Chemistry 102 Chapter 15

ACID-BASE CONCEPTS

General Properties:

ACIDS BASES
Taste sour Bitter
Change color of
 
indicators
Blue Litmus turns red no change
Red Litmus no change turns blue
Phenolphtalein Colorless turns pink
React with bases to React with acids to
Neutralization
form salt and water form salt and water

Arrhenius Concept of Acids and Bases:

 Arrhenius definition of acids and bases in based on their behavior in water (aqueous solutions)

ACIDS BASES

 Substances that dissolved in water  Substances that dissolved in water

to increase the concentration of
H3O+ (hydronium ions)
 Accepted simplification: H+
 H+ is always attached to a water
molecule.
to increase the concentration of
OH–(hydroxide ions)
O H

H O H
H

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Chemistry 102 Chapter 15

STRONG ACIDS AND BASES

 Strong acids and bases completely ionize in aqueous solutions and are therefore strong electrolytes.

STRONG ACIDS STRONG BASES

 Completely ionize in aqueous solution to form  Completely ionize in aqueous solution to
H3O+ and an anion form OH– and a cation

HA (aq) + H2O (l) H3O+ + A– (aq) BOH (s) H 2O

B+ (aq) + OH– (aq)

Examples: Examples:

HCl (aq) + H2O (l) H3O+ (aq) + Cl– (aq) NaOH (s) H2 O
Na+ (aq) + OH– (aq)

HNO3 (aq) + H2O (l) H3O+ (aq) + NO3– (aq) KOH (s) H2 O
K+ (aq) + OH– (aq)

H2SO4 (aq) + H2O (l) H3O+ (aq)+ HSO4– (aq) Ca(OH)2 (s) H2 O
Ca2+ (aq) + 2 OH– (aq)

HClO4 (aq) + H2O (l) H3O+ (aq) + ClO4– (aq) Ba(OH)2 (s) H2 O
Ba2+ (aq) + 2 OH– (aq)

NEUTRALIZATION REACTIONS BETWEEN STRONG ACIDS AND STRONG BASES

HA (aq) + H2O (l) + BOH (aq)  BA (aq) + 2 H2O (l)

strong acid strong base soluble salt water

H3O+ (aq) + A (aq) + B+ (aq) + OH (aq)  B+ (aq) + A (aq) + 2 H2O (aq)

H3O+ (aq) + A (aq) + B+ (aq) + OH (aq)  B+ (aq) + A (aq) + 2 H2O (aq)

Net Ionic Equation H3O+ (aq) + OH (aq)  2 H2O (aq)

Accepted simplification for N.I.E. H+(aq) + OH(aq)  H2O(l)

NOTE: It has been observed that all neutralization reactions between strong acids and bases:
 are exothermic
 have the same enthalpy of reaction per mol of H+ = –55.90 kJ

CONCLUSION:
 The neutralization reaction between any strong acid and any strong base is:

H+(aq) + OH(aq)  H2O(l) H0 = –55.90/mol H+ ions

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Chemistry 102 Chapter 15

WEAK ACIDS AND BASES

 Weak acids and bases partially ionize in aqueous solutions and are therefore weak electrolytes.

 Weak acids and bases exist in reversible reactions (equilibrium) with the corresponding ions.

WEAK ACIDS:

HC2H3O2 (aq) + H2O (l) H3O+ (aq) + C2O3O2 (aq)

HF (aq) + H2O (l) H3O+ (aq) + F (aq)

WEAK BASES:

NH3 (g) + H2O (l) NH4+(aq) + OH (aq)

Limitations of the Arrhenius Concept:

1. Considers acid-base reactions only in aqueous solutions

2. Singles out the OH ion as the source of base character (other species can play a similar role)

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Chemistry 102 Chapter 15

BRONSTED-LOWRY CONCEPT OF ACIDS AND BASES

 Bronsted and Lowry defined acids and bases in terms of H+ (proton) transfer.

ACIDS BASES
H+ (proton) donors H+ (proton) acceptors
NEUTRALIZATION: A reaction in which a H+ (proton) is transferred

HCl (aq) + NH3 (aq)  NH4Cl (aq)

strong acid weak base soluble salt

H+ (aq) + Cl (aq) + NH3 (aq)  NH4+ (aq) + Cl (aq)

N.I.E. H+

H+(aq) + NH3 (aq)  NH4+ (aq)

acid base

 Bronsted-Lowry neutralization can also occur in a non-aqueous system:

H+

HCl (benzene) + NH3(benzene)  NH4Cl (s)

acid base

Examples:
Identify the Bronsted-Lowry acid and base in each of the following equations:

1. C6H5OH + C2H5O− → C6H5O− + C2H5OH

2. H2O + Cl− → HCl + OH−

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Chemistry 102 Chapter 15

BRONSTED-LOWRY CONCEPT OF ACIDS AND BASES

 In a reversible acid-base reaction, both forward and reverse reactions involve H+ transfer

H+ H+

NH3 (aq) + H2O (l) NH4+ (aq) + OH (aq)

base acid acid base

NH4+ and NH3 H2O and OH

 differ by a H+  differ by a H+
 are a conjugate acid-base pair  are a conjugate acid-base pair
 NH4+ is the conjugate acid of NH3  H2O is the conjugate acid of OH−
 NH3 is the conjugate base of NH4+  OH− is the conjugate base of H2O

H+ H+

HC2H3O2 (aq) + H2O (l) C2H3O2 (aq) H3O+ (aq)

acid base base acid

HC2H3O2 and C2H3O2− H2O and H3O+

 differ by a H+
 are a conjugate acid-base pair
 HC2H3O2 is the conjugate acid of
C2H3O2−
 C2H3O2− is the conjugate base of
HC2H3O2
 differ by a H+
 are a conjugate acid-base pair
 H2O is the conjugate base of H3O+
 H3O+ is the conjugate acid of H2O

In General: A conjugate acid-base pair consists of two species in an acid-base reaction

that differ by the loss or gain of a H+ (proton)

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Chemistry 102 Chapter 15

 Species that can act both as an acid and a base are called amphiprotic.

