Acids and Bases PDF

Chapter 14 Acids and Bases
Conjugate Acid-Base Pair: The compounds which

are related to each other by donating and accepting a
single proton. The acid is paired with the conjugate
base (HA with A) and the base is paired with the
conjugate acid (H2O with H3O+).
Arrhenius Model
Arrhenius Acid: A substance which produces
hydrogen ions (H+) when it dissociates in water.
H2 O
e.g., HCl(g) H+(aq) + Cl(aq)
Ex 14.1.1: In each of the following chemical

equations, identify the conjugate acid-base pairs.
Arrhenius Base: A substance which produces

hydroxide ions (OH) when it dissociates in water.
(a) HNO3(aq) + H2O(l) H3O+(aq) + NO3(aq)
H2 O
e.g., NaOH(s) Na+(aq) + OH(aq)

Brnsted-Lowry Model
(b) H2O(l) + HSO4(aq) H3O+(aq) + SO42(aq)
Brnsted-Lowry Acid: A substance which donates a

proton (H+).
Brnsted-Lowry Base: A substance which accepts a
proton (H+).
Hydronium Ion (H3O+): A aqueous hydrogen ion or
hydrated proton that forms anytime a BrnstedLowry acid dissolves in water.
(c) NH2(aq) + H2O(l) OH(aq) + NH3(aq)
HA(aq) + H2O(l) H3O+(aq) + A(aq)
Conjugate Acid: The compound that forms when a

base accepts a proton from an acid.
Ex 14.1.2: Write the conjugate base for each of the

following acids.
Conjugate Base: The compound that remains when

an acid donates a proton from an acid.
(a) H2SO4
In aqueous solution, the acid (HA) donates a proton

to a water molecule (the base) forming a conjugate
acid (H3O+) and a conjugate base (A).
(b) NH3

Acid
Base
Conjugate
Acid
Conjugate
Base
(c) HPO42
Ex 14.1.5: Write a chemical equation showing how

the following substances behave as an acid when
dissolved in water.
Ex 14.1.3: Write the conjugate acid for each of the

following bases.
(a) Cl
(a) H2CO3
(b) SO42
(b) HSO4
(c) NH3
Ex 14.1.6: Write a chemical equation showing how
the following substances behave as a base when
dissolved in water.
(a) NO2
Ex 14.1.4: Determine which of the following sets of
chemical species are conjugate acid-base pairs.
(a) HCl, Cl
(b) HPO42
(b) HPO42, H3PO4
(c) NH2, NH3
(d) Cl, ClO
Common Strong Acids

hydrochloric acid,
nitric acid,
sulfuric acid,
perchloric acid,
hydrobromic acid,
hydroiodic acid,
Acid Strength
The strength of an acid is determined by the
equilibrium position of its dissociation reaction. An
acid dissociates in water according to the following
reaction where HA represents the acid and A
represents the conjugate base.
HCl
HNO3
H2SO4
HClO4
HBr
HI
Weak Acid: An acid which barely dissociates in

water. A weak acid will have an equilibrium position
that lies far to the left in the direction of the reactants
(Ka << 1).
The equilibrium expression for this reaction is as

follows where the equilibrium constant (Ka) is called
the acid dissociation constant.
1. Most acids are weak or moderately weak in

strength.
[H3 O+ ][A ]
a =
[HA]
2. A strong acid has a weak conjugate base, while a

weak acid has a strong conjugate base.
In the forward direction, HA is the acid, H2O is the

base, H3O+ is the conjugate acid, and A is the
conjugate base.
3. A strong acid has a conjugate base that is a weaker

base than water.

Acid
Base
Conjugate
Acid
4. A weak acid has a conjugate base that is a stronger

base than water.
Conjugate
Base
In the reverse direction, H3O+ is the acid, A is the

base, HA is the conjugate acid, and H2O is the
conjugate base.
Monoprotic Acid: An acid that can furnish only one

proton.
e.g., HF(aq) + H2O(l) H3O+(aq) + F(aq)
HA(aq) + H2O(l) H3O (aq) + A (aq)

+
Conjugate Conjugate
Acid
Base
Acid
Base
Diprotic Acid: An acid that can furnish two protons.

Each proton is donated one at a time in separate
dissociation steps.
Acid Strength: A measure of the tendency of an acid

to dissociate in water and donate it proton. The more
an acid dissociates, the stronger the acid.
e.g., H2SO4(aq) + H2O(l) H3O+(aq) + HSO4(aq)

HSO4(aq)+ H2O(l) H3O+(aq) + SO42(aq)
Strong Acid: An acid which almost completely

dissociates in water. A strong acid will have an
equilibrium position that lies far to the right in the
direction of the products (Ka >> 1).
Triprotic Acid: An acid that can furnish three

protons. Each proton is donated one at a time in
separate dissociation steps.
e.g., HCl(aq) H+(aq) + Cl(aq)
e.g., H3PO4(aq) + H2O(l) H3O+(aq) + H2PO4(aq)
H2PO4(aq) + H2O(l) H3O+(aq) + HPO42(aq)
HPO42(aq)+ H2O(l) H3O+(aq) + PO43(aq)
Ex 14.2.1: Calculate the unknown [H+] or [OH] for

each of the following solutions at 25C, and state
whether the solution is acidic, basic, or neutral.
Water as an Acid and a Base

Amphoteric: A property of a substance which can
act like both an acid and a base. The most common
amphoteric substance is water.
(a) 1.41 106 M H+
Autoionization of Water: Regardless of whether

water is a pure substance or part of a mixture, it
always slightly dissociates (self-ionizes) because it is
amphoteric. One molecule of water acts like an acid
while another molecule of water acts like a base.
Solution:
Kw = [H+][OH]
[OH ] =
H2O(l) + H2O(l) H3O+(aq) + OH(aq)

