the calculated pH indicates that the solution is acidic, which
is what we would expect for a weak acid solution. Compare the
calculated pH with that of a 0.036 M strong acid solution such as HCl
to convince yourself of the difference between a strong acid and a
weak acid.
The pH of a 0.10 M solution of formic acid (HCOOH)

is 2.39. What is the Ka of the acid?

Strategy
Formic acid is a weak acid. It only partially ionizes in water. Note that
the concentration of formic acid refers to the initial concentration,
before ionization has started. The pH of the solution, on the other
hand, refers to the equilibrium state. To calculate Ka, then, we need
to know the concentrations of all three species: [H  ,  HCOO ], and
 
[HCOOH] at equilibrium. As usual, we ignore the ionization of water.

The following sketch summarizes the situation.
Jump to Long Description

Solution
We proceed as follows.

Step 1: The major species in solution are HCOOH, H , and the

conjugate base HCOO .
Step 2: First we need to calculate the hydrogen ion concentration from

the pH value
pH   log  H  
2.39   log  H  
Taking the antilog of both sides, we get

 H    102.39  4.1  103 M
Next we summarize the changes:
HCOOH  aq   H   aq   HCOO   aq 
Initial (M) : 0.10 0.00 0.00
Change (M) :  4.1  103  4.1  10 3  4.1  10 3
Equilibrium (M) :  0.10  4.1  10 3  4.1  10 3 4.1  103

Note that because the pH and hence the H ion
concentration is known, it follows that we also know the

concentrations of HCOOH and HCOO at equilibrium.

Step 3: The ionization constant of formic acid is given by
 H    HCOO  
Ka 
 HCOOH 

 4.1  10 3
 4.1  10 3

 0.10  4.1  10 3

 1.8  104
Check
The Ka value differs slightly from the one listed in Table
15.3 because of the rounding-off procedure we used in
the calculation.
Percent Ionization
Ionized acid concentration at equilibrium
percent ionization   100%
Initial concentration of acids
For a monoprotic acid HA,

 H  
Percent Ionization   100%  HA  0  initial concentration
 HA  0

Weak Bases and Base Ionization
Constants
NH 3  aq   H 2O  l   NH 4  aq   OH   aq 
 NH 4   OH  
Kb 
 NH3 
Kb is the base ionization constant
K b  weak base strength 
Solve weak base problems like weak acids except

solve for OH   instead of H   
Ionization Constants of Some Weak
Bases

What is the pH of a 0.40 M ammonia solution?

Strategy
The procedure here is similar to the one used for a weak acid (see
Example 15.8). From the ionization of ammonia, we see that the
major species in solution at equilibrium are NH 3 , NH 4 , and OH  .
The hydrogen ion concentration is very small as we would expect
from a basic solution, so it is present as a minor species. As
before, we ignore the ionization of water. We make a sketch to
keep track of the pertinent species as follows:

Solution
We proceed according to the following steps.
Step 1: The major species in an ammonia solution are NH 3 , NH 4 , and OH  .

We ignore the very small contribution to OH  concentration by
water.
Step 2: Letting x be the equilibrium concentration of

NH 4 and OH  ions in mol L, we summarize :
NH 3  aq   H 2O  l   NH 4  aq   OH   aq 
Initial (M): 0.40 0.00 0.00
Equilibrium (M): 0.40 − x x x

Step 3: Table 15.4 gives us 𝐾b:
 NH 4   OH 
Kb 
 NH3 
2
x
1.8  105 
0.40  x
Applying the approximation 0.40 − 𝑥 ≈ 0.40, we obtain
2 2
x x
1.8  105  
0.40  x 0.40
x 2  7.2  106
x  2.7  10 3 M
To test the approximation, we write
2.7  103 M
 100%  0.68%
0.40 M
Therefore, the approximation is valid.

Step 4: At equilibrium, OH   2.7  10 M.Thus,
 3
pOH   log  2.7  103 

 2.57
pH  14.00  2.75
 11.43

Check
Note that the pH calculated is basic, which is what we

would expect from a weak base solution. Compare the
calculated pH with that of a 0.40 M strong base
solution, such as KOH, to convince yourself of the
difference between a strong base and a weak base.