Consider:
H+

NH3 (aq) + H2O (l) NH4+(aq) + OH (aq)

base acid acid base

H+

HC2H3O2(aq) + H2O (l) C2H3O2 (aq) + H3O+ (aq)

acid base base acid

 H2O can
 lose a H+ and act as an acid (with the weak base NH3)
OR
 gain a H+ and act as a base (with the weak acid HC2H3O2)

 H2O is an amphiprotic species

 Bicarbonate ion(HCO3–) is another example of amphiprotic species, as illustrated by the

following reactions:

H+

HCO3 (aq) + OH (aq) CO32 (aq) + H2O (l)

acid base
+
H

HCO3(aq) + H+(aq) CO2 (g) + H2O (l)

base acid

 The Bronsted-Lowry Concept of Acids & Bases is more general than the Arrhenius concept.

 Bronstead-Lowry Concept introduces additional points of view:

1. A base is a species that accepts H+ ions (OH is only one example of a base)
2. Acids and Bases can be ions as well as molecular substances
3. Acid-Base reactions are not restricted to aqueous solutions
4. Amphiprotic species can act as either acids or bases depending on what the other reactant is.

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Chemistry 102 Chapter 15

LEWIS CONCEPT OF ACIDS AND BASES

 Gilbert Lewis defined acids and bases in terms of electron-pair transfer.

HCl (aq) + NH3 (aq)  NH4Cl (aq)

strong acid weak base

H+(aq) + Cl(aq) + NH3(aq)  NH4+(aq) + Cl(aq)

N.I.E.: H+(aq) + NH3 (aq)  NH4+ (aq)

H H +

H+ : NH  H:NH

H H
electron pair electron pair
acceptor donor
LEWIS ACID LEWIS BASE

Example 1:

BF3 + NH3  BF3NH3

F H F H

FB : N  H  F  B  N  H

F H F H
electron
deficient molecule
electron pair electron pair
acceptor donor
LEWIS ACID LEWIS BASE

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Chemistry 102 Chapter 15

Example 2:

Na2O(s) + SO3 (g)  Na2SO4 (s)

.. .. 2
2 :O: :O:
.. +   .. ..
:O: S = O :  :OSO:
.. .. .. ..
: O: :O:
.. ..
electron pair electron pair
donor acceptor
LEWIS BASE LEWIS ACID

Example 3:
Formation of complex ions

Al3+ (aq) + 6 H2O (l)  Al(H2O)63+

electron pair electron pair hydrated ion
acceptor donor
ACID BASE
In General:

LEWIS ACIDS LEWIS BASES

electron pair acceptors electron pair donors
Usually positive ions or electron Usually negative ions or molecules
deficient molecules with lone pairs
NEUTRALIZATION: A reaction in which an electron pair is transferred

SUMMARY OF ACID – BASE CONCEPTS

ACID BASE NEUTRALIZATION

Substance that Substance that
Arrhenius
dissolved in water dissolved in water
Concept H+(aq) + OH–(aq)  H2O (l)
increases concentration increases concentration
(least general)
of H3O+ of OH–
Bronsted-
Lowry A H+ donor A H+ acceptor A H+ transfer
Concept
Lewis An electron pair An electron pair An electron pair
Concept acceptor donor transfer
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Chemistry 102 Chapter 15

ACID AND BASE STRENGTHS

Relative Strengths of Acids

 A strong acid completely ionizes in solution, whereas a weak acid only partially ionizes.

 Therefore, the strength of the acid depends on the equilibrium:

HA (aq) + H2O (l) 

strong acid if equibrium lies to the right
 
 H3O+ (aq) + A– (aq)
weak acid if equilibrium lies to the left

 An acid is stronger than another acid if it lose H+ more readily.

 To estimate relative acidic strength, comparisons between pairs of acids are made.

HCl (aq) and H3O+ (aq)

 Recall that HCl(aq) is a strong acid and as such it ionizes completely in water:

 H3O+ (aq) + Cl (aq)

HCl (aq) + H2O (aq) 

 The reaction goes completely to products.

 “ASSUME” that a reverse reaction were possible to a very small extent:

H+ H+

HCl (aq) + H2O(aq) H3O+ (aq) + Cl (aq)

loses H+ more loses H+ less

readily readily

HCl(aq) is a stronger acid than H3O+(aq) HCl(aq)  H3O+(aq)

 Similar comparisons between other pairs of acids show the following results:

H3O+(aq) is a stronger acid than HC2H3O2(aq) H3O+(aq)  HC2H3O2(aq)

H3O+(aq) is a stronger acid than HF(aq) H3O+(aq)  HF(aq)
HF(aq) is a stronger acid than HC2H3O2 (aq) HF(aq)  HC2H3O2 (aq)
HI is a stronger acid than HCl HI  HCl

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Chemistry 102 Chapter 15

ACID AND BASE STRENGTHS

SUMMING UP:
1. HCl(aq) is a stronger acid than H3O+(aq) HCl(aq)  H3O+(aq)
2. H3O+(aq) is a stronger acid than HC2H3O2(aq) H3O+(aq)  HC2H3O2(aq)
3. H3O+(aq) is a stronger acid than HF(aq) H3O+(aq)  HF(aq)
4. HF(aq) is a stronger acid than HC2H3O2 (aq) HF(aq)  HC2H3O2 (aq)
5. HI is a stronger acid than HCl HI  HCl

 A Table of Relative Strengths of acids can now be constructed:

Strongest Acid
HI

HCl Strength
of acids
H3O+ increases
HF

HC2H3O2
Weakest Acid

 An acid-base reaction always goes in the direction of the weaker acid:

HCl(aq) + H2O(aq) H3O+(aq) + Cl(aq)

stronger weaker
acid acid

HC2H3O2 (aq) + H2O(l) C2H3O2(aq) + H3O+(aq)

weaker stronger
acid acid

HF (aq) + H2O (l) F(aq) + H3O+(aq)

weaker stronger
acid acid

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Chemistry 102 Chapter 15

ACID AND BASE STRENGTHS

Relative Strengths of Bases

 Similar to acids, a strong base completely ionizes in solution.