Acid
Base
Conjugate
Acid
w
1.00 1014
=
= 7.09 109
[H + ]
1.41 106
[H+] > [OH]
Conjugate
Base
Solution is acidic.
Ion-Product Constant [Kw]: The equilibrium

constant for the autoionization of water.
(b) 0.002215 M OH
Kw = [H3O+][OH]
Solution:
The hydronium ion (H3O+) is commonly abbreviated

as a hydrogen ion or proton (H+).
Kw = [H+][OH]
Kw = [H+][OH]
[H + ] =
At 25C in pure water with 2 significant figures:
w
1.000 1014
=
[OH ]
0.02215
= 4.515 1013
[H+] = [OH] = 1.0 107 M
[H+] < [OH]
w = [H + ][OH ] = (1.0 107 )(1.0 107 )
Solution is basic.
Kw = 1.0 1014
(c) 0.00000010 M H+
Note: The acid dissociation constant for water is

equal to the ion-product constant (Ka = Kw = 1.0
1014).
Solution:
Kw = [H+][OH]
Acidity of Solution:
[OH ] =
neutral solution: [H+] = [OH]

acidic solution:
[H+] > [OH]
basic solution:
[H+] < [OH]
w
1.0 1014
=
= 1.0 107
[H + ] 0.00000010
[H+] = [OH]
Solution is neutral.
Note: Pure water is neutral.
pKw Scale: A scale used for expressing the ionproduct constant as a base 10 logarithm.
The pH Scale
pX Scale: A scale where quantities are expressed as
base 10 logarithms.
pKw = log Kw
pX = log[X]
and its inverse,
and its inverse,
w = 10p
[X] = 10pX
Relationship Between pH, pOH, and pKw:
where: X = formula of chemical species

[X] = concentration of chemical species
pH + pOH = pKw
At 25C in pure water with 2 significant figures:
Significant Figures and pX Scale: Only decimal

places (digits to the right of the decimal) are counted
as significant for logarithmic numbers. The number
of significant figures in the concentration [X] values
is the number of decimal places in the pX value.
Kw = 1.0 1014
pw = log(1.0 1014 ) = 14.00
pH + pOH = 14.00
e.g., The concentration, [X] = 4.21 1013 M, and its

negative logarithm, pX = 12.376, both have 3
significant figures.
pH as an Indicator of Acidity at 25C:

neutral solution: pH = 7.00
e.g., The concentration, [X] = 1 109 M, and its

negative logarithm, pX = 9.0, both have 1 significant
figures.
pH Scale: A scale used for expressing the
concentration of hydrogen ion (H+) solutions as base
10 logarithms.
acidic solution:
pH < 7.00
basic solution:
pH > 7.00
Ex 14.3.1: Complete the following calculations and

indicate whether the solution is acidic, basic, or
neutral at 25C.
pH = log[H+]
(a) If pH = 7.32, then [H+] = ?
and its inverse,
Solution:
[H+] = 10pH
[H+] = 10pH = 107.32 = 4.8 108 M

pOH Scale: A scale used for expressing the
concentration of hydroxide ion (OH) solutions as
base 10 logarithms.
pH > 7.00
Solution is basic.
pOH = log[OH ]
and its inverse,
[OH] = 10pOH
(b) If [H+] = 0.0345 M, then pH = ?
Effect of Temperature on the Autoionization of

Water:
Solution:
Temperature
(C)
Kw
pKw
1.1 1015
14.96
10
2.9 1015
14.54
20
6.8 1015
14.17
25
1.0 1014
14.00
Solution:
30
1.5 1014
13.82
pH + pOH = pKw
40
2.9 1014
13.54
pOH = pKw pH = 14.00 9.87 = 4.13
50
5.5 1014
13.26
100
5.1 1013
12.29
pH = log[H + ] = log(0.0345) = 1.462

pH < 7.00
Solution is acidic.
(c) If pH = 9.87, then pOH =?
pH > 7.00
Ex 14.3.2: Calculate the pH of water at 10C using
the appropriate value of Kw.
Solution is basic.
(d) If [OH] = 1.5 109, then pOH =?
Solution:
Solution:
At 10C: w = 2.9 1015
pOH = log[OH ] = log(1.5 109 ) = 8.82
Since water is neutral: [H + ] = [OH ]
pH + pOH = pKw
w = [H + ][OH ] = [H + ][H + ]
pH = pKw pOH = 14.00 8.82 = 5.18
[H + ]2 = w
pH < 7.00
[H + ] = w = 2.9 1015 = 5.4 108
Solution is acidic.
pH = log[H + ] = log(5.4 108 ) = 7.27
Ex 14.4.1: Calculate the pH and the concentration of

all species in an HClO4 solution with the following
concentrations.
Ex 14.3.3: Calculate the pH of water at 50C using

the appropriate value of pKw.
Solution:
(a) 5.0 103 M
At 50C: pw = 13.26
Solution:
Since water is neutral: pH = pOH
[HClO4]0 = 5.0 103 M
pH + pOH = pw
HClO4(aq) H+(aq) + ClO4(aq)
pH + pH = pw
H2O(l) H+(aq) + OH(aq)
2pH = pw
pH =
Species present in solution: HClO4, H+, ClO4, H2O,

and OH.
pw 13.26
=
= 6.63
2
2
HClO4 is a strong acid and will completely

dissociate. In comparison to a strong acid, the
autoionization of water will not be a significant
contributor of H+ ions.
Chemical Species Present in Solutions Containing

Acids: Strong acids completely dissociate leaving
hydrogen ions and the acids conjugate base in
solution. Weak acids partially dissociate leaving the
weak acid, hydrogen ions, and the acids conjugate
base in solution. Water, the solvent in acid solutions,
contains both hydrogen ions and hydroxide ions.
[HClO4] = 0
[H+] = [HClO4]0 = 5.0 103 M
[ClO4] = [HClO4]0 = 5.0 103 M
water (H2O)
hydrogen ions (H+)
hydroxide ions (OH)
acids (HA)
conjugate bases (A)
Kw = [H+][OH]
[OH ] =
Calculating the pH of Strong Monoprotic Acids:

Strong acids are the major source of hydrogen ions in
a strong acid solution. The concentration of the
hydrogen ions (H+) in a strong monoprotic acid will
be approximately equal to the concentration of the
acid (HA). Pure water is considered a significant
contributor of H+ ions if [HA] < 106 M at 25C.
w
1.0 1014
=
= 2.0 1012
[H + ]
5.0 103
pH = log[H + ] = log(5.0 103 ) = 2.30
[H+] = [HA]0
(b) 5.0 1010 M