Ionization Constants of Conjugate Acid-
Base Pairs
HA  aq   H   aq   A   aq  Ka
A   aq   H 2 O  l   OH   aq   HA  aq  K b
H 2 O  l   H   aq   OH   aq  Kw
Ka Kb  K w
Weak Acid and Its Conjugate Base

Kw Kw
Ka  Kb 
Kb Ka
Diprotic and Triprotic Acids
May yield more than one hydrogen ion per molecule.
Ionize in a stepwise manner; that is, they lose one proton at a time.
An ionization constant expression can be written for each ionization stage.
Consequently, two or more equilibrium constant expressions must often be
used to calculate the concentrations of species in the acid solution.
 H    HCO3 
H 2 CO3  aq   H   aq   HCO3  aq  K a1 
 H 2CO3 
 H   CO32 
HCO  aq   H

3

 aq   CO  aq 
2
3 Ka2 
 HCO3 

Ionization Constants of Some Polyprotic
Acids

Oxalic acid (H2C2O4) is a poisonous substance used

chiefly as a bleaching and cleansing agent (for
example, to remove bathtub rings). Calculate the
concentrations of all the species present at equilibrium
in a 0.10 M solution.

Strategy
Determining the equilibrium concentrations of the

species of a diprotic acid in aqueous solution is more
involved than for a monoprotic acid. We follow the
same procedure as that used for a monoprotic acid for
each stage, as in Example 15.8. Note that the
conjugate base from the first stage of ionization
becomes the acid for the second stage ionization.

Solution
We proceed according to the following steps.
Step 1: The major species in solution at this stage are the nonionized
 
acid, H ions, and the conjugate base, HC2 O4 .

Step 2: Letting x be the equilibrium concentration of H and
HC 2O 4 ions in mol L , we summarize :
H 2C 2O 4  aq   H   aq   HC 2O 4  aq 
Initial (M): 0.10 0.00 0.00
Equilibrium (M): 0.10 − x x x

Step 3: Table 15.5 gives us
 H    HC2 O 4 
Ka 
 H 2 C2O 4 
2 x2
6.5  10 
0.10  x
Applying the approximation 0.10 − x ≈ 0.10, we obtain

2 2
x x
6.5  102  
0.10  x 0.10
x 2  6.5  103
x  8.1  102 M
To test the approximation,
8.1 102 M
 100%  81%
0.10 M
Clearly the approximation is not valid. Therefore,

we must solve the quadratic equation
x 2  6.5  102 x  6.5  103  0
The result is x = 0.054 M.

Step 4: When the equilibrium for the first stage of
ionization is reached, the concentrations are
 H    0.054 M
 HC 2 O 4   0.054 M
 H 2C2O4    0.10  0.054  M  0.046 M
Next we consider the second stage of ionization.
Step 1: At this stage, the major species are HC2O 4 ,

which acts as the acid in the second stage of

ionization, H , and the conjugate base C2O 24 .

Step 2: Letting y be the equilibrium concentration of H and
C2 O 42 ions in mol L, wesummarize:
HC2 O4  aq   H   aq   C 2O 24  aq 
Initial (M): 0.054 0.054 0.00
Change (M): −y +y +y
Equilibrium (M): 0.054 − y 0.054 + y y
Step 3: Table 15.5 gives us

 H    C2 O 42 
Ka 
 HC2 O 4 
 0.054  y   y 
6.1  105 
 0.054  y 

Applying the approximation 0.054 + 𝑦 ≈ 0.054 and

0.054 − 𝑦 ≈ 0.054, we obtain
 0.054   y   y  6.1 105 M

 0.054 
and we test the approximation,
6.1 105 M
 100%  0.11%
0.054 M
The approximation is valid

Step 4: At equilibrium,
 H 2C 2O 4   0.046 M
 HC 2 O 4    0.054  6.1  10 5  M  0.054 M
 H     0.054  6.1  10 5  M  0.054 M
C 2O 42   6.1  10 5 M
OH    1.0  10 14 0.054  1.9  1013 M

Molecular Structure and Acid Strength
H  X  H  X

The stronger The weaker

the bond the acid
HF << HCl < HBr < HI

Bond Enthalpies for Hydrogen Halides
Table 15.6 Bond Enthalpies for hydrogen halides and Acid Strengths
for Hydrohalic Acids
Bond Bond Enthalpy (kJ mol ) Acid Strength

H―F 568.2 weak
H―Cl 431.9 strong
H―Br 366.1 strong
H―I 298.3 strong

Molecular Structure and Oxoacid Strength
(1 of 3)
1. Oxoacids having different central atoms (Z) that are from the
same group and that have the same oxidation number.
Acid strength increases with increasing electronegativity of Z
Cl is more electronegative than Br
HClO3  HBrO3