 Na+ (aq) + OH– (aq)

NaOH (aq) 

 Unlike strong bases that contain OH– , weak bases produce hydroxide by reacting with water.


 BH+ (aq) + OH– (aq)
B (aq) + H2O (aq) 


 When diprotic acids ionize, they do so in 2 different steps.

H2SO4 (aq) + H2O (l) 

 H3O+ (aq) + HSO42–


 H3O+ (aq) + SO4–
HSO4– + H2O (l) 

 When diprotic bases ionize, they do so in 1 step.

 Ca2+ (aq) + 2 OH– (aq)

Ca(OH) (aq) 

 A base is stronger than another base if it gains H+ more readily

 To estimate relative base strength, comparisons between pairs of bases are made.

H2O (l) and Cl(aq)

 Recall that HCl(aq) is a strong acid and as such it ionizes completely in water:

HCl(aq) +  H3O+(aq) + Cl(aq)

H2O(aq) 

 The reaction goes completely to products.

 “ASSUME” that a reverse reaction were possible to a very small extent:

H+ H+

HCl (aq) + H2O(l) H3O+(aq) + Cl(aq)

gains H+ more gains H+ less

readily readily

H2O(l) is a stronger base than Cl(aq) H2O(l)  Cl(aq)

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Chemistry 102 Chapter 15

ACID AND BASE STRENGTHS

 Similar comparisons between other pairs of bass show the following results:

C2H3O2(aq) is a stronger base than H2O(l) C2H3O2(aq)  H2O(l)

F (aq) is a stronger base than H2O(aq) F(aq)  H2O (aq)
C2H3O2(aq) is a stronger base than F(aq) C2H3O2(aq)  F(aq)
Cl is a stronger base than I Cl  I

SUMMING UP:
1. H2O(l) is a stronger base than Cl(aq) H2O(l)  Cl (aq)
2. C2H3O2(aq) is a stronger base than H2O(l) C2H3O2(aq)  H2O(l)
3. F (aq) is a stronger base than H2O(aq) F (aq)  H2O (aq)
4. C2H3O2(aq) is a stronger base than F(aq) C2H3O2(aq)  F (aq)
5. Cl is a stronger base than I Cl   I 

 A Table of Relative Strengths of bases can now be constructed:

Weakest Base
I

Cl  Strength
of bases
H2 O increases

F

C2H3O2
Strongest Base

 The Tables of Relative Strengths of Acids and Relative Strengths of Bases can now be combined:

HI I

Strength HCl Cl Strength

of acids of bases
increases increases
H3 O+ H2 O

HF F

HC2H3O2 C2H3O2

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Chemistry 102 Chapter 15

CONCLUSIONS:
1. When an acid loses its H+ readily, its conjugate base does not hold the H+ very tightly.

Ex: HCl and Cl

strong weak
acid base

 The strongest acids have the weakest conjugate bases

2. When a base holds the H+ very tightly, its conjugate acid does not lose the H+ readily

Ex: C2H3O2 and HC2H3O2

strong weak
base acid

 The strongest bases have the weakest conjugate acids

3. The direction of an acid-base reaction always favors the formation of the weaker acid and the
weaker base:

H+ H+

HC l(aq) + H2O (l) H3O+(aq) + Cl(aq)

stronger stronger weaker weaker
acid base acid base

H+ H+

HC2H3O2(aq) + H2O(l) C2H3O2(aq) + H3O+(aq)

weaker weaker stronger stronger
acid base base acid

H+ H+

HF(aq) + H2O(l) F(aq) + H3O+(aq)

weaker weaker stronger stronger
acid base base acid

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Chemistry 102 Chapter 15

Examples:
For each reaction below, determine the conjugate acid-base pairs and their relative strengths:

1. HSO4– + CH3CO2– CH3CO2H + SO42–

2. HCO3– + F– HF + CO32–

3. NH4+ + CN– HCN + NH3

4. The hydrogen oxalate ion (HC2O4–) is amphiprotic. Write a balanced equation showing
how it reacts as an acid towards water and another equation showing how it reacts as a
base towards water.

5. For each acid shown below, write the formula of its conjugate base:

HPO42– CH3NH3+ NH3

6. For each base shown, write the formula of its conjugate acid:

HAsO42– IO– O2–

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Chemistry 102 Chapter 15

MOLECULAR STRUCTURE AND ACID STRENGTH

 The strength of an acid depends on how easily a H+ is removed from the H  Y bond.

 Ease of H+ loss is determined by 2 factors:

Polarity of the H–Y bond

Strength of the H–Y bond

 To be acidic, the HY bond must be polar with H atom as the positive pole.

+
+
H–Y–
 As a result, compare the following bonds and their corresponding dipole moments:

–
H–Li+ H–C +
H–F–
Not acidic Not acidic Acidic

The Polarity of the H  Y bond

 The polarity of the H–Y bond depends on the EN (electronegativity difference)
between the atoms involved in the bond

The The The

The The
higher higher more
easier to stronger
the E.N. the polar the
lose H+ the acid
of Y ∆E.N. bond

The strength of the H  X bond

 The strength of the H  Y bond depends on the size of Y (smaller atoms form stronger
bonds)

The The less

The The The
weaker tightly
larger Y easier to stronger
the H–Y the H is
is lose H+ the acid
bond held

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Chemistry 102 Chapter 15

MOLECULAR STRUCTURE AND ACID STRENGTH

Trends among Binary Acids (HY)

1. Across a period going from left to right

 The polarity of the H–Y bond determines this trend.