Solution:
4. Determine the concentration of the hydrogen ions

by applying the RICE method for equilibrium
systems.
[HClO4]0 = 5.0 1010 M
5. Calculate the pH.
Since the concentration of HClO4 is so small, the

autoionization of water will be the major source of
H+ ions. The hydrogen ion concentration, hydroxide
ion concentration, and pH of the solution will
essentially be that of pure water.
Percent Dissociation (Percent Ionization): The

amount of weak acid dissociated as the reaction
reaches equilibrium.
percent dissociation
[H+] = 1.0 107 M
[OH] = 1.0 107 M
amount dissociated
100%
initial concentration

all species in 0.500 M hydrocyanic acid (HCN, Ka =
6.2 1010).
[HClO4] = 0
[ClO4] = [HClO4]0 = 5.0 1010 M
Solution:
pH = 7.0
HCN(aq) H+(aq) + CN(aq)
Calculating the pH of Weak Acids:
Ka = 6.2 1010
1. Identify all species in solution.
2. Identify all species producing hydrogen ions.
Kw = 1.0 1014
Acid Dissociation Reaction:
Species present in solution: HCN, H+, CN, H2O, and

OH.
HA(aq) H+(aq) + A(aq)
Since Ka > Kw, HCN will be the major contributor of

H+ ions.
Autoionization of Water:
The initial concentrations will be the concentrations

before any of the HCN has dissociated.
3. Determine which species is the major contributor

of hydrogen ions (H+).
[HCN]0 = 0.500 M, [H+]0 = 0, [CN]0 = 0
(a) In absence of any strong acids, weak acids are the

major contributor of H+ ions if Ka > Kw and
[HA] > 106 M at 25C.
The reaction will shift toward the products.

Make RICE table and input given information.
(b) Pure water is the major contributor of H ions if

Kw > Ka or [HA] < 106 M at 25C.
Reaction
Initial (M)
Change (M)
Equilibrium (M)
(c) In a mixture of weak acids, the acid with the

largest Ka value will be the major contributor of H+
ions.
HCN(aq) H+(aq)
0.500
0
+ CN(aq)
0
The assumption that the addition and subtraction of x

is negligible is valid.
Let x = amount of HCN consumed.

Calculate changes in concentration and input in RICE
table.
Reaction
Initial (M)
Change (M)
Equilibrium (M)
HCN(aq) H+(aq)
0.500
0
x
+x
Equilibrium Concentrations:
+ CN(aq)
0
+x
[HCN] = 0.500 x 0.500 M

[H+] = x = 1.8 105 M
[CN] = x = 1.8 105 M
Calculate equilibrium concentrations and input in

RICE table.
Reaction
Initial (M)
Change (M)
Equilibrium (M)
HCN(aq) H (aq)
0.500
0
x
+x
0.500 x
x
+
Equilibrium Check:
+ CN (aq)
0
+x
x
a =
[H + ][CN ] (1.8 105 )(1.8 105 )

=
[HCN]
(0.500)
= 6.5 1010
Solution with Assumption:
This agrees with given value of Ka (6.5 1010 6.2

1010).
Since Ka << 1, the system will barely shift toward the

right. Assume x is very small, and its addition and
subtraction is negligible.
Therefore:
Final Calculations:
Kw = [H+][OH]
[HCN] = 0.500 x 0.500 M

[H + ][CN ]
()()
a =
=
[HCN]
(0.500)
[OH ] =
w
1.0 1014
=
= 5.6 1010
[H + ]
1.8 105
pH = log[H + ] = log(1.8 105 ) = 4.74
2
a =
0.500
2 = a (0.500)
= a (0.500) = (6.2 1010 )(0.500)

= 1.8 105
Assumption Check:
Compare x to the smallest initial concentration.
1.8 105
(100%) =
(100%)
[HCN]0
0.500
= 0.0036% < 5%

RICE table.
Ex 14.5.2: Calculate the pH and the percent

dissociation of a 0.200 M solution of citric acid
(H3C6H5O7). The acid dissociation constant for citric
acid is 7.45 104.
Reaction
Initial (M)
Change (M)
Equilibrium (M)
Solution:
H3C6H5O7(aq) H+(aq) + H2C6H5O7(aq)
0.200
x
0.200 x
0
+x
x
Ka = 7.45 104

Kw = 1.0 1014
Therefore:
Species present in solution: H3C6H5O7, H+,

H2C6H5O7, H2O, and OH.
[H3C6H5O7] = 0.200 x 0.200 M
Since Ka > Kw, H3C6H5O7 will be the major

a =

before any of the H3C6H5O7 has dissociated.
a =
= 0.0122
Assumption Check:

0.0122
(100%) =
(100%)
[H3 C6 H5 O7 ]0
0.200
Let x = amount of H3C6H5O7 consumed.

table.
Reaction
Initial (M)
Change (M)
Equilibrium (M)
= 6.10% > 5%

is negligible is not valid.
0.200
x
0
+x
2
0.200
= a (0.200) = (7.45 104 )(0.200)
0.200
[H + ][H2 C6 H5 O
()()
7]
=
[H3 C6 H5 O7 ]
(0.200)
2 = a (0.200)
[H3C6H5O7]0 = 0.200 M, [H+]0 = 0, [H2C6H5O7]0 = 0
Reaction
Initial (M)
Change (M)
Equilibrium (M)
0
+x
x
0
+x
10
Explicit Solution:
a =
a =
Final Calculations:
[H + ][H2 C6 H5 O
()()
7]
=
[H3 C6 H5 O7 ]
(0.200 )
pH = log[H + ] = log(0.0118) = 1.928

percent dissociation =
2
(0.200 )
7.45 104 =
2
(0.200 )
2 + (7.45 104 ) 1.49 104 = 0
2 4
2
Solution:
HCOOH(aq) H+(aq) + COOH(aq)
7.45 104 (7.45 104 )2 4(1)(1.49 104 )

=
2(1)
= 0.0126,
0.0118
(100%) = 5.90%
0.200
Ex 14.5.3: Calculate the pH of a solution containing