(2 of 3)
The O-H bond will be more polar and easier to break if:
• Z is very electronegative or
• Z is in a high oxidation state

(3 of 3)
2. Oxoacids having the same central atom (Z) but different
numbers of attached groups.
Acid strength increases as the oxidation number of Z

increases.
HClO 4  HClO3  HClO 2  HClO

Predict the relative strengths of the oxoacids in each

of the following groups:
a) HClO, HBrO, and HIO
b) HNO3 and HNO2

Strategy
Examine the molecular structure. In (a) the two acids

have similar structure but differ only in the central atom
(Cl, Br, and I). Which central atom is the most
electronegative? In (b) the acids have the same
central atom (N) but differ in the number of O atoms.
What is the oxidation number of N in each of these two
acids?

Solution
a) These acids all have the same structure, and the

halogens all have the same oxidation number (+1).
Because the electronegativity decreases from Cl to
I,the Cl atom attracts the electron pair it shares with
the O atom to the greatest extent. Consequently, the
O―H bond is the most polar in HClO and least polar in
HIO. Thus, the acid strength decreases as follows:
HCIO  HBrO  HIO

b) The structures of HNO3 and HNO2 are shown in

Figure 15.5. Because the oxidation number of N is
5 in HNO3 and  3 in HNO 2 , HNO 3 is a stronger
acid than HNO 2 .

Acid-Base Properties of Salts (1 of 2)
Table 15.7 Acid-Base properties of Salts

Type of salt Examples Ions that undergo pH of
Hydrolysis Solution
Cation from strong base; NaCl, KI, KNO3, None ≈7
anion from strong acid RbBr, BaCl2
Cation from strong base; CH3COONa, KNO2 Anion >7
anion from weak acid
Cation from weak base; NH4Cl, NH4NO3 Cation <7
anion from strong acid
Cation from weak base; NH4NO2, Anion and cation <7 if Kb < Ka
anion from weak acid CH3COONH4, ≈7 if Kb ≈ Ka
NH4CN >7 if Kb > Ka
Small, highly charged cation; AlCl3, Fe(NO3)3 Hydrated cation <7
anion from strong acid

Acid-Base Properties of Salts: Neutral and
Basic Solutions
Neutral Solutions:
Salts containing an alkali metal or alkaline earth metal
2
ion (except Be ) and the conjugate base of a strong acid
 e.g.Cl , Br
 
, and NO3  .
Nacl  s  
H 2O
 Na   aq   Cl   aq 
Basic Solutions:
Salts derived from a strong base and a weak acid.
CH 3COONa  s  
H 2O
 Na   aq   CH3 COO  aq 
CH 3COO   aq   H 2 O  l   CH3 COOH  aq   OH   aq 

Calculate the pH of a 0.15 M solution of sodium

acetate (CH3COONa). What is the percent
hydrolysis?

Strategy
What is a salt? In solution, CH3COONa dissociates

  
completely into Na and CH 3 COO ions. The Na ion, as
we saw earlier, does not react with water and has no

effect on the pH of the solution. The CH 3 COO ion is the
conjugate base of the weak acid CH3COOH. Therefore,
we expect that it will react to a certain extent with water
to produce CH3COOH and OH , and the solution will be
basic.

Solution
Step 1: Because we started with a 0.15 M sodium acetate
solution, the concentrations of the ions are also
equal to 0.15 M after dissociation:
CH 3COONa  aq   Na   aq   CH 3COO   aq 
Initial (M): 0.15 0 0

Change (M): −0.15 +0.15 +0.15
Final (M): 0 0.15 0.15
Of these ions, only the acetate ion will react with water
CH 3COO   aq   H 2O  l   CH 3COOH  aq   OH   aq 

At equilibrium, the major species in solution are CH3COOH,
CH 3COO  , and OH  .
H
The concentration of the ion is very small as we would
expect for a basic solution, so it is treated as a minor species.
We ignore the ionization of water.

OH
Step 2: Let x be the equilibrium concentration of CH3COOH and
ions in mol/L, we summarize:
   
CH COO  aq  H O l  CH COOH aq  OH  aq
3 2 3    
Initial (M): 0.15 0.00 0.00
Equilibrium (M): 0.15−x x x

Step 3: From the preceding discussion and Table 15.3 we write
the equilibrium constant of hydrolysis, or the base
ionization constant, as
 CH3COOH  OH  
Kb 
CH 3COO  
x2
5.6  1010 
0.15  x
Because Kb is very small and the initial concentration of the

base is large, we can apply the approximation 0.15 − x ≈ 0.15:
2 2
x x
5.6  1010  
0.15  x 0.15
x  9.2  106
Step 4: At equilibrium:
OH    9.2  10 6 M
pOH   log  9.2  10 6 
 5.04
pH  14.00  5.04
 8.96
Thus the solution is basic, as we would expect. The

percent hydrolysis is given by
9.2  106 M
%hydrolysis   100%
0.15 M
 0.0061%
Check
The result shows that only a very small amount of

the anion undergoes hydrolysis. Note that the
calculation of percent hydrolysis takes the same
form as the test for the approximation, which is valid
in this case.

Acid-Base Properties of Salts: Acidic
Solutions
Acid Solutions:
Salts derived from a strong acid and a weak base.
NH 4 Cl  s  
H 2O
 NH 4  aq   Cl   aq 
NH 4  aq   NH3  aq   H   aq 
Salts with small, highly charged metal cations

 e.g. Al 3
, Cr 3 , and Be2 
and the conjugate base of a strong acid.

Al  H 2 O  6  aq   Al  OH   H 2O  5  aq   H   aq 
3 2

3
Acid Hydrolysis of AI
AI  H 2O  6 AI  OH   H 2O  5 
3 2
 H 2O  H 3O 

Acid-Base Properties of Salts (2 of 2)
Solutions in which both the cation and the anion

hydrolyze:
Kb for the anion > Ka for the cation, solution will be

basic
Kb for the anion < Ka for the cation, solution will be
acidic
Kb for the anion ≈ Ka for the cation, solution will be
neutral

Predict whether the following solutions will be

acidic, basic, or nearly neutral:
 a  NH 4I
 b  NaNO 2
 c  FeCl3
 d  NH 4F
Strategy
In deciding whether a salt will undergo hydrolysis, ask

yourself the following questions: Is the cation a highly
charged metal ion or an ammonium ion? Is the anion the
conjugate base of a weak acid? If yes to either question,
then hydrolysis will occur. In cases where both the cation
and the anion react with water, the pH of the solution will
depend on the relative magnitudes of Ka for the cation
and Kb for the anion (see Table 15.7).

Solution
We first break up the salt into its cation and anion components
and then examine the possible reaction of each ion with water.
 a  The cation is NH 4 ,
 
which will hydrolyze to produce NH3 and H . The I anion is

I
the conjugate base of the strong acid HI. Therefore, will
not hydrolyze and the solution is acidic.
 
(b) The Na cation does not hydrolyze. The NO 2
is the conjugate base of the weak acid HNO2 and will

hydrolyze to give HNO2 and OH . The solution will be basic.
3+
(c) Fe s a small metal ion with a high charge and

hydrolyzes to produce H  ions. The Cl does not
hydrolyze. Consequently, the solution will be acidic.
 d Both the NH 4 and F

ions will hydrolyze. From Tables 15.3 and 15.4 we
see that the K a of NH 4  5.6  10 10 
is greater than the K b for F (1.4  1011 ). Therefore, the
solution will be acidic.

Oxides of the Representative Elements In
Their Highest Oxidation States
Na 2 O  s   H 2 O  l   2NaOH  aq 
CO 2  g   H 2 O  l   H 2 CO3  aq 
N 2 O5  g   H 2 O  l   2HNO3  aq 

Definition of An Acid
 
Arrhenius acid is a substance that produces H (H 3O ) in water
A Brønsted acid is a proton donor
A Lewis acid is a substance that can accept a pair of electrons
A Lewis base is a substance that can donate a pair of electrons

Lewis Acids and Bases
No protons donated or accepted!

Chemistry In Action: Antacids and the
Stomach pH Balance
Some Common Commercial NaHCO 3  aq   HCl  aq 
Antacid Preparations  NaCl  aq   H 2 O  l 
Commercial Name Active Ingredients  CO 2  g 
Alka-2 Calcium carbonate
Alka-Seltzer Aspirin, sodium bicarbonate,
citric acid
Bufferin Aspirin, magnesium carbonate,
aluminum glycinate
Buffered aspirin Aspirin, magnesium carbonate,
aluminum hydroxide-glycine
Milk of magnesia Magnesium hydroxide
Rolaids Dihydroxy aluminum sodium
carbonate
Tums Calcium carbonate
Mg  OH  2  s   2HCl  aq 
 MgCl 2  aq  Jump to long description
 2H 2 O  l 
Identify the Lewis acid and Lewis base in each of

the following reactions:
 a  C2 H5OC2 H5  AlCl3   C2 H5  2 OAlCl3
 b  Hg  aq   4CN  aq   Hg  CN  4  aq 
2  2

Strategy
In Lewis acid-base reactions, the acid is usually a cation

or an electron-deficient molecule, whereas the base is an
anion or a molecule containing an atom with lone pairs
a) Draw the molecular structure for C2H5OC2H5. What is

the hybridization state of Al in AlCl3?
b) Which ion is likely to be an electron acceptor? An

electron donor?

Solution
2
(a) The Al is sp -hybridized in AlCl3 with an empty 2pz orbital. It is
electron deficient, sharing only six electrons. Therefore, the Al
atom has a tendency to gain two electrons to complete its octet.
This property makes AlCl3 a Lewis acid. On the other hand, the
lone pairs on the oxygen atom in C2H5OC2H5 make the
compound a Lewis base:

2
(b) Here the Hg ion accepts four pairs of electrons
 2
from the CN ions. Therefore, Hg is the Lewis
acid and CN  is the Lewis base.

Appendix of Image Long Descriptions
© 2019 McGraw-Hill Education. 3-105

Acid-Base Properties of Water Long
Description
The products of this reaction are H3O+ and OH−.
The system is in equilibrium, so H3O+ and OH− can
react to produce two molecules of water.
Jump to image
Acids and Conjugate Bases Long
Description
Weak acids, such as HCOOH and NH3, produce
stronger conjugate bases (HCOO− and NH2−,
respectively).
In general, the stronger the acid, the weaker the
conjugate base.
Jump to image
Strong vs. Weak Acids Long
Description(1 of 2)
Before ionization, only HCl molecules (a strong
acid) exist, but at equilibrium, the solution contains
only H+ and Cl− ions.
Jump to image
Strong vs. Weak Acids Long
Description(2 of 2)
Before ionization, only HF molecules (a weak acid)
exist, but at equilibrium, HF molecules, H+ ions, and
F− ions exist in solution.
Jump to image
(1 of 2) Long Description
4
HF has a Ka of 7.1  10 , while carboxylic acids,
such as formic and acetic acids, have Ka values on
5
the order of 104 and 10 . HCN and phenol are much
weaker acids than carboxylic acids and have Ka
10
values on the order of 10 .
Because conjugate base strength increases as acid
strength decreases, the Kb values of CN− and
phenolate are on the order of 105 , and the Kb
values of the conjugate bases of carboxylic acids are
on the order of 1010.
Jump to image
Example 15.8 (2 of 6) Long Description
A sketch of the solution at equilibrium shows that

the solution contains H+ ions, NO2− ions, and
HNO2. The autoionization of water can be ignored
because it is not a major source of H+ ions in
solution.
Jump to image
A sketch of the solution at equilibrium shows that

the solution contains H+ ions, HCOO− ions, and
HCOOH. The pH of the solution is 2.39, so the
2.39
concentration of H+ ions in solution is 10 M.
Jump to image
Percent Ionization Long Description
As the initial concentration of a weak acid increases,

the percent ionization decreases quickly from 100%
ionization, approaching 0% ionization as the initial
acid concentration increases.
At very low concentrations, both strong and weak
acids ionize completely.
Jump to image
A sketch of the solution at equilibrium shows that the

solution contains NH4+ ions, OH− ions, and NH3. The
autoionization of water can be ignored because it is
not a major source of OH− ions in solution.
Jump to image
Ionization Constants of Some Polyprotic
Acids Long Description
For example, carbonic acid (H2SO3) has two ionizable
protons. The first Ka of carbonic acid is 4.2 x 10^−7,
and the second Ka is 4.8 x 10^−11.
Jump to image
In comparing the acidity of HClO3, HBrO3, and
HIO3, HClO3 is the most acidic because Cl is the
most electronegative. HIO3 is the least acidic of the
series because I is the least electronegative.
Jump to image
Nitrous acid and nitric acid both only have one OH
bond and thus only one ionizable proton. Carbonic
acid, phosphorous acid, and sulfuric acid each
have two OH bonds and thus each has two
ionizable protons. Phosphoric acid has three OH
bonds and thus three ionizable protons.
Jump to image
The strength of the acid increases as the oxidation
number of the central atom increases. Consider a series
of chlorine-containing oxoacids. The Cl atom of
perchloric acid, HClO4, has an oxidation number of +7,
while the Cl in chloric acid, HClO3, has an oxidation
number of +5. The oxidation number of Cl in chlorous
acid is +3, while it is +1 in hypochlorous acid, HOCl.
The most acidic acid is HClO4, which has the highest Cl
oxidation number, while the weakest of the series is
HOCl, which has the lowest Cl oxidation number in the
series.
Jump to image
3
Acid Hydrolysis of AI Long Description
A solvent water molecule can take a proton from a

coordinated water molecule on the aluminum ion.
The resulting aluminum species has five
coordinated water molecules and one hydroxide ion,
and a hydronium ion (H3O+) ion is formed.
Jump to image
Oxides of the Representative Elements In
Their Highest Oxidation States Long
Description
Lithium oxide reacts with water to produce lithium
hydroxide. Nonmetal oxides tend to produce acidic
solutions. SO3 reacts with water to produce sulfuric
acid.
Some elements, including Be, Al, Ga, Sn, and Pb,
form amphoteric oxides. These compounds produce
water under both acidic and basic conditions.
Jump to image
Chemistry In Action: Antacids and the
Stomach pH Balance Long Description
H+ and Cl− ions enter the stomach through active transport
from the blood plasma, but the mucous membranes prevent
ion transfer from the stomach back to the blood plasma. Under
normal conditions, stomach lining regenerates every three
days, so the presence of acid doesn't cause problems.
However, if the acid is very high, the cells of the stomach wall
will contract, causing discomfort and pain.
Taking antacids can temporarily neutralize the stomach acid
and relieve pain. Antacids most often contain bases that react
with excess acid in the stomach. The products of the acid-
base reaction, water and a salt, can be excreted from the body
through the intestines.
Jump to image
End of Presentation
© McGraw-Hill Education. All rights reserved. Authorized only for instructor use in the
classroom. No reproduction or further distribution permitted without the prior written consent
15-122
of McGraw-Hill Education.

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Chapter 15

Acids and Bases

React with certain metals to produce hydrogen gas.

React with carbonates and bicarbonates to produce

Feel slippery. Many soaps contain bases.

© McGraw-Hill Education. 15-2

A Brønsted acid is a proton donor

NH 3 (aq)  H 2 O(l )  NH 4 (aq)  OH  ( aq)

© McGraw-Hill Education. 15-3

Remember that a conjugate base always has one fewer H

Identify the conjugate acid-base pairs in the reaction

© McGraw-Hill Education. 15-5

H 2 O(l )  H  (aq)  OH  (aq)

Jump to long description

© McGraw-Hill Education. 15-6

The ion-product constant (Kw) is the product of

At 25C  H    OH   neutral

K w   H    OH    1.0  1014  H    OH   acidic

© McGraw-Hill Education. 15-8

We are given the concentration of the OH  ions and

© McGraw-Hill Education. 15-9

Rearranging Equation (15.3), we write

© McGraw-Hill Education. 15-11

*Water exposed to air for a long pH Meter

© McGraw-Hill Education. 15-13

We are given the H  ion concentration and asked to

© McGraw-Hill Education. 15-14

On the second occasion,[H  ]  1.0  10 3 M,so that

pH   log(1.0  103 )  3.00

The increase in hydrogen ion concentration (or

© McGraw-Hill Education. 15-16

The pH of rainwater collected in a certain region of

© McGraw-Hill Education. 15-17

Here we are given the pH of a solution and asked to

by taking the antilog of the pH; that is,  H    10 pH ,

© McGraw-Hill Education. 15-18

From Equation (15.4)

To calculate  H   , We need to take the antilog of  4.82

 H    104.82  1.5  105 M

Because the pH is between 4 and 5, we can expect

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In a NaOH solution OH   is 2.9  104 M.

Calculate the pH of the solution.

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Solving this problem takes two steps. First, we need to calculate

We use Equation (15.7):

Alternatively, we can use the ion-product constant of water,

Weak Electrolyte – not completely dissociated

Strong Acids are strong electrolytes

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Strong Bases are strong electrolytes

F ( aq)  H 2 O (l )  OH  ( aq)  HF( aq)

Conjugate acid-base pairs:

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Strong Acid (HCl) Weak Acid (HF)

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