Electronegativity of Y increases

 Polarity of the H–Y increases

Consequently:
 H2O is a weaker acid than HF H2O  HF
 H2S is a weaker acid than HCl H2S  HCl

2. Going down a group

 The strength of the H–Y bond determines this trend

F HF
Atomic Strength Acidic
Cl Size H  Cl of Strength
Increases Bond Increases
Br (more H  Br Decreases
electron
I shells) HI

 The diagram below illustrates the combined effect of bond polarity and strength on the acids of
group VI and VII.

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Chemistry 102 Chapter 15

MOLECULAR STRUCTURE AND ACID STRENGTH

Trends among Oxoacids

 Oxoacids are O containing acids

+ 
HOY

acidic H is always attached to an O atom

 The polarity of the H  O bond determines the relative acidic strength

 The polarity of the H  O bond depends on 2 factors:

The Electronegativity of the Y atom

The more
The The The
polar the
more EN easier to stronger
H–O
Y is lose H+ the acid
bond

H  O  Cl  H  O  Br  HOI
EN(Cl) = 3.16 EN(Br) = 2.96 EN(I) = 2.66
(strongest) (weakest)

ACIDIC STRENGTH INCREASES

The number of O atoms bonded to Y (excluding O in OH groups)

The more The more

The more polar The
O atoms electro-
the H–O–Y stronger
bonded negative Y
bond becomes the acid
to Y becomes

HClO  HClO2  HClO3  HClO4

(weakest) (strongest)
ACIDIC STRENGTH INCREASES
O O

H  O  Cl H  O  Cl  O H  O  Cl  O H  O  Cl  O

O
least polar most polar
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Chemistry 102 Chapter 15

MOLECULAR STRUCTURE AND ACID STRENGTH

SUMMARY
 BINARY ACIDS

Acidic Strength Increases

Acidic strength
(H–Y polarity increases) increases
(H–Y bonds
weakens as size
of Y increases)

 OXOACIDS (H attached to Y through O)

Acidic strength
increases
(polarity of
H–O increases)

The more O atoms attached to Y, the stronger the acid

 POLYPROTIC ACIDS
 contain more than one acidic H
 are stronger than their corresponding anions

H2SO4  HSO4–
strong weak
acid acid

H3PO4  H2PO4  HPO42

Acidic Strength Increases

Reason: The acid strength of a polyprotic acid and its anion(s) decreases with increasing
negative charge (it becomes increasingly difficult to lose a H+)

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Chemistry 102 Chapter 15

MOLECULAR STRUCTURE AND ACID STRENGTH

Examples:
1. Which member of each of the following pair is the stronger acid?

a) NH3 and PH3

b) HI and H2Te

c) H2SO3 and H2SeO3

d) HBrO4 and HBrO3

e) HBr and H2Se

2. List the following compounds in order of increasing acid strength:

a) HBr, H2Se, H2S

b) HBrO3, HClO2, HBrO

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Chemistry 102 Chapter 15

SELF-IONIZATION OF WATER

 Pure Water is generally considered a non-electrolyte.

 It is actually a very, very weak electrolyte:

H+

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

[H 3O+ ][OH ]  Kc is very small

Kc =
[H 2O]2
 The equilibrium is strongly shifted to the left

 [H2O]2 = is essentially constant

 [H2O] for 1L of water can be calculated as follows:

moles 1000 g 1 mole

?  = 1 L x  x   55 M
L 1L 18.02 g

 [H2O]2 x Kc = [H3O+] [OH] = Kw = 1.0 x 1014

Kw = is called THE ION-PRODUCT OF WATER

= 1.0 x 1014 at 250C (is temperature dependent)

 CONCLUSION: Kw = [H3O+] [OH] = 1.0 x 1014 (250C)

In Pure Water: [H3O+] = [OH] = x

Kw = x2 x = K w = 1.0x10 14

[H3O+] = [OH] = 1.0 x 107 M

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Chemistry 102 Chapter 15

Solution of a Strong Acid:

Example: A 0.1 M solution of HCl

HCl (aq) + H2O (l) complete

ionization
H3O+ (aq) + Cl (aq)
0 0.1 M 0.1 M

 The TOTAL CONCENTRATION OF THE [H3O+] can be thought of as the sum of the:

 concentration of [H3O+] provided by the acid; [H3O+] = 1.0 x 101 M

 concentration of [H3O+] provided by the self-ionization of water; [H3O+] = 1.0 x 107 M

Total Conc. of [H3O+] = [H3O+] + [H3O+]

from acid from self-ionization of water
= 1.0 x 101 M + less than 1.0 x 107 M (negligible)
= 1.0 x 101 M

 Concentration of the [OH] can now easily be calculated:

1.0 x 10 14 1.0 x 10 14
[H3O+] [OH] = 1.0 x 1014 [OH] = +
= 1
= 1.0 x 10 13 M
[H3O ] 1.0 x 10
 +
In a solution of a strong acid the concentration of the [H3O ] produced by the self-ionization of
water can be ignored.

In a solution of a Strong Base:

Example: A 0.010 M solution of NaOH

NaOH (aq) complete

ionization
Na+(aq) + OH (aq)
0 0.010 M 0.010 M

 The TOTAL CONCENTRATION OF THE [OH] can be thought of as the sum of the :
 concentration of [OH] provided by the base; [OH] = 1.0 x 102 M
 concentration of [OH] provided by the self-ionization of water; [OH] = 1.0 x 107 M

Total Conc. of [OH–] = [OH–] + [OH–]

from base from self-ionization of water
= 1.0 x 102 M + less than 1.0 x 107 M (negligible)
= 1.0 x 102 M
 Concentration of the [H3O+] can now easily be calculated:

1.0 x 10 14 1.0 x 10 14
[H3O+] [OH] = 1.0 x 1014 [H3O+ ] = = 2
= 1.0 x 10 12
[OH ] 1.0 x 10

 In a solution of a strong base the concentration of the [OH ] produced by the self-ionization
of water can be ignored.