2.00 M formic acid (HCOOH, Ka = 1.77 104) and
1.50 M hypobromous acid (HOBr, Ka = 2.06 109).
What are the concentrations of hypobromite (OBr)
and hydroxide (OH) ions at equilibrium? (Note: The
molarity of the acids was determined after the two
acids were mixed together.)
(7.45 104 )(0.200 ) = 2
(100%)
[H3 C6 H5 O7 ]0
a1 = 1.77 104
0.0118
HOBr(aq) H+(aq) + OBr(aq)
Since x cannot be negative:
a2 = 2.06 109
x = 0.0118 M
Kw = 1.0 1014
[H3C6H5O7] = 0.200 x 0.200 0.0118 = 0.188 M
Species present in solution: HCOOH, HOBr, H+,

COOH, OBr, H2O, and OH.
[H+] = x = 0.0118 M
Since a1 > a2 > , HCOOH will be the major

[H2C6H5O7] = x = 0.0118 M
Equilibrium Check:

before any of the HCOOH has dissociated.
[H + ][H2 C6 H5 O
(0.0118)(0.0118)
7]
a =
=
[H3 C6 H5 O7 ]
(0.188)
[HCOOH]0 = 0.500 M, [H+]0 = 0, [COOH]0 = 0
= 7.45 1010
This agrees with given value of Ka.
11

Reaction
Initial (M)
Change (M)
Equilibrium (M)
Assumption Check:

2.00
0
0

0.0188
(100%) =
(100%)
[HCOOH]0
2.00
Let x = amount of HCOOH consumed.
= 0.940% < 5%

table.
Reaction
Initial (M)
Change (M)
Equilibrium (M)


2.00
0
0
x
+x
+x
[HCOOH] = 2.00 x 2.00 M

RICE table.
Reaction
Initial (M)
Change (M)
Equilibrium (M)
[H+] = x = 0.0188 M
[COOH] = x = 0.0188 M

2.00
0
0
x
+x
+x
2.00 x
x
x
Equilibrium Check:
a1 =
[H + ][COOH ] (0.0188)(0.0188)
=
[HCOOH]
(2.00)
= 1.77 104

This agrees with given value of Ka.
Therefore:
Final Calculations:
[HCOOH] = 2.00 x 2.00 M
HOBr will have negligible dissociation, therefore:
a1 =
a1 =
2
[H + ][COOH ] ()()
=
[HCOOH]
(2.00)
[HOBr] = [HOBr]0 = 1.50 M

a2 =
2.00
[H + ][OBr ]
[HOBr]
a2 [HOBr] (2.06 109 )(1.50)

=
[H + ]
(0.0188)
7
= 1.64 10
[OBr ] =
= a1 (2.00)
= a1 (2.00) = (1.77 104 )(2.00)
Kw = [H+][OH]
= 0.0188
[OH ] =
w
1.00 1014
=
= 5.32 1013
[H + ]
0.0188
pH = log[H + ] = log(0.0188) = 1.726
12
Ex 14.5.4: In a 0.500 M solution, uric acid

(HC5H3N4O4) is 1.6% dissociated. Calculate the
value of Ka for uric acid.
Solution:
= 0.492 M
HC5H3N4O4(aq) H+(aq) + C5H3N4O4(aq)
[H+] = x = 0.0080 M
[HC5H3N4O4] = 0.500 x = 0.500 0.0080
[C5H3N4O4] = x = 0.0080 M
Let x = amount of HC5H3N4O4 consumed.

percent dissociation =
=
(100%)
[HC5 H3 N4 O4 ]0
Final Calculations:
a =
(percent dissociation)[HC5 H3 N4 O4 ]0
(100%)
= 1.3 104
(1.6%)(0.500)
=
= 0.0080
(100%)

before any of the HC5H3N4O4 has dissociated.
[HC5H3N4O4]0 = 0.500 M, [H+]0 = 0,
[C5H3N4O4]0 = 0
Reaction
Initial (M)
Change (M)
Equilibrium (M)
HC5H3N4O4(aq) H+(aq)
0.500
+ C5H3N4O4(aq)

table.
Reaction
Initial (M)
Change (M)
Equilibrium (M)
0.500
x
0
+x
+ C5H3N4O4(aq)
0
+x

RICE table.
Reaction
Initial (M)
Change (M)
Equilibrium (M)
0.500
x
0.500 x
0
+x
x
[H + ][C5 H3 N4 O
(0.0080)(0.0080)
4]
=
[HC5 H3 N4 O4 ]
(0.500)
+ C5H3N4O4(aq)
0
+x
x
13
Strong Base: A compound which completely

dissociates into metal ions and hydroxide ions (OH)
when dissolved in water. Strong bases are hydroxides
where the metal cation is an alkali metal or one of
three alkaline earth metals: calcium, barium, or
strontium.
Chemical Species Present in Solutions Containing

Bases: Strong bases completely dissociate leaving
metal and hydroxide ions in solution. Weak bases
partially react with water leaving the weak base,
hydroxide ions, and the bases conjugate acid in
solution. Water, the solvent in base solutions,
contains both hydrogen ions and hydroxide ions.
e.g., NaOH(aq) Na+(aq) + OH(aq)

Common Strong Bases
lithium hydroxide,
sodium hydroxide,
potassium hydroxide,
rubidium hydroxide,
cesium hydroxide,
calcium hydroxide,
barium hydroxide,
strontium hydroxide,
water (H2O)
hydrogen ions (H+)
hydroxide ions (OH)
bases (B)
conjugate acids (BH+)
LiOH
NaOH
KOH
RbOH
CsOH
Ca(OH)2
Ba(OH)2
Sr(OH)2
Calculating the pH of Strong Bases: Strong bases

are the major source of hydroxide ions in a strong
base solution. The concentration of the hydroxide
ions [OH] will be approximately equal to an integer
multiple of the concentration of the base. This integer
is the number of hydroxide ions in each molecule of
the base. Pure water is considered a significant
contributor of OH ions if [B] < 106 M at 25C.
Weak Base: A substance that accepts a proton (H+)

from water forming the conjugate acid of the base
and hydroxide ions.
B(aq) + H2O(l) BH+(aq) + OH(aq)
Base
Acid
Conjugate
Acid
e.g., NaOH:
Ca(OH)2:
Conjugate
Base
The equilibrium expression for this reaction is as

follows where the equilibrium constant (Kb) is called
the base dissociation constant or base ionization
constant.
b =
[BH + ][OH ]
[B]
Note: The base doesnt actually dissociate which is

why many chemists prefer the name base ionization
constant.
14
[OH] = [NaOH]0
[OH] = 2[Ca(OH)2]0
Ex 14.6.1: Calculate the pH of a 0.0100 M Ba(OH)2

solution.
Calculating the pH of Weak Bases:

1. Identify all species in solution.
Solution:
2. Identify all species producing hydroxide ions.
[Ba(OH)2]0 = 0.0100 M
General Reaction of Base with Water:
Ba(OH)2(aq) Ba2+(aq) + 2OH(aq)

2+
B(aq) + H2O(l) BH+(aq) + OH(aq)
Species present in solution: Ba(OH)2, Ba , OH ,

H2O, and H+.
Autoionization of Water:
Ba(OH)2 is a strong base and will completely

dissociate. In comparison to a strong base, the
autoionization of water will not be a significant
contributor of OH ions.
3. Determine which species is the major contributor

of hydroxide ions (OH).
[OH ] = 2[Ba(OH)2 ]0 = 2(0.0100) = 0.0200
(a) In the absence of any strong bases, weak bases are

the major contributor of OH ions if Kb > Kw and
[B] > 106 M at 25C.
Kw = [H+][OH]
[H + ] =
(b) Pure water is the major contributor of OH ions if

Kw > Kb or [B] < 106 M at 25C.
w
1.00 1014
=
= 5.00 1013
[OH ]
0.0200
pH = log[H + ] = log(5.00 1013 ) = 12.301
(c) In a mixture of weak bases, the base with the

largest Kb value will be the major contributor of OH
ions.
4. Determine the concentration of the hydroxide ions
by applying the RICE method for equilibrium
systems.
5. Calculate the concentration of hydrogen ions using
Kw.
6. Calculate the pH.
15

all species in a 0.350 M solution of methylamine
(CH3NH2, Kb = 4.38 104).

Since Kb << 1, the system will barely shift toward the
Solution:
CH3NH2(aq) + H2O(l) CH3NH3+(aq) + OH(aq)
Therefore:
Kb = 4.38 104
[CH3NH2] = 0.350 x 0.350 M
b =
Kw = 1.0 1014
b =
Species present in solution: CH3NH2, CH3NH3 ,

OH, H2O, and H+,
[CH3 NH3+ ][OH ]

()()
=
[CH3 NH2 ]
(0.350)
2
0.350
2 = b (0.350)
Since Kb > Kw, CH3NH2 will be the major contributor

of OH ions.
= b (0.350) = (4.38 104 )(0.350)

before any of the CH3NH2 has reacted.
= 0.0124
Assumption Check:
[CH3NH2]0 = 0.350 M, [CH3NH3+]0 = 0, [OH]0 = 0

0.0124
(100%) =
(100%)
[CH3 NH2 ]0
0.350

Reaction
Initial (M)
Change (M)
Equilibrium (M)
CH3NH2(aq) + H2O(l)
0.350
-------
CH3NH3+(aq) + OH(aq)
= 3.54% < 5%

Let x = amount of CH3NH2 consumed.

table.
Reaction
Initial (M)
Change (M)
Equilibrium (M)
CH3NH2(aq) + H2O(l)
0.350
x
-------
[CH3NH2] = 0.350 x 0.350 M
0
+x
[CH3NH3+] = x = 0.0124 M
0
+x
[OH] = x = 0.0124 M

RICE table.
Reaction
Initial (M)
Change (M)
Equilibrium (M)
CH3NH2(aq) + H2O(l)
0.350
x
0.350 x
-------
0
+x
x
0
+x
x
16
e.g., Stepwise dissociation of sulfuric acid.
Equilibrium Check:
b =
H2SO4(aq) H+(aq) + HSO4(aq)
[CH3 NH3+ ][OH ] (0.0124)(0.0124)

=
[CH3 NH2 ]
(0.350)
= 4.39 104
a1 =
[H + ][HSO
4]
>> 1
[H2 SO4 ]
a2 =
[H + ][SO2
4 ]
= 1.2 102
[HSO
4]
HSO4(aq) H+(aq) + SO42(aq)
This agrees with given value of Kb.
Final Calculations:
Kw = [H+][OH]
a1 > a2
w
1.00 1014
[H + ] =
=
= 8.06 1013
[OH ]
0.0124
Note: Sulfuric acid is the only polyprotic acid that is

a strong acid in its first dissociation step.
pH = log[H + ] = log(8.06 1013 ) = 12.094
Calculating the pH of a Polyprotic Acid: The pH of

a polyprotic acid solution is determined using the
same method for finding the pH of a mixture of acids.
The acids for each dissociation step make up the
mixture.
Polyprotic Acid: An acid that can furnish more than

one proton. Each proton is donated one at a time in
separate dissociation steps. The conjugate base of the
first step becomes the acid for the second step. The
conjugate base of the second step becomes the acid
for the third step. The acids become progressively
weaker after each step.
Ex 14.7.1: Using the data from Table 14.4 in the

textbook, calculate the pH and the concentration of
all species in a 1.40 M H2C2O4 (oxalic acid) solution.
e.g., Stepwise dissociation of phosphoric acid.

Solution:
H3PO4(aq) H+(aq) + H2PO4(aq)

a1
H2C2O4(aq) H+(aq) + HC2O4(aq)
[H + ][H2 PO
4]
=
= 7.5 103
[H3 PO4 ]
a1 = 6.5 102
H2PO4(aq) H+(aq) + HPO42(aq)

a2 =
HC2O4(aq) H+(aq) + C2O42(aq)
[H + ][HPO2
4 ]
= 6.2 108
[H2 PO4 ]
a2 = 6.1 105
HPO4 (aq) H (aq) + PO4 (aq)
Kw = 1.0 1014
a3
Species present in solution: H2C2O4, H+, HC2O4,

C2O42, H2O, and OH.
[H + ][PO3
4 ]
=
= 4.8 1013
2
[HPO4 ]
a1 > a2 > a3
Since a1 > a2 > w , H2C2O4 will be the major

17

before any of the H2C2O4 has dissociated.
= a1 (1.40) = (6.5 102 )(1.40)
[H2C2O4]0 = 1.40 M, [H+]0 = 0, [HC2O4]0 = 0