21
Chemistry 102 Chapter 15

CONCLUSIONS:
1. In a neutral solution: [H3O+] = [OH] = 1.0 x 107 M

2. In an acidic solution: [H3O+]  [OH]

[H3O+]  1.0 x 107 M

[OH]  1.0 x 107 M

2. In a basic solution: [H3O+]  [OH]

[H3O+]  1.0 x 107 M

[OH]  1.0 x 107 M

22
Chemistry 102 Chapter 15

Examples:
1. What is the concentration of the [H3O+] and [OH] in a 0.25 M solution of Ba(OH)2?

Ba(OH)2 (aq) Ba2+ (aq) + 2OH (aq)

0 0.25 M 2 x 0.25 M

[OH] = 0.50 M

[H3O+] =

2. What is the concentration of the [H3O+] and [OH] in a 0.040 M solution of HNO3?

3. Identify each of the following solutions are acidic, basic or neutral:

a) [OH–] = 1.0 x10–5 M

b) [H3O+] = 3.8 x10–9 M

c) [H3O+] = 6.2 x10–3 M

d) [OH–] = 4.5 x10–10 M

23
Chemistry 102 Chapter 15

pH SCALE

 pH is an important chemical quantity introduced by Sorensen, to simplify handling of negative

exponents, when expressing the acidity or basicity of aqueous solutions
 pH can be loosely referred to as “power of hydrogen)

 By Sorensen’s definition, widely accepted today:

pH =  log [H3O+] or simply: pH =  log [H+]

 For a neutral solution: [H3O+] = 1.0 x 107 M

pH =  log (1.0 x 107) = 7.00

 For an acidic solution: [H3O+]  1.0 x 107 M

pH  7.00

 For a basic solution: [H3O+]  1.0 x 107 M

pH  7

 pH calculations can be greatly simplified by a rearrangement of the expression:

[H3O+] [OH] = 1.0 x 1014

Taking logs of both sides:

log [H3O+] + log [OH] = log (1.0 x 1014)

 pH  pOH =  14.00

pH + pOH = 14.00

 NOTE: pOH =  (log [OH])

A pHorseshoe
[H+] [OH]
Up arrows indicate changing the sign
and then calculating inverse log

Down arrows indicate calculating log

and then changing the sign

pH pH + pOH = 14 pOH

24
Chemistry 102 Chapter 15

Examples:
1. Obtain the pH corresponding to a hydroxide-ion concentration of 2.7 x1010 M.

pOH =  log (2.7 x 1010) = 9.568

pH = 14.00  9.568 = 4.43

2. A wine was tested for acidity, and it pH was found to be 3.85 at 25 C. What is the
hydronium ion concentration?

log [H3O+] = pH = 3.85

[H3O+] = antilog (–3.85) = 103.85 = 1.4 x 104 M

3. A 1.00 L aqueous solution contains 6.78 g of Ba(OH)2. What is the pH of the solution?

First: Calculate the molarity of the Ba(OH)2 solution:

moles 6.78 g Ba(OH)2 1mol Ba(OH)2

?  =  x  = 0.03956 M Ba(OH)2
L 1.00 L solution 171.4 g Ba(OH)2

2 moles OH
[OH] = 0.03956 M Ba(OH)2 x  = 0.07912 M
1 mole Ba(OH)2

1.0 x 1014
[H3O+] =  = 1.264 x 1013 M
0.07912 M

pH = - log (1.264 x 1013 M) = 12.90

4. What is concentration of a solution of KOH with a pH of 11.89?

25
Chemistry 102 Chapter 15

MEASUREMENT OF pH

Acid-Base Indicators
 Acid-Base indicators change color within a small range.
 Reason: Indicators establish an equilibrium between their acid form and their base form,
respectively:

HIn = acid form of indicator

In = base form of indicator

 These two forms of the Indicator have different colors (not necessarily red and blue)

HIn (aq) + H2O (aq) H3O+ (aq) + In (aq)

Example: Phenolphthalein: HIn (aq) is colorless In(aq) is pink

 When a base is added to the acidic solution of phenolphthalein:

HIn (aq) + H2O (l) H3O+(aq) + In(aq)

 OH– reacts with H3O+(aq) to produce H2O

 Equilibrium shifts 

 In(aq) is produced. Solution turns pink

 Phenolphthalein begins to turn pink at about pH = 8.0

Universal pH paper
 This paper is impregnated with several indicators

 It gives different colors to different pH ranges (to the nearest integer value)

pH-meter
 Consists of two electrodes (or one combination electrode) dipped into the solution whose pH is
to be measured.

 Measures the voltage that is generated between the electrodes.

 This voltage depends on pH and is read on a meter calibrated directly in pH units.

26
Chemistry 102 Chapter 15

ACID IONIZATION CONSTANT

Solutions of a Weak Acid or Base

 Weak acids ionize (dissociate) partially in water

HA + H2O H3O+ (aq) + A (aq)

?????
+
[H3O ][A ]
Kc =
[HA][H 2O]

[H2O]  can be considered constant for dilute solutions

 can be included in Kc

[H3O+ ][A ]
= K c x [H 2O] = Ka = ACID IONIZATION CONSTANT
[HA]

Ka  expresses the extent of ionization of a weak acid

 is a measure of the relative strength of weak acids

Weak Acids Acid-Ionization Constant (at 250C)

HF Ka = 6.8 x 10–4  strongest weak acid

Strength
–5 Of
HC2H3O2 Ka = 1.7 x 10
Weak
Acids
HClO Ka = 3.5 x 10–8
Increases
HCN Ka = 4.9 x 10–10  weakest weak acid

27
Chemistry 102 Chapter 15

ACID IONIZATION CONSTANT

 The smaller the acid ionization constant (Ka), the less the acid ionizes and the weaker the
acid.

 The acid ionization constant can also be related to the pH of an acid solution. For a given
concentration, the smaller the Ka, the lower the [H3O+] and therefore the higher the pH.

Examples:
1. Rank the following 0.1 M solutions of acids in order of increasing ionization (lowest to
highest):

H2S Ka = 1.0 x 10–7

HCN Ka = 6.2 x 10–10

HNO2 Ka = 7.2 x 10–4

HOCl Ka = 2.9 x 10–8

2. Rank the following 0.1 M solutions of acids in order of decreasing pH (highest to lowest):

H2S Ka = 1.0 x 10–7

HCN Ka = 6.2 x 10–10

HNO2 Ka = 7.2 x 10–4

HOCl Ka = 2.9 x 10–8

28
Chemistry 102 Chapter 15

CALCULATIONS WITH Ka

Examples:
1. Lactic acid, HC3H5O3, is a weak acid found in sour milk. A 0.025 M solution of lactic
acid has a pH of 2.75. What is the ionization constant, Ka for this acid? What is the
degree of ionization?

HC3H5O3 (l) + H2O (l) H3O+ (aq) + C3H5O3 (aq)

Initial 0.025 M ---- 0 0
 –x ---- +x +x
Equilibrium 0.025–x ----- x x

[H3O+ ][C2 H3O2 ] x2

Ka = =
[HC2 H3O2 ] 0.025 x

[H3O+] = x = antilog (-pH) = antilog (- 2.75) = 1.78 x 103

[C3H5O3] = x = 1.78 x 103

[HC3H5O3] = (25 x 103) – (1.78 x 103) = 23.2 x 103

(1.78 x 10 3 )2 4
Ka = = 1.4 x 10
23.2 x 10 3

Molar concentration of Ionized Acid

Degree of Ionization = 
Total Molar concentration of Acid

1.78 x 103
Degree of Ionization =  = 0.071 or 7.1%
25 103

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Chemistry 102 Chapter 15

Examples:
2. What are the concentrations of hydrogen ion and acetate ion in a solution of 0.10 M acetic acid?
What is the pH of the solution? What is the degree of ionization? (Ka of acetic acid = 1.7 x 105)

HC2H3O2 (l) + H2O (l) H3O+ (aq) + C2H3O2 (aq)

Initial 0.10 ---- 0 0
 –x ---- +x +x
Equilibrium 0.10–x ----- x x

[H3O+ ][C2 H3O2 ] x2 5

Ka = = = 1.7 x 10
[HC2 H3O2 ] 0.10 x

 This yields a quadratic equation: x2 = 1.7 x 106 – 1.7 x 105 x

x2 + 1.7 x 105 X – 1.7 x 106 = 0

 The equation can be greatly simplified, by realizing that:

x   0.10

 Therefore: 0.10 – x  0.10

can be neglected

x2 x2
It follows:    = 1.7 x 105 x2 = 1.7 x 106
0.10 – X 0.10

x = [H3O+] = [C2H3O2] = 1.30 x 103 M

 Now we can check if the assumption: 0.10 – X  0.10 is valid or not

0.10 – 0.00130 = 0.09870 = 0.10 YES, the assumption is valid!

pH = - log (H3O+) = - log (1.30 x 103) = 2.89

1.30 x 103
Degree of Ionization =  = 0.013 or 1.3%
1.0 x 101

 This method is commonly referred to as the “Approximation Method”

30
Chemistry 102 Chapter 15

Examples:
3. Calculate the pH and % ionization of a 0.250 M solution of HF. (Ka = 3.5x10–4)

Initial

Equilibrium

31
Chemistry 102 Chapter 15

POLYPROTIC ACIDS

 Polyprotic acids are acids that can release more than one H+ per molecules of acid

Examples:

1. H2SO4 (strong acid) and HSO4 (weak acid)

H2SO4 (aq) + H2O (l) 

complete dissociation
 H3O+ (aq) + HSO4 (aq)

HSO4 (aq) + H2O (l) 

partial dissociation
  H3O+ (aq) + SO42 (aq)

2. H2CO3 (weak acid) and HCO3 (weak acid)

H2CO3 (aq) + H2O (l) H3O+ (aq) + HCO3 (aq) Ka = 4.3 x 107

HCO3 (aq) + H2O (l) H3O+ (aq) + CO32 (aq) Ka = 4.8 x 1011

3. H3PO4 (weak acid), H2PO4 (weak acid), and HPO42 (weak acid)

H3PO4 (aq) + H2O (l) H3O+ (aq) + H2PO4 (aq) Ka = 6.9 x 103

H2PO4 (aq) + H2O (l) H3O+ (aq) + HPO42(aq) Ka = 6.2 x 108

HPO42 (aq) + H2O (l) H3O+ (aq) + PO43 (aq) Ka = 4.8 x 1013

NOTE: Ka1  Ka2  Ka3

Meaning: A diprotic acid - loses the first H+ easier than the second one.
A triprotic acid: - loses the first H+ easier than the second one
- loses the second H+ easier than the third one.

Reason: The 1st H+ separates from an ion of a single negative charge

The 2nd H+ separates from an ion of an ion of a double negative charge
The 3rd H+ separates from an ion of a triple negative charge

32
Chemistry 102 Chapter 15

CALCULATING THE CONCENTRATION OF VARIOUS SPECIES

IN A SOLUTION OF A POLYPROTIC ACID

Ascorbic acid (H2Asc) is a diprotic acid with Ka1 = 7.9 x 105 and Ka2 = 1.6 x 1012. What is the pH of a 0.10 M
solution of ascorbic acid? What is the concentration of the ascorbate ion (Asc2), in the solution?

First Part: Calculate the pH of the solution:

 Note that Ka2 (1.6 x 1012)  Ka1 (7.9 x 105)
 As such: - the 2nd ionization can be neglected
- any H+ produced by the 2nd ionization can be ignored.

H2Asc (aq) + H2O (l) H3O+ (aq) + HAsc (aq)

Initial 0.10 M ---- 0 0
 –x ---- +x +x
Equilibrium 0.10–x ----- x x

[H3O+ ][HAsc ] x2 5
K a1 = = = 7.9x10
[H 2 Asc] 0.10 x

x2 = (0.10)(7.9x10–5) = 7.9x10–6 x = [H3O+] = 2.8x10–3

pH = - log (2.8x10–3) = 2.55

Second Part: Calculate the concentration of the sulfite ion (SO32) :

H2Asc(aq) + H2O(l) HAsc(aq) + H3O+(aq) Ka1 = 7.9 x105

HAsc(aq) + H2O(l) Asc2 (aq) + H3O+(aq) Ka2 = 1.6 x1012

HAsc– (aq) + H2O (l) H3O+ (aq) + Asc2– (aq)

Initial 0.0028 ---- 0.0028 0
 –y ---- +y +y
Equilibrium 0.0028 – y ----- 0.0028 + y y

[H3O+ ][Asc2 ] (0.0028 + y)(y) 12

K a2 = = = 1.6x10
[HAsc ] 0.0028 y

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Chemistry 102 Chapter 15

 Assume that: y <<<<<< 0.0028

 Therefore: 0.0028 + y  0.0028 and 0.0028 – y  0.0028

(0.0028 + y)(y) (0.0028)(y) 12

K a2 = = = 1.6x10
0.0028 y 0.0028

y = [Asc2] = 1.6 x 1012 M

 General Rule: The concentration of the ion A2– equals the second ionization constant, Ka2

Examples:
1. Carbonic acid (H2CO3) is a weak acid with Ka1= 4.3x10–7 and Ka2= 4.8x10–11. Calculate the pH
and the carbonate ion concentration of a 0.050M solution of carbonic acid.

34
Chemistry 102 Chapter 15

BASE–IONIZATION EQUILIBRIA

 Weak bases ionize (dissociate) partially in water.

NH3 (aq) + H2O (l) NH4+ (aq) + OH (aq)

[NH +4 ][OH ]
Kc =
[NH3 ][H 2O]

[H2O]  can be considered constant for dilute solutions

 can be included in Kc

[NH +4 ][OH ]
= K c x [H 2O] = Kb = BASE IONIZATION CONSTANT
[NH3 ]

Kb  expresses the extent of ionization of a weak base

 is a measure of the relative strength of weak bases

Weak Bases Formula Base-Ionization Constant (at 25 C)

Dimethylamine (CH3)2NH Kb = 5.1 x 10–4  strongest weak base

Strength
Of
Ammonia NH3 Kb = 1.8 x 10–5
Weak
Bases
Aniline C6H5–NH2 Kb = 4.2 x 10–10
Increases
Urea NH2–CO–NH2 Kb = 1.5 x 10–14  weakest weak base

35
Chemistry 102 Chapter 15

CALCULATIONS WITH Kb

Examples:
1. Quinine is an alkaloid, or naturally occurring base, used to treat malaria. A 0.0015 M
solution of quinine has a pH of 9.84. What is Kb of quinine?

Step 1: Convert the pH to pOH, and then to [OH]

pOH = 14.00 – pH = 14.00 – 9.84 = 4.16

[OH] = antilog (–4.16) = 6.92 x 105 M

Step 2: Using the symbol Qu for quinine, assemble reaction table

Qu (aq) + H2O (l) HQu+ (aq) + OH (aq)

Initial 0.0015 M ---- 0 0
 –x ---- +x +x
Equilibrium 0.0015–x ----- x x

[HQu + ][OH ] x2 (6.92 x 10 5 )2 6

Kb = = = = 3.3 x 10
[Qu] 0.0015 x (0.0015 6.92 x 10 5 )

2. What is the pH of a 0.20 M solution of ammonia in water (Kb = 1.8 x 105)?

NH3 (aq) + H2O (l) NH4+ (aq) + OH (aq)

Initial 0.20 M ---- 0 0
 –x ---- +x +x
Equilibrium 0.20–x ----- x x

 Assume that x is small enough to neglect compared with 0.20.

[NH +4 ][OH ] x2 x2
Kb = = = = 1.8 x 10 5
x2 = 3.6 x 106
[NH3 ] 0.20 x 0.20

x = [OH] = 1.89 x 103 M (Note that x is negligible compared to 0.20)

1.0 x 10 14
[H3O+ ]= = 5.3 x 10 12
pH = –log (5.3 x 1012) = 11.28
1.89 x 10 3

36
Chemistry 102 Chapter 15

RELATIONSHIP BETWEEN Ka AND Kb

 The quantitative relationship between an acid and its conjugate base can be seen in the
examples below:

NH4+ (aq) + H2O (l) H3O+ (aq) + NH3 (aq)

NH3 (aq) + H2O (l) NH4+ (aq) + OH– (aq)

 Each of these equilibria can be expressed by an ionization constant:

[H3O+ ][NH3 ] [NH +4 ][OH ]

Ka = and Kb =
[NH +4 ] [NH3 ]

 Addition of the two equations above results the following:

NH4+ (aq) + H2O (l) H3O+ (aq) + NH3 (aq) Ka

NH3 (aq) + H2O (l) NH4+ (aq) + OH– (aq) Kb

2 H2O (l) H3O+ (aq) + OH– (aq) Kw

 Recall that when two reactions are added to form a third reaction, the equilibrium constant
for the third reaction is the products of the two added reactions. Therefore,

Kw = Ka x Kb

 Note that Ka and Kb are inversely proportional for an acid-base conjugate pair. This is
expected, since as the strength of an acid increases (larger Ka), the strength of its conjugate
base decreases (smaller Kb).

Examples:
1. Hydrofluoric acid (HF) has Ka = 6.8 x 10–4. What is Kb for the fluoride ion?

Kw
Kb = =
Ka

2. Which of the following anions has the largest Kb value: NO3–, PO43–, HCO3– ?

37
Chemistry 102 Chapter 15

ACID-BASE PROPERTIES OF SALT SOLUTIONS

 A salt is an ionic substance resulting from a neutralization reaction:

Acid + Base  Salt + Water

 The aqueous solution of a salt may be: basic, acidic, or neutral

 Reason: Soluble salts derived from weak acids or weak bases undergo hydrolysis (reaction
with
H2O) in aqueous solution.

I. Salt of a strong base (NaOH) and a weak acid (HC2H3O2)

completely
NaC2H3O2 (aq)  Na+ (aq) + C2H3O2 (aq)
dissociated

Na+ (aq) + H2O (l)  No Reaction

H+ H+

C2H3O2 (aq) + H2O (l) H C2H3O2 (aq) + OH (aq)

Bronsted Bronsted Bronsted Bronsted
base acid acid base

NOTE: The resulting solution is basic

 This reaction is referred to as the Hydrolysis of the acetate (C2H3O2) ion

38
Chemistry 102 Chapter 15

II. Salt of a weak base (NH4OH) and a strong acid (HCl)

completely
NH4Cl (aq)  NH4+ (aq) + Cl (aq)
dissociated

Cl (aq) + H2O (l)  No Reaction

H+ H+

NH4+ (aq) + H2O (l) NH3 (aq) + H3O+ (aq)

Bronsted Bronsted Bronsted Bronsted
acid base base acid

NOTE: The resulting solution is acidic

 The reaction is referred to as the Hydrolysis of the ammonium(NH4+)ion

III. Salt of a strong base (NaOH) and a strong acid (HCl)

completely
NaCl (aq)  Na+ (aq) + Cl (aq)
dissociated

Na+ (aq) + H2O (l)  No Reaction

Cl (aq) + H2O (l)  No Reaction

 The resulting solution is neutral

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Chemistry 102 Chapter 15

IV. Salt of a weak base (NH4OH) and a weak acid (HC2H3O2)

completely
NH4C2H3O2(aq)  NH4+(aq) + C2H3O2(aq)
dissociated

Both ions undergo hydrolysis:

C2H3O2 (aq) + H2O (l) HC2H3O2 (aq) + OH (aq)

Is the solution basic?

NH4 (aq) + H2O (l) NH3 (aq) + H3O+ (aq)

Is the solution acidic?

 Acidity or Basicity of solution depends on the relative acid-base strength of the two ions.

Ka of NH4+ must be compared with Kb of C2H3O2

 If: Ka  Kb  Solution is acidic

 If: Ka  Kb Solution is basic

CONCLUSIONS:

 Solution of a salt of a strong base and weak acid is basic

 Solution of a salt of a weak base and a strong acid is acidic

 Solution of a salt of a strong acid and a strong base is neutral.

 Solution of a salt of a weak base and a weak acid is:

 neutral, if: Ka(cation)  Kb(anion)

 acidic, if: Ka(cation)  Kb(anion)

 basic, if: Ka(cation)  Kb(anion)

40
Chemistry 102 Chapter 15

Examples:
1. For each of the following salts, indicate whether the aqueous solution will be acidic, basic or neutral.

Salt Parent Base Parent Acid Solution of salt is:

Fe(OH)3 HNO3
Fe(NO3)3 acidic
insoluble strong acid
Ca(OH)2 HCN
Ca(CN)2 Basic
strong base weak acid

Na2CO3

Na2S

KClO4

Al(NO3)3

2. Write hydrolysis equation(s) for each of the following salts:

a) Na2CO3

Na2CO3 
 2 Na+ + CO32–

Na+ + H2O 
 no reaction (cation of a strong base, NaOH)


CO32– + H2O 
 HCO3– + OH– (conjugate base of a weak acid HCO3–)

b) Na2S

c) KClO4

41
Chemistry 102 Chapter 15

THE pH OF A SALT SOLUTION

What is the pH of a 0.10 M NaCN (sodium cyanide) solution?

NOTE: NaCN is the salt of a strong base (NaOH) with a weak acid (HCN). Therefore:

 we expect the solution to be basic

 we know beforehand that the pH  7

Consider the hydrolysis of NaCN:

NaCN (aq)  Na+ (aq) + CN (aq)

Na+ (aq) + H2O (l)  No Reaction

CN (aq) + H2O (l) HCN (aq) + OH (aq) Kb(CN) = ? (not readily available)

 Solution: Consider the ionization equilibrium of HCN:

HCN (aq) + H2O (l) H3O+ (aq) + CN(aq) Ka = 4.9 x 1010

14
Kw 1.0 x 10
Ka (HCN) x Kb (CN) = Kw K b (CN ) = = 10
= 2.0 x 10 5

K a (HCN) 4.9 x 10

 Now we can calculate the pH of the solution from equilibrium data:

CN– (aq) + H2O (l) HCN(aq) + OH (aq)

Initial 0.10 ---- 0 0
 –x ---- +x +x
Equilibrium 0.10–x ----- x x

[HCN][OH ] x2 5
Kb = = = 2.0 x 10
[CN ] 0.10 x

Consider the usual assumption: 0.10 – x  0.10

x2
2.0 x 105 =  x = [OH] = 1.4 x 103
0.10

pOH = – log (1.4 x 103) = 2.85 pH = 14.00 – 2.85 = 11.15

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Chemistry 102 Chapter 15

Examples:
1. Household bleach is a 5% solution of sodium hypochlorite (NaClO). This corresponds to a
molar concentration of about 0.70 M NaClO. Ka for HClO (hypochlorous acid) is 3.5 x 108.
What is the pH of household bleach?

NaClO(aq)  Na+(aq) + ClO(aq)

 NaClO is the salt of a _____________base with a ____________ acid.

 Therefore the solution of this salt is expected to be _____________

ClO (aq) + H2O (l) HClO (aq) + OH (aq) Kb = ?

Kb (ClO) =

ClO– (aq) + H2O (l) HClO(aq) + OH (aq)

Initial 0.70 ---- 0 0
 –x ---- +x +x
Equilibrium 0.70–x ----- x x

[HClO][OH ] x2
Kb = = =
[ClO ] 0.70 x

Consider the usual assumption: 0.70 – x  0.70

x2
Kb =  = x = [OH] =
0.70

pOH = – log [OH–] =

pH = 14.00 –

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