= 0.30
Reaction
Initial (M)
Change (M)
Equilibrium (M)
Assumption Check:
0.30
(100%) =
(100%)
[H2 C2 O4 ]0
1.40

1.40
0
0
= 21% > 5%
Let x = amount of H2C2O4 consumed.

is negligible is not valid.

table.
Explicit Solution:
Reaction
Initial (M)
Change (M)
Equilibrium (M)
H2C2O4(aq) H (aq) + HC2O4 (aq)

1.40
0
0
x
+x
+x
+
a1 =
6.5 102 =

RICE table.
Reaction
Initial (M)
Change (M)
Equilibrium (M)
2 + (0.065) 0.091 = 0
=
Since a1 < 1, the system will barely shift toward the

2 4
2
0.065 (0.065)2 4(1)(0.091)

2(1)
= 0.34,
Therefore:
0.27
Since x cannot be negative:
[H2C2O4] = 1.40 x 1.40 M
a1 =
2
(1.40 )
(6.5 102 )(1.40 ) = 2

1.40
0
0
x
+x
+x
1.40 x
x
x
a1 =
[H + ][HC2 O4 ]
()()
2
=
=
[H2 C2 O4 ]
(1.40 ) (1.40 )
= 0.27
[H + ][HC2 O4 ] ()()
=
[H2 C2 O4 ]
(1.40)
2
1.40
[H2C2O4] = 1.40 x = 1.40 0.27 = 1.13 M

[H+] = x = 0.27 M
2 = a1 (1.40)
[HC2O4] = x = 0.27 M
18
Salts That Produce Basic Solutions: Salts that

consist of a cation of a strong base and an anion
which is a weak base (or the conjugate base of a
weak acid) will decrease the hydrogen ion (H+)
concentration when dissolved in water. The pH of the
solution will increase. A solution containing only
such a salt will be basic.
Equilibrium Check:
a1 =
[H + ][HC2 O4 ] (0.27)(0.27)
=
= 6.5 102
[H2 C2 O4 ]
(1.13)
This agrees with given value of a1 .

Final Calculations:
a2 =
e.g., The addition of KNO2 increases the pH of a

solution because K+ is the cation of the strong base
KOH and NO2 a weak base (or conjugate base of a
weak acid).
2
2 O4 ]
[HC2 O
4]
[H + ][C
[C2 O2
4 ] =
(6.1 105 )(0.27)

a2 [HC2 O
4]
=
+
[H ]
(0.27)
KNO2(aq) K+(aq) + NO2(aq)

KOH(aq) K+(aq) + OH(aq)
= 6.1 105
NO2(aq) + H2O(l) HNO2(aq) + OH(aq)
Kw = [H+][OH]
[OH ]
Kb = 2.2 1011
w
1.0 1014
= + =
= 3.7 1014
[H ]
0.27
or
pH = log[H + ] = log(0.27) = 0.57
HNO2(aq) H+(aq) + NO2(aq)
Salt: An ionic compound.
Salts That Produce Neutral Solutions: Salts that

consist of a cation of a strong base and an anion of a
strong acid have no effect on the hydrogen ion (H+)
solution will remain unchanged. A solution
containing only this type of salt will be neutral.
e.g., The addition of NaCl has no effect on the pH of
a solution because Na+ is the cation of the strong base
NaOH and Cl is the anion of the strong acid HCl.
NaCl(aq) Na+(aq) + Cl(aq)
HCl(aq) H+(aq) + Cl(aq)
Ka >> 1
NaOH(aq) Na+(aq) + OH(aq)
Kb >> 1
Kb >> 1
19
Ka = 4.6 104
Salts That Produce a Weak Acid and Weak Base

Mixture: Salts that consist of a cation which is a
weak acid (or conjugate acid of a weak base) and an
anion which is a weak base (or conjugate base of a
weak acid) will produce a weak acid and weak base
mixture when dissolved in water. The change in pH
of the solution will depend on the relative values of
Ka for the weak acid and Kb for the weak base.
Salts That Produce Acidic Solutions:

1. Salts that consist of a cation which is a weak acid
(or the conjugate acid of a weak base) and an anion
of a strong acid will increase the hydrogen ion (H+)
solution will decrease. A solution containing only
such a salt will be acidic.
e.g., The addition of NH4Cl decreases the pH of a
solution because NH4+ is a weak acid (or conjugate
acid of a weak base) and Cl is the anion of a strong
acid.
Relative Ka and Kb
Values
Acidity of Solution
Ka > Kb
acidic
Ka < Kb
basic
Ka = Kb
neutral
NH4Cl(aq) NH4 (aq) + Cl (aq)

+
Ka >> 1
Relationship Between Ka and Kb:
NH4 (aq) H (aq) + NH3(aq)

+
Ka = 5.6 10
10
HA(aq) H+(aq) + A(aq)
or
NH3(aq) + H2O(l) NH4 (aq) + OH (aq)

+
a =
[H + ][A ]
[HA]
b =
[HA][OH ]
[A ]
A(aq) + H2O(l) HA(aq) + OH(aq)
Kb = 1.8 105
2. Salts containing a highly charged metal ion

decrease the pH when dissolved in solution. The
hydrated ion that forms when the metal ion is
dissolved in water is a weak acid which dissociates
acidic protons increasing the hydrogen ion (H+)
concentration. A solution containing only such a salt
will be acidic.
a b =
[H + ][A ] [HA][OH ]
[HA]
[A ]
= [H + ][OH ] = w
a b = w
e.g., The addition of AlCl3 decreases the pH of a

solution because Al3+ forms the hydrated ion
Al(H2O)63+ which is a weak acid.
Al(H2O)63+(aq) H+(aq) + Al(OH)(H2O)52+(aq)
Ka = 1.4 105
20
a b = w
Ex 14.8.1: Using the data below, calculate Ka or Kb

and write the reaction with water for each of the
aqueous ions.
b =
(a) NO2 (HNO2, Ka = 4.0 104)
Na+ is a cation of a strong base and will not affect the

pH of the solution. PO43 is a fairly strong base. The
solution will be moderately basic.
Solution:
(b) KI
a b = w
Solution:
w 1.0 1014
b =
=
= 2.5 1011
a
4.0 104
KI(aq) K+(aq) + I(aq)
(b) C6H5NH3+, anilinium (C6H5NH2, aniline, Kb =

2.35 105)
Solution:
C6H5NH3 (aq) H (aq) + C6H5NH2(aq)
a b = w
a =
KOH(aq) K+(aq) + OH(aq)
Kb >> 1
HI(aq) H+(aq) + I(aq)
Ka >> 1
K+ is the cation of a strong base and I is the anion of

a strong acid. Since neither of these ions affects the
pH, the solution will be neutral.
w 1.0 1014
=
= 2.1 102
a 4.8 1013
(c) HC5H5NCl, pyridinium chloride (C5H5N,

pyridine, Kb = 1.7 109)
14
w 1.00 10
=
= 4.26 1010
b
2.35 105
Solution:
Ex 14.8.2: Predict whether each of the following

salts will create an acidic, basic, or neutral aqueous
solution.
HC5H5NCl (aq) HC5H5N+(aq) + Cl(aq)

C5H5N(aq) + H2O(l) HC5H5N+(aq) + OH(aq)
(a) Na3PO4 (HPO42, Ka = 4.8 1013)
Kb = 1.7 109
Solution:
or
Na3PO4(aq) 3Na+(aq) + PO43(aq)
HC5H5N+(aq) H+(aq) + C5H5N(aq)
NaOH(aq) Na+(aq) + OH(aq)
a b = w
Kb >> 1
2
a =
HPO4 (aq) H (aq) + PO4 (aq)

+
w 1.0 1014
=
= 5.9 106
b
1.7 109
Ka = 4.8 1013
Ka >> 1
Cl is an anion of a strong acid and will not affect the

pH of the solution. HC5H5N+ is a weak acid. The
solution will be acidic.
or
PO43(aq) + H2O(l) HPO42(aq) + OH(aq)
21
(d) NH4F (NH3, Kb = 1.8 105; HF, Ka = 7.2 104)
a b = w
NH4F(aq) NH4+(aq) + F(aq)
b =
NH3(aq) + H2O(l) NH4+(aq) + OH(aq)
b1 = 1.8 10
Kw = 1.0 1014
or
Species present in solution: NaNO2, Na+, NO2, H2O,

H+, and OH.
NH4 (aq) H (aq) + NH3(aq)

+
Na+ is a cation of a strong base and will not affect the

pH of the solution. NO2 is a weak base and will
affect the pH.
a1 b1 = w
a1 =
w 1.0 1014
=
= 5.6 1010
b1
1.8 105
Since Kb > Kw, NO2 will be the major contributor of

OH ions.
HF(aq) H+(aq) + F(aq)

before any of the NO2 has reacted.
a2 = 7.2 104
F(aq) + H2O(l) HF(aq) + OH(aq)
[NO2]0 [NaNO2]0 = 0.500 M, [HNO2]0 = 0,

[OH]0 = 0
a2 b2 = w
b2
w 1.0 1014
=
=
= 1.4 1011
a2
7.2 104
NH4+ is a weak acid and F is a weak base. Since

a1 > b2 , the solution will be slightly acidic.
Reaction
Initial (M)
Change (M)
Equilibrium (M)
Ex 14.8.3: Calculate the pH of a 0.500 M NaNO2

solution. (HNO2, Ka = 4.0 104)
NaOH(aq) Na (aq) + OH (aq)
H2O(l) HNO2(aq) + OH(aq)

--0
0
-----

table.
NaNO2(aq) Na+(aq) + NO2(aq)
NO2(aq) +
0.500
Let x = amount of NO2 consumed.
Solution:
w 1.0 1014
=
= 2.5 1011
a
4.0 104
Reaction
Initial (M)
Change (M)
Equilibrium (M)
Kb >> 1
HNO2(aq) H+(aq) + NO2(aq)
NO2(aq) +
0.500
x

--0
0
--+x
+x
---

RICE table.
Ka = 4.0 104
or
Reaction
Initial (M)
Change (M)
Equilibrium (M)
22
NO2(aq) +
0.500
x
0.500 x

--0
0
--+x
+x
--x
x
This agrees with given value of Kb.
Since Kb << 1, the system will barely shift toward the

Final Calculations:
Therefore:
[H + ] =
Kw = [H+][OH]
[NO2] = 0.500 x 0.500 M

b =
b =
][OH ]
[HNO2
[NO
2]
2
0.500
pH = log[H + ] = log(2.9 109 ) = 8.54
()()
(0.500)
Structural Factors Affecting the Properties of

Brnsted-Lowry Acids: Let XH represent a bond
between any element or molecular group of atoms
(X) and hydrogen (H). In general, the following
factors determine whether an XH bond will exhibit
acidic properties.
2 = b (0.500)
1. Strength of Bond The stronger the XH bond,

the more difficult it is to remove the hydrogen ion.
Strong XH bonds decrease acidic behavior.
= b (0.500) = (2.5 1011 )(0.500)

= 3.5 106
2. Polarity of Bond The more polar the XH bond,

the easier it is for a molecule to dissociate and
produce hydrogen ions when dissolved in water.
High XH bond polarity increases acidic behavior.
Assumption Check:
3.5 106
(100%) =
(100%)
[NO2 ]0
0.500
Oxyacids: Oxyacids contain the grouping HOX,

where X is any element or molecular group of atoms.
In general, the following factors determine whether
an OH bond will exhibit acidic properties.
= 0.00070% < 5%

1. Number of Oxygen Atoms The greater the

number of oxygen atoms bonded to the central atom,
the easier it is for a molecule to dissociate and
produce hydrogen ions when dissolved in water.
Increasing the number of oxygen atoms bonded to the
central atom increases the acidic behavior.
[NO2] = 0.500 x 0.500 M
[HNO2 ] = x = 3.5 106 M
2. Electronegativity The greater the

electronegativity of element X, the greater the acidic
behavior.
[OH] = x = 3.5 106 M
Equilibrium Check:
b =
[HNO2 ][OH ] (3.5 106 )(3.5 106 )

=
[NO
(0.500)
2]
= 2.4 104
w
1.0 1014
=
= 2.9 109
[OH ]
3.5 106
23
Ex 14.10.1: Determine whether the following oxides

will give an acidic or basic solution when added to
water.
Ex 14..1: Place the following species in order of

increasing acidic strength.
HIO3 HIO, HIO4, HIO2
(a) SO3
Solution:
Solution:
Acidic strength increases with increasing number of
oxygen atoms bonded to the central atom.
SO3(g) + H2O(l) H2SO4(aq)
HIO < HIO2 < HIO3 < HIO4
The solution will be acidic.
Ex 14.9.1: Place the following species in order of

increasing basic strength.
(b) K2O
Solution:
OCl, OI, OBr
K2O (s) + H2O(l) 2KOH(aq)

Solution:
The solution will be basic.
Acidic strength increases with increasing
electronegativity on the atom X of HOX.
(c) NO2
electronegativity Cl = 3.0
electronegativity I = 2.5
electronegativity Br = 2.8
Solution:
NO2(g) + H2O(l) HNO3(aq) + H(g)
H(g) + NO2(g) HNO2(aq)
2NO2(g) + H2O(l) HNO2(aq) + HNO3(aq)
Acidic strength:
HOI < HOBr < HOCl
The solution will be acidic.

Basic strength (conjugate base of weakest acid is the
strongest base):
OCl < OBr < OI
Acidic Oxide: An oxide where the oxygen atoms are
bonded to the central atom by covalent bonds. These
oxides will produce acidic solutions when dissolved
in water.
e.g., CO2(g) + H2O(l) H2CO3(aq)
Basic Oxide: An oxide where the oxygen atoms are
bonded to a metal atom by ionic bonds. These oxides
will produce basic solutions when dissolved in water.
e.g., MgO(s) + H2O(l) Mg(OH)2(aq)
24
(c) CO2(g) + H2O(l) H2CO3(aq)
Lewis Acid: A substance that can accept a pair of

electrons. In general, Lewis acids contain a fully or
partial positively charged atom with an empty or
underused valence orbital.
Solution:
Lewis acid: CO2

Lewis Base: A substance that can donate a pair of
electrons. In general, Lewis bases contain atoms with
lone pairs.
Lewis base: H2O
Summary of Acid-Base Models:
The carbon atom in CO2 accepts an electron pair

from the H2O molecule which is followed by a proton
(H+) shift to form H2CO3.
Model
Definition of
Acid
Definition of
Base
Arrhenius
H+ producer
OH producer
BrnstedLowry
H+ donor
H+ acceptor
Lewis
electron-pair
acceptor
electron-pair
donor
Ex 14.11.1: Identify the Lewis acid and Lewis base

in the following reactions.
(a) Cu2+(aq) + 4NH3(aq) Cu(NH3)42+(aq)
Solution:
Lewis acid: Cu2+

Lewis base: NH3
Cu2+ accepts one electron pair from each of the four
NH3 molecules.
(b) I(aq) + I2(aq) I3(aq)
Solution:
Lewis acid: I2
Lewis base: I
The Lewis structure of I3 has he extra electron pair
on the central atom. Therefore I donates one electron
pair to one of the atoms of I2.
AP Chemistry Notes 14
25

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Chapter 14 Acids and Bases

Conjugate Acid-Base Pair: The compounds which

e.g., HCl(g) H+(aq) + Cl(aq)

Ex 14.1.1: In each of the following chemical

Arrhenius Base: A substance which produces

(a) HNO3(aq) + H2O(l) H3O+(aq) + NO3(aq)

e.g., NaOH(s) Na+(aq) + OH(aq)

(b) H2O(l) + HSO4(aq) H3O+(aq) + SO42(aq)

Brnsted-Lowry Acid: A substance which donates a

(c) NH2(aq) + H2O(l) OH(aq) + NH3(aq)

HA(aq) + H2O(l) H3O+(aq) + A(aq)

Conjugate Acid: The compound that forms when a

Ex 14.1.2: Write the conjugate base for each of the

Conjugate Base: The compound that remains when

In aqueous solution, the acid (HA) donates a proton

HA(aq) + H2O(l) H3O+(aq) + A(aq)

Ex 14.1.5: Write a chemical equation showing how

Ex 14.1.3: Write the conjugate acid for each of the

(b) HPO42, H3PO4

(c) NH2, NH3

(d) Cl, ClO

Common Strong Acids

Weak Acid: An acid which barely dissociates in

The equilibrium expression for this reaction is as

1. Most acids are weak or moderately weak in

2. A strong acid has a weak conjugate base, while a

In the forward direction, HA is the acid, H2O is the

3. A strong acid has a conjugate base that is a weaker

HA(aq) + H2O(l) H3O+(aq) + A(aq)

4. A weak acid has a conjugate base that is a stronger

In the reverse direction, H3O+ is the acid, A is the

Monoprotic Acid: An acid that can furnish only one

HA(aq) + H2O(l) H3O (aq) + A (aq)

Diprotic Acid: An acid that can furnish two protons.

Acid Strength: A measure of the tendency of an acid

e.g., H2SO4(aq) + H2O(l) H3O+(aq) + HSO4(aq)

Strong Acid: An acid which almost completely

Triprotic Acid: An acid that can furnish three

e.g., HCl(aq) H+(aq) + Cl(aq)

e.g., H3PO4(aq) + H2O(l) H3O+(aq) + H2PO4(aq)

H2PO4(aq) + H2O(l) H3O+(aq) + HPO42(aq)

HPO42(aq)+ H2O(l) H3O+(aq) + PO43(aq)

Ex 14.2.1: Calculate the unknown [H+] or [OH] for

Water as an Acid and a Base

(a) 1.41 106 M H+

Autoionization of Water: Regardless of whether

H2O(l) + H2O(l) H3O+(aq) + OH(aq)

[H+] > [OH]

Ion-Product Constant [Kw]: The equilibrium

The hydronium ion (H3O+) is commonly abbreviated

At 25C in pure water with 2 significant figures:

[H+] = [OH] = 1.0 107 M

[H+] < [OH]

w = [H + ][OH ] = (1.0 107 )(1.0 107 )

Note: The acid dissociation constant for water is

neutral solution: [H+] = [OH]

[H+] > [OH]

[H+] < [OH]

Note: Pure water is neutral.

and its inverse,

and its inverse,

Relationship Between pH, pOH, and pKw: