Acid-Base Equilibria - Libre Texts

CHAPTER OVERVIEW
16: Acid–Base Equilibria

A general chemistry Libretexts Textmap organized around the textbook
Chemistry: The Central Science

by Brown, LeMay, Bursten, Murphy, and Woodward
Acids and bases have been defined differently by three sets of theories. One is the Arrhenius definition, which revolves around the
idea that acids are substances that ionize (break off) in an aqueous solution to produce hydrogen (H+) ions while bases produce
hydroxide (OH-) ions in solution. On the other hand, the Bronsted-Lowry definition defines acids as substances that donate protons
(H+) whereas bases are substances that accept protons. Also, the Lewis theory of acids and bases states that acids are electron pair
acceptors while bases are electron pair donors. Acids and bases can be defined by their physical and chemical observations.
16.1: Acids and Bases - A Brief Review
16.2: Brønsted–Lowry Acids and Bases
16.3: The Autoionization of Water
16.4: The pH Scale
16.5: Strong Acids and Bases
16.6: Weak Acids
16.7: Weak Bases
16.8: Relationship Between Ka and Kb
16.9: Acid-Base Properties of Salt Solutions
16.10: Acid-Base Behavior and Chemical Structure
16.11: Lewis Acids and Bases
16.E: Acid–Base Equilibria (Exercises)
16.S: Acid–Base Equilibria (Summary)
16: Acid–Base Equilibria is shared under a CC BY-NC-SA 3.0 license and was authored, remixed, and/or curated by LibreTexts.
1
16.1: Acids and Bases - A Brief Review
Acids and bases have been known for a long time. When Robert Boyle characterized them in 1680, he noted that acids dissolve
many substances, change the color of certain natural dyes (for example, they change litmus from blue to red), and lose these
characteristic properties after coming into contact with alkalis (bases). In the eighteenth century, it was recognized that acids have a
sour taste, react with limestone to liberate a gaseous substance (now known to be CO2), and interact with alkalis to form neutral
substances. In 1815, Humphry Davy contributed greatly to the development of the modern acid-base concept by demonstrating that
hydrogen is the essential constituent of acids. Around that same time, Joseph Louis Gay-Lussac concluded that acids are substances
that can neutralize bases and that these two classes of substances can be defined only in terms of each other. The significance of
hydrogen was reemphasized in 1884 when Svante Arrhenius defined an acid as a compound that dissolves in water to yield
hydrogen cations (now recognized to be hydronium ions) and a base as a compound that dissolves in water to yield hydroxide
anions.
Acids and bases are common solutions that exist everywhere. Almost every liquid that we encounter in our daily lives consists of
acidic and basic properties, with the exception of water. They have completely different properties and are able to neutralize to
form H2O, which will be discussed later in a subsection. Acids and bases can be defined by their physical and chemical
observations (Table 16.1.1).
Table 16.1.1 : General Properties of Acids and Bases
ACIDS BASES
produce a piercing pain in a wound. give a slippery feel.
taste sour. taste bitter.
are colorless when placed in phenolphthalein (an indicator). are pink when placed in phenolphthalein (an indicator).
are red on blue litmus paper (a pH indicator). are blue on red litmus paper (a pH indicator).
have a pH<7. have a pH>7.
produce hydrogen gas when reacted with metals.
produce carbon dioxide when reacted with carbonates.
Common examples: Lemons, oranges, vinegar, urine, sulfuric acid, Common Examples: Soap, toothpaste, bleach, cleaning agents,
hydrochloric acid limewater, ammonia water, sodium hydroxide.
Acids and bases in aqueous solutions will conduct electricity because they contain dissolved ions. Therefore, acids and bases are
electrolytes. Strong acids and bases will be strong electrolytes. Weak acids and bases will be weak electrolytes. This affects the
amount of conductivity.
The Arrhenius Definition of Acids and Bases

In 1884, the Swedish chemist Svante Arrhenius proposed two specific classifications of compounds, termed acids and bases. When
dissolved in an aqueous solution, certain ions were released into the solution. The Arrhenius definition of acid-base reactions is a
development of the "hydrogen theory of acids". It was used to provide a modern definition of acids and bases, and followed from
Arrhenius's work with Friedrich Wilhelm Ostwald in establishing the presence of ions in aqueous solution in 1884. This led to
Arrhenius receiving the Nobel Prize in Chemistry in 1903.
An Arrhenius acid is a compound that increases the concentration of H ions that are present when added to water. These H ions
+ +
form the hydronium ion (H O ) when they combine with water molecules. This process is represented in a chemical equation by
3
+
adding H2O to the reactants side.

+ −
H C l(aq) → H + Cl
(aq) (aq)
In this reaction, hydrochloric acid (H C l) dissociates into hydrogen (H ) and chlorine (C l ) ions when dissolved in water, thereby
+ −
releasing H+ ions into solution. Formation of the hydronium ion equation:

+ −
H C l(aq) + H2 O(l) → H3 O + Cl
(aq) (aq)
16.1.1 https://chem.libretexts.org/@go/page/25225
The Arrhenius definitions of acidity and alkalinity are restricted to aqueous solutions and refer to the concentration of the solvated
ions. Under this definition, pure H SO or H C l dissolved in toluene are not acidic, despite the fact that both of these acids will
2 4
donate a proton to toluene. In addition, under the Arrhenius definition, a solution of sodium amide (N aN H ) in liquid ammonia is
2
not alkaline, despite the fact that the amide ion (N H ) will readily deprotonate ammonia. Thus, the Arrhenius definition can only
−
2
describe acids and bases in an aqueous environment.
 Limitation of the Arrhenius Definition of Acids and Bases
The Arrhenius definition can only describe acids and bases in an aqueous environment.
In chemistry, acids and bases have been defined differently by three sets of theories: One is the Arrhenius definition defined above,
which revolves around the idea that acids are substances that ionize (break off) in an aqueous solution to produce hydrogen (H ) +
ions while bases produce hydroxide (OH ) ions in solution. The other two definitions are discussed in detail alter in the chapter
−
and include the Brønsted-Lowry definition the defines acids as substances that donate protons (H ) whereas bases are substances
+
that accept protons and the Lewis theory of acids and bases states that acids are electron pair acceptors while bases are electron pair
donors.
Contributors and Attributions

Anonymous
16.1: Acids and Bases - A Brief Review is shared under a CC BY-NC-SA 3.0 license and was authored, remixed, and/or curated by LibreTexts.
16.2: Brønsted–Lowry Acids and Bases
 Learning Objectives
Identify acids, bases, and conjugate acid-base pairs according to the Brønsted-Lowry definition
Write equations for acid and base ionization reactions
Use the ion-product constant for water to calculate hydronium and hydroxide ion concentrations
Describe the acid-base behavior of amphiprotic substances
Acids and bases have been known for a long time. When Robert Boyle characterized them in 1680, he noted that acids dissolve
many substances, change the color of certain natural dyes (for example, they change litmus from blue to red), and lose these
characteristic properties after coming into contact with alkalis (bases). In the eighteenth century, it was recognized that acids have a
sour taste, react with limestone to liberate a gaseous substance (now known to be CO2), and interact with alkalis to form neutral
substances. In 1815, Humphry Davy contributed greatly to the development of the modern acid-base concept by demonstrating that
hydrogen is the essential constituent of acids. Around that same time, Joseph Louis Gay-Lussac concluded that acids are substances
that can neutralize bases and that these two classes of substances can be defined only in terms of each other. The significance of
hydrogen was reemphasized in 1884 when Svante Arrhenius defined an acid as a compound that dissolves in water to yield
hydrogen cations (now recognized to be hydronium ions) and a base as a compound that dissolves in water to yield hydroxide
anions.
Previously, we defined acids and bases as Arrhenius did: An acid is a compound that dissolves in water to yield hydronium ions (
H O ) and a base as a compound that dissolves in water to yield hydroxide ions (OH ). This definition is not wrong; it is simply
+ −
3
limited. We extended the definition of an acid or a base using the more general definition proposed in 1923 by the Danish chemist
Johannes Brønsted and the English chemist Thomas Lowry. Their definition centers on the proton, H . A proton is what remains +
when a normal hydrogen atom, H , loses an electron. A compound that donates a proton to another compound is called a Brønsted-
1
1
Lowry acid, and a compound that accepts a proton is called a Brønsted-Lowry base. An acid-base reaction is the transfer of a
proton from a proton donor (acid) to a proton acceptor (base). In a subsequent chapter of this text we will introduce the most
general model of acid-base behavior introduced by the American chemist G. N. Lewis.
Acids may be compounds such as H C l or H SO , organic acids like acetic acid (CH COOH ) or ascorbic acid (vitamin C), or
2 4 3
H O . Anions (such as HSO , H PO , HS , and HCO ) and cations (such as H O , NH , and [Al (H O) ] ) may also act
− − − − + + 3 +
2 4 4 3
2 3 4 2 6
as acids. Bases fall into the same three categories. Bases may be neutral molecules (such as H O , NH , and CH NH ), anions 2 3 3 2
2 +
(such as OH , HS , HCO , CO , F , and PO ), or cations (such as [Al(H O) OH] ). The most familiar bases are ionic
− − −
3
2 −
3
− 3 −
4 2 5
compounds such as NaOH and Ca(OH) , which contain the hydroxide ion, OH . The hydroxide ion in these compounds accepts
2
−
a proton from acids to form water:

+ −
H + OH → H O (16.2.1)
2
We call the product that remains after an acid donates a proton the conjugate base of the acid. This species is a base because it can
accept a proton (to re-form the acid):
acid ⇌ proton + conjugate base (16.2.2)
+ −
HF ⇌ H +F (16.2.3)
+ −
H SO ⇌ H + HSO 4 (16.2.4)
2 4
+ −
H O⇌ H + OH (16.2.5)
2
− + 2 −
HSO ⇌ H + SO (16.2.6)
4 4
+ +
NH ⇌ H + NH (16.2.7)
4 3
We call the product that results when a base accepts a proton the base’s conjugate acid. This species is an acid because it can give
up a proton (and thus re-form the base):
base + proton ⇌ conjugate acid (16.2.8)
− +
OH +H ⇌ H O (16.2.9)
2
+ +
H O+H ⇌ H O (16.2.10)
2 3
+ +
NH +H ⇌ NH (16.2.11)
3 4
2 − + −
S +H ⇌ HS (16.2.12)
2 − + −
CO3 +H ⇌ HCO3 (16.2.13)
\[\ce{F^- +H^+ \rightleftharpoons HF} \label{16.2.3g} \]

In these two sets of equations, the behaviors of acids as proton donors and bases as proton acceptors are represented in isolation. In
reality, all acid-base reactions involve the transfer of protons between acids and bases. For example, consider the acid-base reaction
that takes place when ammonia is dissolved in water. A water molecule (functioning as an acid) transfers a proton to an ammonia
molecule (functioning as a base), yielding the conjugate base of water, OH , and the conjugate acid of ammonia, NH :
− +
4
A conjugate acid base pair if when we remove a H plus from the acid to get the conjugate base. Another conjugate acid base pair is
when we add H plus to a base to get a conjugate acid. In a reaction: the acid and base are the reactants and the products are the
conjugate base and conjugate acid.
The reaction between a Brønsted-Lowry acid and water is called acid ionization. For example, when hydrogen fluoride dissolves in
water and ionizes, protons are transferred from hydrogen fluoride molecules to water molecules, yielding hydronium ions and
fluoride ions:
In this reaction HF is treated as the acid and water is treated as the base. The products as H3O plus and F minus. H3O plus is the
acid and F minus is the base.
When we add a base to water, a base ionization reaction occurs in which protons are transferred from water molecules to base
molecules. For example, adding pyridine to water yields hydroxide ions and pyridinium ions:
<div data-mt-source="1" "This " height="167" width="612" src="/@api/deki/files/56740/CNX_Chem_14_01_NH3_img.jpg">
Notice that both these ionization reactions are represented as equilibrium processes. The relative extent to which these acid and
base ionization reactions proceed is an important topic treated in a later section of this chapter. In the preceding paragraphs we saw
that water can function as either an acid or a base, depending on the nature of the solute dissolved in it. In fact, in pure water or in
any aqueous solution, water acts both as an acid and a base. A very small fraction of water molecules donate protons to other water
molecules to form hydronium ions and hydroxide ions:
Here we have 2 water molecules reacting together. One water molecule is an acid while the second water molecule acts as a base.
For the products, we get H3O plus and OH minus. H3O plus is the acid and OH minus is the base.
This type of reaction, in which a substance ionizes when one molecule of the substance reacts with another molecule of the same
substance, is referred to as autoionization. Pure water undergoes autoionization to a very slight extent. Only about two out of
every 10 molecules in a sample of pure water are ionized at 25 °C. The equilibrium constant for the ionization of water is called
9
the ion-product constant for water (Kw):

+ − + −
H O(l) + H O(l) ⇌ H O + HO Kw = [ H O ][ OH ] (16.2.14)
2 2 3 (aq) (aq) 3
The slight ionization of pure water is reflected in the small value of the equilibrium constant; at 25 °C, Kw has a value of
1.0 × 10
−14
. The process is endothermic, and so the extent of ionization and the resulting concentrations of hydronium ion and
hydroxide ion increase with temperature. For example, at 100 °C, the value for K is approximately 5.1 × 10 , roughly 100-
w
−13
times larger than the value at 25 °C.
Conjugate Acid-Base Pairs
A Video Discussing Conjugate Acid-Base Pairs: Conjugate Acid-Base Pairs [youtu.be]
 Example 16.2.1: Ion Concentrations in Pure Water
What are the hydronium ion concentration and the hydroxide ion concentration in pure water at 25 °C?
Solution
The autoionization of water yields the same number of hydronium and hydroxide ions. Therefore, in pure water,
[ H O ] = [ OH ] . At 25 °C:
+ −
+ − + 2+ − 2+ −14
Kw = [ H O ][ OH ] = [H O ] = [ OH ] = 1.0 × 10
3 3
So:
− −−−−−−− −
+ − −14 −7
[H O ] = [ OH ] = √ 1.0 × 10 = 1.0 × 10 M
3
The hydronium ion concentration and the hydroxide ion concentration are the same, and we find that both equal
M .
−7
1.0 × 10
 Exercise 16.2.1
The ion product of water at 80 °C is 2.4 × 10 −13

. What are the concentrations of hydronium and hydroxide ions in pure water
at 80 °C?
Answer
+ − −7
[H O ] = [ OH ] = 4.9 × 10 M
3
It is important to realize that the autoionization equilibrium for water is established in all aqueous solutions. Adding an acid or base
to water will not change the position of the equilibrium determined by the autoionization reaction but it does shift the relative
concentrations of [OH−] and [H 3
+
O . Example 16.2.2 demonstrates the quantitative aspects of this relation between hydronium
]
and hydroxide ion concentrations.
Self-Ionization of Water (Kw)
A Video Describing the Self-Ionization of Water (Kw): Self-Ionization of Water (Kw) [youtu.be]
 Example 16.2.2: The Inverse Proportionality of [H 3

O
+
] and [OH −
]
A solution of carbon dioxide in water has a hydronium ion concentration of 2.0 × 10

−6
M . What is the concentration of
hydroxide ion at 25 °C?
Solution
We know the value of the ion-product constant for water at 25 °C:
+ −
2 H O(l) ⇌ H O + OH
2 3 (aq) (aq)
+ − −14
Kw = [ H O ][ OH ] = 1.0 × 10
3
Thus, we can calculate the missing equilibrium concentration.

Rearrangement of the Kw expression yields that [OH −
] is directly proportional to the inverse of [H3O+]:
−14
−
Kw 1.0 × 10
−9
[ OH ] = = = 5.0 × 10
+ −6
[H O ] 2.0 × 10
3
The hydroxide ion concentration in water is reduced to 5.0 × 10 M as the hydrogen ion concentration increases to
−9
M . This is expected from Le Chatelier’s principle; the autoionization reaction shifts to the left to reduce the stress
−6
2.0 × 10
of the increased hydronium ion concentration and the [OH ] is reduced relative to that in pure water.
−
A check of these concentrations confirms that our arithmetic is correct:

+ − −6 −9 −14
Kw = [ H O ][ OH ] = (2.0 × 10 )(5.0 × 10 ) = 1.0 × 10
3
 Exercise 16.2.2
What is the hydronium ion concentration in an aqueous solution with a hydroxide ion concentration of 0.001 M at 25 °C?
Answer
+ −11
[H O ] = 1 × 10 M
3
Amphiprotic Species
Like water, many molecules and ions may either gain or lose a proton under the appropriate conditions. Such species are said to be
amphiprotic. Another term used to describe such species is amphoteric, which is a more general term for a species that may act
either as an acid or a base by any definition (not just the Brønsted-Lowry one). Consider for example the bicarbonate ion, which
may either donate or accept a proton as shown here:
− 2 − +
HCO + H O(l) ⇌ CO +H O (16.2.15)
3(aq) 2 3(aq) 3 (aq)
− −
HCO + H O(l) ⇌ H CO3(aq) + OH (16.2.16)
3(aq) 2 2 (aq)
 Example 16.2.3: The Acid-Base Behavior of an Amphoteric Substance
Write separate equations representing the reaction of HSO −
a. as an acid with OH −
b. as a base with HI
Solution
a. H SO
−
3(aq)
+ OH
−
(aq)
⇌ SO
2−
3(aq)
+ H2 O(l)
b. H SO −
3(aq)
+ H I(aq) ⇌ H2 S O3(aq) + I
−
(aq)
 Example 16.2.4
Write separate equations representing the reaction of H 2

PO
−
a. as a base with HBr

b. as an acid with OH −
Answer
a. H2 P O
−
4(aq)
+ H Br(aq) ⇌ H3 P O4(aq) + Br
−
(aq)
b. H 2P O
−
4(aq)
+ OH
−
(aq)
⇌ HP O
2−
4(aq)
+ H2 O(l)
Summary
A compound that can donate a proton (a hydrogen ion) to another compound is called a Brønsted-Lowry acid. The compound that
accepts the proton is called a Brønsted-Lowry base. The species remaining after a Brønsted-Lowry acid has lost a proton is the
conjugate base of the acid. The species formed when a Brønsted-Lowry base gains a proton is the conjugate acid of the base. Thus,
an acid-base reaction occurs when a proton is transferred from an acid to a base, with formation of the conjugate base of the
reactant acid and formation of the conjugate acid of the reactant base. Amphiprotic species can act as both proton donors and
proton acceptors. Water is the most important amphiprotic species. It can form both the hydronium ion, H3O+, and the hydroxide
ion, OH when it undergoes autoionization:
−
+ −
2 H O(l) ⇌ H3 O + OH
2 (aq) (aq)
The ion product of water, Kw is the equilibrium constant for the autoionization reaction:
+ − −14
Kw = [ H2 O ][OH ] = 1.0 × 10 at 25°C
Key Equations
+ − −14
Kw = [ H O ][ OH ] = 1.0 × 10 (at 25 °C)
3
Glossary
acid ionization
reaction involving the transfer of a proton from an acid to water, yielding hydronium ions and the conjugate base of the acid
amphiprotic
species that may either gain or lose a proton in a reaction
amphoteric
species that can act as either an acid or a base
autoionization
reaction between identical species yielding ionic products; for water, this reaction involves transfer of protons to yield
hydronium and hydroxide ions
base ionization
reaction involving the transfer of a proton from water to a base, yielding hydroxide ions and the conjugate acid of the base
Brønsted-Lowry acid
proton donor
Brønsted-Lowry base
proton acceptor
conjugate acid
substance formed when a base gains a proton
conjugate base
substance formed when an acid loses a proton
ion-product constant for water (Kw)

equilibrium constant for the autoionization of water

Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley
(Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed
under a Creative Commons Attribution License 4.0 license. Download for free at http://cnx.org/contents/85abf193-
2bd...a7ac8df6@9.110).
16.2: Brønsted–Lowry Acids and Bases is shared under a CC BY-NC-SA 3.0 license and was authored, remixed, and/or curated by LibreTexts.
16.3: The Autoionization of Water
To understand the autoionization reaction of liquid water.
To know the relationship among pH, pOH, and pK . w
As you learned previously acids and bases can be defined in several different ways (Table 16.3.1). Recall that the Arrhenius
definition of an acid is a substance that dissociates in water to produce H ions (protons), and an Arrhenius base is a substance
+
that dissociates in water to produce OH (hydroxide) ions. According to this view, an acid–base reaction involves the reaction of a
−
proton with a hydroxide ion to form water. Although Brønsted and Lowry defined an acid similarly to Arrhenius by describing an
acid as any substance that can donate a proton, the Brønsted–Lowry definition of a base is much more general than the Arrhenius
definition. In Brønsted–Lowry terms, a base is any substance that can accept a proton, so a base is not limited to just a hydroxide
ion. This means that for every Brønsted–Lowry acid, there exists a corresponding conjugate base with one fewer proton.
Consequently, all Brønsted–Lowry acid–base reactions actually involve two conjugate acid–base pairs and the transfer of a proton
from one substance (the acid) to another (the base). In contrast, the Lewis definition of acids and bases, focuses on accepting or
donating pairs of electrons rather than protons. A Lewis base is an electron-pair donor, and a Lewis acid is an electron-pair
acceptor.
Table 16.3.1 : Definitions of Acids and Bases
Definition Acids Bases
Arrhenius H
+
donor OH
−
donor
Brønsted–Lowry H
+
donor H
+
acceptor
Lewis electron-pair acceptor electron-pair donor
Because this chapter deals with acid–base equilibria in aqueous solution, our discussion will use primarily the Brønsted–Lowry
definitions and nomenclature. Remember, however, that all three definitions are just different ways of looking at the same kind of
reaction: a proton is an acid, and the hydroxide ion is a base—no matter which definition you use. In practice, chemists tend to use
whichever definition is most helpful to make a particular point or understand a given system. If, for example, we refer to a base as
having one or more lone pairs of electrons that can accept a proton, we are simply combining the Lewis and Brønsted–Lowry
definitions to emphasize the characteristic properties of a base.
Acid–Base Properties of Water

Recall that because of its highly polar structure, liquid water can act as either an acid (by donating a proton to a base) or a base (by
using a lone pair of electrons to accept a proton). For example, when a strong acid such as HCl dissolves in water, it dissociates into
chloride ions (C l ) and protons (H ). The proton, in turn, reacts with a water molecule to form the hydronium ion (H O ):
− +
3
+
+ −
H C l(aq) + H2 O(l) → H3 O + Cl (16.3.1)
(aq) (aq)
acid base acid base
In this reaction, H C l is the acid, and water acts as a base by accepting an H +

ion. The reaction in Equation 16.3.1 is often written
in a simpler form by removing H O from each side:
2
+ −
H C l(aq) → H + Cl (16.3.2)
(aq) (aq)
In Equation 16.3.2, the hydronium ion is represented by H

+
, although free H
+
ions do not exist in liquid water as this reaction
demonstrates:
+ +
H + H2 O(l) → H3 O
(aq) (aq)
Water can also act as an acid, as shown in Equation 16.3.3. In this equilibrium reaction, H 2O donates a proton to N H , which acts
3
as a base:
+ −
H2 O(l) + N H3(aq) ⇌ N H + OH (16.3.3)
4(aq) (aq)
acid base
acid base
Water is thus termed amphiprotic, meaning that it can behave as either an acid or a base, depending on the nature of the other
reactant. Notice that Equation 16.3.3 is an equilibrium reaction as indicated by the double arrow and hence has an equilibrium
constant associated with it.
The Ion-Product Constant of Liquid Water

Because water is amphiprotic, one water molecule can react with another to form an OH
−
ion and an H3 O
+
ion in an
autoionization process:
+ −
2 H2 O(l) ⇌ H3 O + OH (16.3.4)
(aq) (aq)
The equilibrium constant K for this reaction can be written as follows:

+ −
aH O
+ ⋅ aOH − [ H3 O ][H O ]
3 + −
Ka = ≈ = [ H3 O ][H O ] (16.3.5)
2 2
a (1)
H2 O
where a is the activity of a species. Because water is the solvent, and the solution is assumed to be dilute, the activity of the water
is approximated by the activity of pure water, which is defined as having a value of 1. The activity of each solute is approximated
by the molarity of the solute.
 Note
It is a common error to claim that the molar concentration of the solvent is in some way involved in the equilibrium law. This
error is a result of a misunderstanding of solution thermodynamics. For example, it is often claimed that Ka = Keq[H2O] for
aqueous solutions. This equation is incorrect because it is an erroneous interpretation of the correct equation Ka = Keq(a ). H2 O
Because a = 1 for a dilute solution, Ka = Keq(1), or Ka = Keq.

H2 O
In this reaction, one water molecule acts as an acid and one water molecule acts as a base. Thus, this reaction actually can be
designated as the K of water and as the K of water. It is most common, however, to designate this reaction and the associated
a b
law of mass action as the K of water:

w
+ −
Kw = [ H3 O ][H O ] (16.3.6)
When pure liquid water is in equilibrium with hydronium and hydroxide ions at 25 °C, the concentrations of the hydronium ion and
the hydroxide ion are equal:
+ − −7
[ H3 O ] = [OH ] = 1.003 × 10 M (16.3.7)
Thus the number of dissociated water molecules is very small indeed, approximately 2 ppb.
Substituting the values for [H 3O
+
] and [OH −
] at 25 °C into this expression
−7 −7 −14
Kw = (1.003 × 10 )(1.003 × 10 ) = 1.006 × 10 (16.3.8)
Thus, to three significant figures, K w = 1.01 × 10

−14
at room temperature, and
−14 + −
Kw = 1.01 × 10 = [ H3 O ][OH ] (16.3.9)
.
Like any other equilibrium constant, K varies with temperature, ranging from 1.15 × 10
w
−15
at 0 °C to 4.99 × 10 −13
at 100 °C.
In pure water, the concentrations of the hydronium ion and the hydroxide ion are equal, and the solution is therefore neutral. If
[ H O ] > [OH ] , however, the solution is acidic, whereas if [ H O ] < [OH ] , the solution is basic. For an aqueous solution,
+ − + −
3 3
the H O concentration is a quantitative measure of acidity: the higher the H O concentration, the more acidic the solution.
3
+
3
+
Conversely, the higher the OH concentration, the more basic the solution. In most situations that you will encounter, the H O
−
3
+
and OH concentrations from the dissociation of water are so small (1.003 × 10 M ) that they can be ignored in calculating the
− −7
H O 3 or OH concentrations of solutions of acids and bases, but this is not always the case.
+ −
Self-Ionization of Water (Kw)
A Video Describing the Self-Ionization of Water (Kw): Self-Ionization of Water (Kw): [youtu.be]
The Relationship among pH, pOH, and pK w
The pH scale is a concise way of describing the H O concentration and hence the acidity or basicity of a solution. Recall that pH
3
+
and the H (H O ) concentration are related as follows:

+
3
+
+
pH = − log10 [ H ] (16.3.10)
+ −pH
[H ] = 10 (16.3.11)
Because the scale is logarithmic, a pH difference of 1 between two solutions corresponds to a difference of a factor of 10 in their
hydronium ion concentrations. Recall also that the pH of a neutral solution is 7.00 ([H O ] = 1.0 × 10 M ), whereas acidic
3
+ −7
solutions have pH < 7.00 (corresponding to [H O ] > 1.0 × 10 ) and basic solutions have pH > 7.00 (corresponding to
3
+ −7
+
[ H O ] < 1.0 × 10
3 ).
−7
Similar notation systems are used to describe many other chemical quantities that contain a large negative exponent. For example,
chemists use an analogous pOH scale to describe the hydroxide ion concentration of a solution. The pOH and [OH ] are related as −
follows:
−
pOH = − log10 [OH ] (16.3.12)
− −pOH
[OH ] = 10 (16.3.13)
The constant K can also be expressed using this notation, where pK

w w = − log Kw .
Because a neutral solution has [OH ] = 1.0 × 10 , the pOH of a neutral solution is 7.00. Consequently, the sum of the pH and
− −7
the pOH for a neutral solution at 25 °C is 7.00 + 7.00 = 14.00. We can show that the sum of pH and pOH is equal to 14.00 for any
aqueous solution at 25 °C by taking the negative logarithm of both sides of Equation ??? :
− log10 Kw = pKw (16.3.14)
+ −
= − log([ H3 O ][OH ]) (16.3.15)
+ −
= (− log[ H3 O ]) + (− log[OH ]) (16.3.16)
= pH + pOH (16.3.17)
Thus at any temperature, pH + pOH = pK , so at 25 °C, where K = 1.0 × 10

w w , pH + pOH = 14.00. More generally, the pH
−14
of any neutral solution is half of the pK at that temperature. The relationship among pH, pOH, and the acidity or basicity of a
w
solution is summarized graphically in Figure 16.3.1 over the common pH range of 0 to 14. Notice the inverse relationship between
the pH and pOH scales.
Figure 16.3.1 : The Inverse Relationship between the pH and pOH Scales. As pH decreases, [H ] and the acidity increase. As pOH
+
increases, [OH ] and the basicity decrease. Common substances have pH values that range from extremely acidic to extremely
−
basic.
Zero is the most acidic and fourteen is the most basic on the pH scale. Zero is the most basic and fourteen is the most acidic on the
pOH scale.
For any neutral solution, pH + pOH = 14.00 (at 25 °C) with pH=pOH=7.
Introduction to pH
A Video Introduction to pH: Introduction to pH [youtu.be]
 Example 16.3.1
The Kw for water at 100 °C is 4.99 × 10 . Calculate pK for water at this temperature and the pH and the pOH for a neutral
−13
w
aqueous solution at 100 °C. Report pH and pOH values to two decimal places.
Given: K w
Asked for: pK , pH, and pOH

w
Strategy:
A. Calculate pK by taking the negative logarithm of K .
w w
B. For a neutral aqueous solution, [H O ] = [OH ] . Use this relationship and Equation 16.3.9 to calculate [H
3
+ −
3O
+
] and
[OH ]. Then determine the pH and the pOH for the solution.
−
Solution:
A
Because pK is the negative logarithm of Kw, we can write
w
−13
p Kw = − log Kw = − log(4.99 × 10 ) = 12.302
The answer is reasonable: K is between 10

w
−13
and 10 −12
, so pK must be between 12 and 13.
w
B
Equation ??? shows that Kw = [ H3 O
+
][OH
−
] . Because [ H3 O
+
] = [OH
−
] in a neutral solution, we can let
] = [OH ] :
+ −
x = [ H3 O
+ −
Kw = [ H3 O ][OH ]
2
= (x)(x) = x
−−
−
x = √Kw
− −−−−−−−− −
−13
= √ 4.99 × 10
−7
= 7.06 × 10 M
Because x is equal to both [H 3O

+
] and [OH −
,
]
−7
pH = pOH = − log(7.06 × 10 )
= 6.15 (to two decimal places)
We could obtain the same answer more easily (without using logarithms) by using the pK . In this case, we know that w
pK w= 12.302, and from Equation 16.3.17, we know that p K = pH + pOH . Because pH = pOH in a neutral solution, we
w
can use Equation 16.3.17 directly, setting pH = pOH = y . Solving to two decimal places we obtain the following:
pKw = pH + pOH
= y +y
= 2y
pKw
y =
2
12.302
=
2
= 6.15 = pH = pOH
 Exercise 16.3.1
Humans maintain an internal temperature of about 37 °C. At this temperature, K = 3.55 × 10 w
−14
. Calculate pK and the pH
w
and the pOH of a neutral solution at 37 °C. Report pH and pOH values to two decimal places.
Answer
p Kw = 13.45
pH = pOH = 6.73
Summary
Water is amphiprotic: it can act as an acid by donating a proton to a base to form the hydroxide ion, or as a base by accepting a
proton from an acid to form the hydronium ion (H O ). The autoionization of liquid water produces OH and H O ions. The
3
+ −
3
+
equilibrium constant for this reaction is called the ion-product constant of liquid water (Kw) and is defined as
= [ H O ][OH ] . At 25 °C, K is 1.01 × 10 ; hence pH + pOH = pK = 14.00 .
+ − −14
K w 3 w w
For any neutral solution, pH + pOH = 14.00 (at 25 °C) and pH = 1/2pK . w
Ion-product constant of liquid water:
+ −
Kw = [ H3 O ][OH ]
Definition of pH:
+
pH = − log 10[ H ]
or
+ −pH
[H ] = 10
Definition of pOH :
+
pOH = − log [OH ]
10
or
− −pOH
[OH ] = 10
Relationship among pH, pOH , and pK : w
p Kw = pH + pOH
16.3: The Autoionization of Water is shared under a CC BY-NC-SA 3.0 license and was authored, remixed, and/or curated by LibreTexts.
16.4: The pH Scale
To define the pH scale as a measure of acidity of a solution
Because of its amphoteric nature (i.e., acts as both an acid or a base), water does not always remain as H 2O molecules. In fact, two
water molecules react to form hydronium and hydroxide ions:
+ −
2 H2 O (l) ⇌ H3 O (aq) + OH (aq) (16.4.1)
This is also called the self-ionization of water. The concentration of H O and OH are equal in pure water because of the 1:1
3
+ −
stoichiometric ratio of Equation 1. The molarity of H3O+ and OH- in water are also both 1.0 × 10 M at 25° C. Therefore, a
−7
constant of water (K ) is created to show the equilibrium condition for the self-ionization of water. The product of the molarity of
w
hydronium and hydroxide ion is always 1.0 × 10 . −14
+ − −14
Kw = [ H3 O ][OH ] = 1.0 × 10 (16.4.2)
This equations also applies to all aqueous solutions. However, Kw does change at different temperatures, which affects the pH
range discussed below.
H
+
and H O is often used interchangeably to represent the hydrated proton, commonly
3
+
call the hydronium ion.

The equation for water equilibrium is:
+ −
H2 O ⇌ H + OH (16.4.3)
If an acid (H ) is added to the water, the equilibrium shifts to the left and the OH ion concentration decreases
+ −
If base ( OH ) is added to water, the equilibrium shifts to left and the H concentration decreases.
− +
pH and pOH
The constant of water determines the range of the pH scale. To understand what the pKw is, it is important to understand first what
the "p" means in pOH, and pH. The Danish biochemist Søren Sørenson proposed the term pH to refer to the "potential of hydrogen
ion." He defined the "p" as the negative of the logarithm, -log, of [H+]. Therefore the pH is the negative logarithm of the molarity
of H. The pOH is the negative logarithm of the molarity of OH- and the pKw is the negative logarithm of the constant of water.
These definitions give the following equations:
+
pH = − log[ H ] (16.4.4)
−
pOH = − log[OH ] (16.4.5)
p Kw = − log[ Kw ] (16.4.6)
At room temperature (25 °C),

−14
Kw = 1.0 × 10 (16.4.7)
So
−14
p Kw = − log[1.0 × 10 ] (16.4.8)
Using the properties of logarithms, Equation 16.4.8 can be rewritten as

−pKw −14
10 = 10 . (16.4.9)
By substituting, we see that pKw is 14. The equation also shows that each increasing unit on the scale decreases by the factor of ten
on the concentration of H . For example, a pH of 1 has a molarity ten times more concentrated than a solution of pH 2.
+
Since
p Kw = 14 (16.4.10)
p Kw = pH + pOH = 14 (16.4.11)
 Definitions
A solution with more OH ions than H ion is basic; for aqueous solutions at 25°C that corresponds to pH > 7.
− +
A solution with more H ions than OH ions is acidic; for aqueous solutions at 25°C that corresponds to pH < 7.
+ −
A solution with that same concentration of H ions than OH ions is neutral; for aqueous solutions at 25°C that
+ −
corresponds to pH = 7.
Since the autoionization constant K is temperature dependent, these correlations between pH values and the acidic/neutral/basic
w
adjectives will be different at temperatures other than 25 °C. For example, the hydronium molarity of pure water at 80 °C is 4.9 ×
10−7 M, which corresponds to pH and pOH values of:
+ −7
pH = − log[ H3 O ] = − log(4.9 × 10 ) = 6.31 (16.4.12)
− −7
pOH = − log[OH ] = − log(4.9 × 10 ) = 6.31 (16.4.13)
At this temperature, then, neutral solutions exhibit pH = pOH = 6.31, acidic solutions exhibit pH less than 6.31 and pOH greater
than 6.31, whereas basic solutions exhibit pH greater than 6.31 and pOH less than 6.31. This distinction can be important when
studying certain processes that occur at nonstandard temperatures, such as enzyme reactions in warm-blooded organisms. Unless
otherwise noted, references to pH values are presumed to be those at standard temperature (25 °C) (Table 16.4.1).
The pH scale is logarithmic, meaning that an increase or decrease of an integer value

changes the concentration by a tenfold. For example, a pH of 3 is ten times more acidic
than a pH of 4. Likewise, a pH of 3 is one hundred times more acidic than a pH of 5.
Similarly a pH of 11 is ten times more basic than a pH of 10.
Figure 16.4.1 depicts the pH scale with common solutions and where they are on the scale.
Figure 16.4.1 : The pH and pOH scales represent concentrations of [H3O+] and OH−, respectively. The pH and pOH values of some
common substances at standard temperature (25 °C) are shown in this chart. Image used with permisison (CC -BY; OpenStax)
 The pH scale does not have upper nor lower bounds!
It is common that the pH scale is argued to range from 0-14 or perhaps 1-14, but neither is correct. The pH range does not have
an upper nor lower bound, since as defined above, the pH is an indication of concentration of H+. For example, at a pH of zero
the hydronium ion concentration is one molar, while at pH 14 the hydroxide ion concentration is one molar. Typically the
concentrations of H+ in water in most solutions fall between a range of 1 M (pH=0) and 10-14 M (pH=14). Hence a range of 0
to 14 provides sensible (but not absolute) "bookends" for the scale. One can go somewhat below zero and somewhat above 14
in water, because the concentrations of hydronium ions or hydroxide ions can exceed one molar.
 Example 16.4.1
If the concentration of N aOH in a solution is 2.5 × 10 −4

M , what is the concentration of H 3O
+
?
Solution
Because
−14 + −
1.0 × 10 = [ H3 O ][OH ]
to find the concentration of H3O+, solve for the [H3O+].

−14
1.0 × 10 +
= [ H3 O ]
−
[OH ]
−14
1.0 × 10 + −11
= [ H3 O ] = 4.0 × 10 M
−4
2.5 × 10
 Example 16.4.2
a. Find the pH of a solution of 0.002 M of HCl.
b. Find the pH of a solution of 0.00005 M NaOH.
Solution
a. The equation for pH is -log [H+]
+ −3
[H ] = 2.0 × 10 M
−3
pH = − log[2.0 × 10 ] = 2.70
b. The equation for pOH is -log [OH-]

− −5
[OH ] = 5.0 × 10 M
−5
pOH = − log[5.0 × 10 ] = 4.30
p Kw = pH + pOH
and
pH = p Kw − pOH
then
pH = 14 − 4.30 = 9.70
 Example 16.4.3: Soil
If moist soil has a pH of 7.84, what is the H+ concentration of the soil solution?
Solution
+
pH = − log[ H ]
+
7.84 = − log[ H ]
+ −8
[H ] = 1.45 × 10 M
Hint: Place -7.84 in your calculator and take the antilog (often inverse log or 10x) = 1.45 x 10-8M
Introduction to pH
A Video Introduction to pH: Introduction to pH [youtu.be]
Summary
The concentration of hydronium ion in a solution of an acid in water is greater than 1.0 × 10 M at 25 °C. The concentration of
−7
hydroxide ion in a solution of a base in water is greater than 1.0 × 10 M at 25 °C. The concentration of H3O+ in a solution can
−7
be expressed as the pH of the solution; pH = − log H O . The concentration of OH− can be expressed as the pOH of the solution:
3
+
pOH = − log[ OH ] . In pure water, pH = 7.00 and pOH = 7.00.

−
References
1. Petrucci, et al. "Self-Ionization of Water and the pH Scale." General Chemistry: Principles & Modern Applications. 7th ed.
Upper Saddle River: Pearson Prentice Hall, 2007. 669-71.
2. Segel, Irwin H. "Acid and Base." Biochemical Calculations. 2nd ed. Wiley: BK Book, 1976. 12.
3. Christopher G. McCarty and Ed Vitz, Journal of Chemical Education, 83(5), 752 (2006)

Emmellin Tung (UCD), Sharon Tsao (UCD), Divya Singh (UCD), Patrick Gormley (Lapeer Community School District)
Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley
(Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed
under a Creative Commons Attribution License 4.0 license. Download for free at http://cnx.org/contents/85abf193-
2bd...a7ac8df6@9.110).
16.4: The pH Scale is shared under a CC BY-NC-SA 3.0 license and was authored, remixed, and/or curated by LibreTexts.
16.5: Strong Acids and Bases
To know the relationship between acid or base strength and the magnitude of K , K , pK , and pK . a b a b
To understand the leveling effect.
The magnitude of the equilibrium constant for an ionization reaction can be used to determine the relative strengths of acids and
bases. For example, the general equation for the ionization of a weak acid in water, where HA is the parent acid and A− is its
conjugate base, is as follows:
+ −
H A(aq) + H2 O(l) ⇌ H3 O +A (16.5.1)
(aq) (aq)
The equilibrium constant for this dissociation is as follows:

+ −
[ H3 O ][ A ]
K = (16.5.2)
[ H2 O][H A]
As we noted earlier, because water is the solvent, it has an activity equal to 1, so the [H 2 O] term in Equation 16.5.2 is actually the
a , which is equal to 1.
H2 O
Again, for simplicity, H 3O

+
can be written as H +
in Equation 16.5.3.
+ −
H A(aq) ⇌ H +A (16.5.3)
(aq) (aq)
Keep in mind, though, that free H does not exist in aqueous solutions and that a proton is transferred to H O in all acid
+
2
ionization reactions to form hydronium ions, H O . The larger the K , the stronger the acid and the higher the H concentration
3
+
a
+
at equilibrium. Like all equilibrium constants, acid–base ionization constants are actually measured in terms of the activities of H +
or OH , thus making them unitless. The values of K for a number of common acids are given in Table 16.5.1.
−
a
Table 16.5.1 : Values of K , pK , K , and pK for Selected Acids (H A and Their Conjugate Bases (A )
a a b b
−
Acid HA Ka pKa A
−
Kb pKb
hydroiodic acid HI 2 × 10
9
−9.3 I
−
5.5 × 10
−24
23.26
sulfuric acid (1)* H2 S O4 1 × 10

2
−2.0 HSO
−
4
1 × 10
−16
16.0
nitric acid HN O3 2.3 × 10

1
−1.37 NO
−
3
4.3 × 10
−16
15.37
hydronium ion H3 O
+
1.0 0.00 H2 O 1.0 × 10
−14
14.00
sulfuric acid (2)* HSO

−
4
1.0 × 10
−2
1.99 SO
2−
4
9.8 × 10
−13
12.01
hydrofluoric acid HF 6.3 × 10

−4
3.20 F
−
1.6 × 10
−11
10.80
nitrous acid HN O2 5.6 × 10

−4
3.25 N O2
−
1.8 × 10
−11
10.75
formic acid HC O2 H 1.78 × 10

−4
3.750 HC O2 − 5.6 × 10
−11
10.25
benzoic acid C6 H5 C O2 H 6.3 × 10

−5
4.20 C6 H5 C O
−
2
1.6 × 10
−10
9.80
acetic acid C H3 C O2 H 1.7 × 10

−5
4.76 C H3 C O
−
2
5.8 × 10
−10
9.24
pyridinium ion C5 H5 N H
+
5.9 × 10
−6
5.23 C5 H5 N 1.7 × 10
−9
8.77
hypochlorous acid HOCl 4.0 × 10

−8
7.40 OCl
−
2.5 × 10
−7
6.60
hydrocyanic acid HCN 6.2 × 10

−10
9.21 CN
−
1.6 × 10
−5
4.79
ammonium ion NH
+
4
5.6 × 10
−10
9.25 N H3 1.8 × 10
−5
4.75
water H2 O 1.0 × 10
−14
14.00 OH
−
1.00 0.00
acetylene C2 H2 1 × 10
−26
26.0 HC
−
2
1 × 10
12
−12.0
*The number in parentheses indicates the ionization step referred to for a polyprotic acid.
Acid HA Ka pKa A
−
Kb pKb
ammonia N H3 1 × 10
−35
35.0 NH
−
2
1 × 10
21
−21.0
Weak bases react with water to produce the hydroxide ion, as shown in the following general equation, where B is the parent base
and BH+ is its conjugate acid:
+ −
B(aq) + H2 O(l) ⇌ BH + OH (16.5.4)
(aq) (aq)
The equilibrium constant for this reaction is the base ionization constant (Kb), also called the base dissociation constant:
+ −
[BH ][OH ]
Kb = (16.5.5)
[B]
Once again, the activity of water has a value of 1, so water does not appear in the equilibrium constant expression. The larger the
K , the stronger the base and the higher the OH concentration at equilibrium. The values of K for a number of common weak
−
b b
bases are given in Table 16.5.2.

Table 16.5.2 : Values of K , pK , K , and pK for Selected Weak Bases (B) and Their Conjugate Acids (BH+)
b b a a
Base B Kb pKb BH
+
Ka pKa
hydroxide ion OH
−
1.0 0.00* H2 O 1.0 × 10
−14
14.00
phosphate ion PO
3−
4
2.1 × 10
−2
1.68 HP O
2−
4
4.8 × 10
−13
12.32
dimethylamine (C H3 )2 N H 5.4 × 10
−4
3.27 (C H3 )2 N H
+
2
1.9 × 10
−11
10.73
methylamine C H3 N H2 4.6 × 10
−4
3.34 C H3 N H
3
+
2.2 × 10
−11
10.66
trimethylamine (C H3 )3 N 6.3 × 10
−5
4.20 (C H3 )3 N H
+
1.6 × 10
−10
9.80
ammonia N H3 1.8 × 10
−5
4.75 NH
+
4
5.6 × 10
−10
9.25
pyridine C5 H5 N 1.7 × 10
−9
8.77 C5 H5 N H
+
5.9 × 10
−6
5.23
aniline C6 H5 N H2 7.4 × 10
−10
9.13 C6 H5 N H
+
3
1.3 × 10
−5
4.87
water H2 O 1.0 × 10
−14
14.00 H3 O
+ ∗
1.0 0.00
*As in Table 16.5.1.
There is a simple relationship between the magnitude of K for an acid and K for its conjugate base. Consider, for example, the
a b
ionization of hydrocyanic acid (H C N ) in water to produce an acidic solution, and the reaction of C N with water to produce a −
basic solution:
+ −
H C N(aq) ⇌ H + CN (16.5.6)
(aq) (aq)
− −
CN + H2 O(l) ⇌ OH + H C N(aq) (16.5.7)
(aq) (aq)
The equilibrium constant expression for the ionization of HCN is as follows:

+ −
[H ][C N ]
Ka = (16.5.8)
[H C N ]
The corresponding expression for the reaction of cyanide with water is as follows:
−
[OH ][H C N ]
Kb = (16.5.9)
−
[C N ]
If we add Equations 16.5.6 and 16.5.7, we obtain the following:

add Equations 16.5.6 and 16.5.7 , we obtain
Reaction Equilibrium Constants
Reaction Equilibrium Constants
+ − + −
HCN(aq ) ⇌ H + CN Ka = [H ] [C N ] / [HCN ]
(aq ) (aq )
− − − −
CN + H2 O(l) ⇌ O H + HCN(aq ) Kb = [O H ] [HCN ] / [C N ]
(aq ) (aq )
+ − + −
H2 O(l) ⇌ H + OH K = Ka × Kb = [H ][O H ]
(aq ) (aq )
In this case, the sum of the reactions described by K and K is the equation for the autoionization of water, and the product of the
a b
two equilibrium constants is K : w
Ka Kb = Kw (16.5.10)
Thus if we know either K for an acid or

a Kb for its conjugate base, we can calculate the other equilibrium constant for any
conjugate acid–base pair.
Just as with pH, pOH , and pKw, we can use negative logarithms to avoid exponential notation in writing acid and base ionization
constants, by defining pK as follows:
a
pKa = − log10 Ka (16.5.11)
−pKa
Ka = 10 (16.5.12)
and pK as
b
p Kb = − log10 Kb (16.5.13)
−pKb
Kb = 10 (16.5.14)
Similarly, Equation 16.5.10, which expresses the relationship between K and K , can be written in logarithmic form as follows:
a b
p Ka + p Kb = p Kw (16.5.15)
At 25 °C, this becomes
p Ka + p Kb = 14.00 (16.5.16)
The values of pK and pK are given for several common acids and bases in Tables 16.5.1 and 16.5.2, respectively, and a more
a b
extensive set of data is provided in Tables E1 and E2. Because of the use of negative logarithms, smaller values of pK correspond a
to larger acid ionization constants and hence stronger acids. For example, nitrous acid (H N O ), with a pK of 3.25, is about a
2 a
million times stronger acid than hydrocyanic acid (HCN), with a pK of 9.21. Conversely, smaller values of pK correspond to
a b
larger base ionization constants and hence stronger bases.
Figure 16.5.1 : The Relative Strengths of Some Common Conjugate Acid–Base Pairs. The strongest acids are at the bottom left,
and the strongest bases are at the top right. The conjugate base of a strong acid is a very weak base, and, conversely, the conjugate
acid of a strong base is a very weak acid.
Strong acids are H3O plus, HNO3, H2SO4, HCl, and HBr. Negligible acids are HS minus and OH minus. Stron bases are O
negative 2, S negative 2. Negligible bases are NO3 minus, HSO4 minus, Cl minus, and Br minus.
The relative strengths of some common acids and their conjugate bases are shown graphically in Figure 16.5.1. The conjugate
acid–base pairs are listed in order (from top to bottom) of increasing acid strength, which corresponds to decreasing values of pK . a
This order corresponds to decreasing strength of the conjugate base or increasing values of pK . At the bottom left of Figure
b
16.5.2 are the common strong acids; at the top right are the most common strong bases. Notice the inverse relationship between the
strength of the parent acid and the strength of the conjugate base. Thus the conjugate base of a strong acid is a very weak base, and
the conjugate base of a very weak acid is a strong base.
The conjugate base of a strong acid is a weak base and vice versa.
We can use the relative strengths of acids and bases to predict the direction of an acid–base reaction by following a single rule: an
acid–base equilibrium always favors the side with the weaker acid and base, as indicated by these arrows:
stronger acid + stronger base −⇀

↽ weaker acid + weaker base
In an acid–base reaction, the proton always reacts with the stronger base.
For example, hydrochloric acid is a strong acid that ionizes essentially completely in dilute aqueous solution to produce H O and 3
+
C l ; only negligible amounts of H C l molecules remain undissociated. Hence the ionization equilibrium lies virtually all the way
−
to the right, as represented by a single arrow:

+ −
H C l(aq) + H2 O(l) → H3 O + Cl (16.5.17)
(aq) (aq)
In contrast, acetic acid is a weak acid, and water is a weak base. Consequently, aqueous solutions of acetic acid contain mostly
acetic acid molecules in equilibrium with a small concentration of H O and acetate ions, and the ionization equilibrium lies far to
3
+
the left, as represented by these arrows:
⇀ + −
CH CO H +H O ↽− H O + CH CO
3 2 (aq) 2 (l) 3 (aq) 3 2 (aq)
Similarly, in the reaction of ammonia with water, the hydroxide ion is a strong base, and ammonia is a weak base, whereas the
ammonium ion is a stronger acid than water. Hence this equilibrium also lies to the left:
⇀ + −
H2 O(l) + N H3(aq) ↽− NH + OH
4(aq) (aq)
All acid–base equilibria favor the side with the weaker acid and base. Thus the proton is
bound to the stronger base.
 Example 16.5.1: Butyrate and Dimethylammonium Ions

a. Calculate K and pK of the butyrate ion (C H C H C H C O ). The pK of butyric acid at 25°C is 4.83. Butyric acid is
b b 3 2 2
−
2 a
responsible for the foul smell of rancid butter.

b. Calculate K and pK of the dimethylammonium ion ((C H ) N H ). The base ionization constant K of dimethylamine
a a 3 2
+
2 b
((C H ) N H) is 5.4 × 10 at 25°C.

3 2
−4
Given: pK and K
a b
Asked for: corresponding K and pK , K and pK b b a a
Strategy:
The constants K and K are related as shown in Equation 16.5.10. The pK and pK for an acid and its conjugate base are
a b a b
related as shown in Equations 16.5.15 and 16.5.16. Use the relationships pK = −log K and K = 10−pK (Equations 16.5.11 and
16.5.13) to convert between K and pK or K and pK . a a b b
Solution:
We are given the pK for butyric acid and asked to calculate the K and the pK for its conjugate base, the butyrate ion.
a b b
Because the pK value cited is for a temperature of 25°C, we can use Equation 16.5.16: pK + pK = pKw = 14.00.
a a b
Substituting the pK and solving for the pK ,

a b
4.83 + p Kb = 14.00
p Kb = 14.00 − 4.83 = 9.17
Because pK b = − log Kb , K is 10
b
−9.17
= 6.8 × 10
−10
.
In this case, we are given K for a base (dimethylamine) and asked to calculate K and pK for its conjugate acid, the
b a a
dimethylammonium ion. Because the initial quantity given is K rather than pK , we can use Equation 16.5.10: K K = K .
b b a b w
Substituting the values of K and K at 25°C and solving for K ,

b w a
−4 −14
Ka (5.4 × 10 ) = 1.01 × 10
−11
Ka = 1.9 × 10
Because pK = −loga Ka , we have p Ka = − log(1.9 × 10

−11
) = 10.72 . We could also have converted Kb to pKb to obtain
the same answer:
−4
p Kb = − log(5.4 × 10 ) = 3.27
pKa + p Kb = 14.00
p Ka = 10.73
−pKa −10.73 −11

Ka = 10 = 10 = 1.9 × 10
If we are given any one of these four quantities for an acid or a base (K , pK , K , or pK ), we can calculate the other three.a a b b
 Exercise 16.5.1: Lactic Acid
Lactic acid (C H C H (OH )C O H) is responsible for the pungent taste and smell of sour milk; it is also thought to produce
3 2
soreness in fatigued muscles. Its pK is 3.86 at 25°C. Calculate K for lactic acid and pK and K for the lactate ion.
a a b b
Answer
Ka = 1.4 × 10
−4
for lactic acid;
pKb = 10.14 and
Kb = 7.2 × 10
−11
for the lactate ion
Calculating pH in Strong Acid or Strong …
A Video Calculating pH in Strong Acid or Strong Base Solutions: Calculating pH in Strong Acid or Strong Base Solutions
[youtu.be]
Solutions of Strong Acids and Bases: The Leveling Effect

You will notice in Table 16.5.1 that acids like H SO and H N O lie above the hydronium ion, meaning that they have pK
2 4 3 a
values less than zero and are stronger acids than the H O ion. Recall from Chapter 4 that the acidic proton in virtually all
3
+
oxoacids is bonded to one of the oxygen atoms of the oxoanion. Thus nitric acid should properly be written as H ON O . 2
Unfortunately, however, the formulas of oxoacids are almost always written with hydrogen on the left and oxygen on the right,
giving H N O instead. In fact, all six of the common strong acids that we first encountered in Chapter 4 have pK values less than
3 a
zero, which means that they have a greater tendency to lose a proton than does the H O ion. Conversely, the conjugate bases of
3
+
these strong acids are weaker bases than water. Consequently, the proton-transfer equilibria for these strong acids lie far to the
right, and adding any of the common strong acids to water results in an essentially stoichiometric reaction of the acid with water to
form a solution of the H O ion and the conjugate base of the acid.
3
+
Although K for H I is about 108 greater than K for H N O , the reaction of either H I or H N O with water gives an essentially
a a 3 3
stoichiometric solution of H O and I− or N O . In fact, a 0.1 M aqueous solution of any strong acid actually contains 0.1 M
3
+ −
3
H O , regardless of the identity of the strong acid. This phenomenon is called the leveling effect: any species that is a stronger
+
3
acid than the conjugate acid of water (H O ) is leveled to the strength of H O in aqueous solution because H O is the
3
+
3
+
3
+
strongest acid that can exist in equilibrium with water. Consequently, it is impossible to distinguish between the strengths of acids
such as HI and HNO3 in aqueous solution, and an alternative approach must be used to determine their relative acid strengths.
One method is to use a solvent such as anhydrous acetic acid. Because acetic acid is a stronger acid than water, it must also be a
weaker base, with a lesser tendency to accept a proton than H O. Measurements of the conductivity of 0.1 M solutions of both HI
2
and H N O in acetic acid show that HI is completely dissociated, but H N O is only partially dissociated and behaves like a weak
3 3
acid in this solvent. This result clearly tells us that HI is a stronger acid than H N O . The relative order of acid strengths and
3
approximate K and pK values for the strong acids at the top of Table 16.5.1 were determined using measurements like this and
a a
different nonaqueous solvents.
In aqueous solutions, H O is the strongest acid and OH

3
+ −
is the strongest base that can
exist in equilibrium with H O. 2
The leveling effect applies to solutions of strong bases as well: In aqueous solution, any base stronger than OH− is leveled to the
strength of OH− because OH− is the strongest base that can exist in equilibrium with water. Salts such as K O, N aOC H 2 3
(sodium methoxide), and N aN H (sodamide, or sodium amide), whose anions are the conjugate bases of species that would lie
2
below water in Table 16.5.2, are all strong bases that react essentially completely (and often violently) with water, accepting a
proton to give a solution of OH and the corresponding cation:
−
− +
K2 O(s) + H2 O(l) → 2OH + 2K (16.5.18)
(aq) (aq)
− +
N aOC H3(s) + H2 O(l) → OH +Na + C H3 OH(aq) (16.5.19)
(aq) (aq)
− +
N aN H2(s) + H2 O(l) → OH +Na + N H3(aq) (16.5.20)
(aq) (aq)
Other examples that you may encounter are potassium hydride (KH ) and organometallic compounds such as methyl lithium (
C H Li).
3
Polyprotic Acids and Bases

As you learned, polyprotic acids such as H SO , H P O , and H C O contain more than one ionizable proton, and the protons
2 4 3 4 2 3
are lost in a stepwise manner. The fully protonated species is always the strongest acid because it is easier to remove a proton from
a neutral molecule than from a negatively charged ion. Thus acid strength decreases with the loss of subsequent protons, and,
correspondingly, the pK increases. Consider H SO , for example:
a 2 4
− −⇀ 2− +
H SO ↽ SO +H p Ka = −2
4(aq) 4(aq) (aq)
The equilibrium in the first reaction lies far to the right, consistent with H SO being a strong acid. In contrast, in the second
2 4
reaction, appreciable quantities of both H SO and SO are present at equilibrium.

−
4
2−
4
For a polyprotic acid, acid strength decreases and the pK increases with the sequential a
loss of each proton.

The hydrogen sulfate ion (H SO ) is both the conjugate base of H SO and the conjugate acid of SO . Just like water, HSO4−
−
4 2 4
2−
can therefore act as either an acid or a base, depending on whether the other reactant is a stronger acid or a stronger base.
Conversely, the sulfate ion (SO ) is a polyprotic base that is capable of accepting two protons in a stepwise manner:
2−
4
2− − −
SO + H2 O(aq) −⇀
↽ H SO + OH
4(aq) 4(aq) (aq)
− −
H SO + H2 O(aq) −⇀
↽ H2 S O4(aq) + OH (16.5.21)
4(aq) (aq)
Like any other conjugate acid–base pair, the strengths of the conjugate acids and bases are related by pK + pK = pKw. Consider, a b
for example, the H SO /SO conjugate acid–base pair. From Table 16.5.1, we see that the pK of H SO is 1.99. Hence the
−
4
2−
4 a
−
pK of SO is 14.00 − 1.99 = 12.01. Thus sulfate is a rather weak base, whereas OH is a strong base, so the equilibrium shown
2− −
b 4
in Equation 16.5.21 lies to the left. The H SO ion is also a very weak base (pK of H SO = 2.0, pK of
−
4 a 2 4 b
= 14 − (−2.0) = 16 ), which is consistent with what we expect for the conjugate base of a strong acid.
−
H SO
4
 Example 16.5.2
Predict whether the equilibrium for each reaction lies to the left or the right as written.
+ 3− 2−
NH +PO ⇌ N H3(aq) + H P O
4(aq) 4(aq) 4(aq)
− −
C H3 C H2 C O2 H(aq) + C N ⇌ C H3 C H2 C O + H C N(aq)
(aq) 2(aq)
Given: balanced chemical equation

Asked for: equilibrium position
Strategy:
Identify the conjugate acid–base pairs in each reaction. Then refer to Tables 16.5.1and16.5.2 and Figure 16.5.2 to determine
which is the stronger acid and base. Equilibrium always favors the formation of the weaker acid–base pair.
Solution:
The conjugate acid–base pairs are N H /N H and H P O /P O . According to Tables 16.5.1 and 16.5.2, N H is a
+
4
3
2−
4
3−
4 4
+
stronger acid (pK = 9.25) than H P O

a (pKa = 12.32), and P O
2−
4
is a stronger base (pK = 1.68) than N H (
3−
4 b 3
p K = 4.75 ). The equilibrium will therefore lie to the right, favoring the formation of the weaker acid–base pair:
b
+ 3− 2−
NH + PO −
↽⇀ NH + HP O
4(aq) 4(aq) 3(aq) 4(aq)
stronger acid stronger base weaker base weaker acid
The conjugate acid–base pairs are C H C H C O H /C H C H C O and H C N /C N . According to Table 16.5.1, HCN is a
3 2 2 3 2
−
2
−
weak acid (pKa = 9.21) and C N is a moderately weak base (pKb = 4.79). Propionic acid (C H C H C O H) is not listed in
−
3 2 2
Table 16.5.1, however. In a situation like this, the best approach is to look for a similar compound whose acid–base properties
are listed. For example, propionic acid and acetic acid are identical except for the groups attached to the carbon atom of the
carboxylic acid (−CH CH versus −CH ), so we might expect the two compounds to have similar acid–base properties. In
2 3 3
particular, we would expect the pK of propionic acid to be similar in magnitude to the pK of acetic acid. (In fact, the pK
a a a
of propionic acid is 4.87, compared to 4.76 for acetic acid, which makes propionic acid a slightly weaker acid than acetic acid.)
Thus propionic acid should be a significantly stronger acid than H C N . Because the stronger acid forms the weaker conjugate
base, we predict that cyanide will be a stronger base than propionate. The equilibrium will therefore lie to the right, favoring
the formation of the weaker acid–base pair:
− −
C H3 C H2 C O2 H(aq) + CN −⇀
↽ C H3 C H2 C O + H C N(aq)
(aq) 2(aq)
stronger acid weaker acid
stronger base weaker base
 Exercise 16.5.1
Predict whether the equilibrium for each reaction lies to the left or the right as written.
a. H2 O(l) + H S
−
(aq)
⇌ OH
−
(aq)
+ H2 S(aq)
b. H C O −
2(aq)
+ H SO
−
4(aq)
⇌ H C O2 H(aq) + S O
2−
4(aq)
Answer a
left
Answer b
left
Polyprotic Acids
A Video Discussing Polyprotic Acids: Polyprotic Acids [youtu.be]
Summary
Acid–base reactions always contain two conjugate acid–base pairs. Each acid and each base has an associated ionization constant
that corresponds to its acid or base strength. Two species that differ by only a proton constitute a conjugate acid–base pair. The
magnitude of the equilibrium constant for an ionization reaction can be used to determine the relative strengths of acids and bases.
For an aqueous solution of a weak acid, the dissociation constant is called the acid ionization constant (K ). Similarly, the
a
equilibrium constant for the reaction of a weak base with water is the base ionization constant (K ). For any conjugate acid–base
b
pair, K K = K . Smaller values of pK correspond to larger acid ionization constants and hence stronger acids. Conversely,
a b w a
smaller values of pK correspond to larger base ionization constants and hence stronger bases. At 25°C, pK + pK = 14.00 .
b a b
Acid–base reactions always proceed in the direction that produces the weaker acid–base pair. No acid stronger than H O and no 3
+
base stronger than OH can exist in aqueous solution, leading to the phenomenon known as the leveling effect. Polyprotic acids
−
(and bases) lose (and gain) protons in a stepwise manner, with the fully protonated species being the strongest acid and the fully
deprotonated species the strongest base.
Key Equations
Acid ionization constant:
+ −
[ H3 O ][ A ]
Ka =
[H A]
Base ionization constant:

+ −
[BH ][OH ]
Kb =
[B]
Relationship between K and K of a conjugate acid–base pair:

a b
Ka Kb = Kw
Definition of pK : a
pKa = − log10 Ka
−pKa
Ka = 10
Definition of pK : b
p Kb = − log10 Kb
−pKb
Kb = 10
Relationship between pK and pK of a conjugate acid–base pair:

a b
p Ka + p Kb = p Kw
p Ka + p Kb = 14.00 at 25°C

Stephen Lower, Professor Emeritus (Simon Fraser U.) Chem1 Virtual Textbook
16.5: Strong Acids and Bases is shared under a CC BY-NC-SA 3.0 license and was authored, remixed, and/or curated by LibreTexts.
16.6: Weak Acids
Assess the relative strengths of acids and bases according to their ionization constants
Rationalize trends in acid–base strength in relation to molecular structure
Carry out equilibrium calculations for weak acid–base systems
We can rank the strengths of acids by the extent to which they ionize in aqueous solution. The reaction of an acid with water is
given by the general expression:
+ −
HA(aq) + H O(l) ⇌ H O (aq) + A (aq)
2 3
Water is the base that reacts with the acid HA, A is the conjugate base of the acid HA, and the hydronium ion is the conjugate
−
acid of water. A strong acid yields 100% (or very nearly so) of H O and A when the acid ionizes in water; Figure 16.6.1 lists
3
+ −
several strong acids. A weak acid gives small amounts of H O and A . 3

+ −
Figure 16.6.1 : Some of the common strong acids and bases are listed here.
Six Strong Acids Six Strong Bases
HClO
4
perchloric acid LiOH lithium hydroxide
HCl hydrochloric acid NaOH sodium hydroxide
HBr hydrobromic acid KOH potassium hydroxide
HI hydroiodic acid Ca(OH)

2
calcium hydroxide
HNO
3
nitric acid Sr(OH)
2
strontium hydroxide
H SO
2 4
sulfuric acid Ba(OH)
2
barium hydroxide
The relative strengths of acids may be determined by measuring their equilibrium constants in aqueous solutions. In solutions of the
same concentration, stronger acids ionize to a greater extent, and so yield higher concentrations of hydronium ions than do weaker
acids. The equilibrium constant for an acid is called the acid-ionization constant, Ka. For the reaction of an acid HA:
+ −
2 3
we write the equation for the ionization constant as:

+ −
[H O ][ A ]
3
Ka =
[HA]
where the concentrations are those at equilibrium. As noted in the section on equilibrium constants, although water is a reactant in
the reaction, it is the solvent as well, so its activity has a value of 1, which does not change the value of K . a
 Note
It is a common error to claim that the molar concentration of the solvent is in some way involved in the equilibrium law. This
error is a result of a misunderstanding of solution thermodynamics. For example, it is often claimed that Ka = Keq[H2O] for
aqueous solutions. This equation is incorrect because it is an erroneous interpretation of the correct equation Ka = Keq(a ). H2 O
Because a H2 O= 1 for a dilute solution, Ka = Keq(1), or Ka = Keq.
Ka H O
+
A
− The larger the of an acid, the larger the concentration of and relative to the concentration of the nonionized acid, .
3
HA
Thus a stronger acid has a larger ionization constant than does a weaker acid. The ionization constants
increase as the strengths of the acids increase.
The following data on acid-ionization constants indicate the order of acid strength: CH 3
CO H < HNO
2 2
< HSO
−
+ − −5
CH CO H(aq) + H O(l) ⇌ H O (aq) + CH CO (aq) Ka = 1.8 × 10
3 2 2 3 3 2
+ − −4
HNO (aq) + H O(l) ⇌ H O (aq) + NO (aq) Ka = 4.6 × 10
2 2 3 2
− + 2− −2
HSO 4 (aq) + H O(l) ⇌ H O (aq) + SO 4 (aq) Ka = 1.2 × 10
2 3
Another measure of the strength of an acid is its percent ionization. The percent ionization of a weak acid is the ratio of the
concentration of the ionized acid to the initial acid concentration, times 100:
+
[H O ]
3 eq
% ionization = × 100% (16.6.1)
[HA]
0
Because the ratio includes the initial concentration, the percent ionization for a solution of a given weak acid varies depending on
the original concentration of the acid, and actually decreases with increasing acid concentration.
 Example 16.6.1: Calculation of Percent Ionization from pH
Calculate the percent ionization of a 0.125-M solution of nitrous acid (a weak acid), with a pH of 2.09.
Solution
The percent ionization for an acid is:
+
[H O ]
3 eq
× 100
[ HNO ]
2 0
The chemical equation for the dissociation of the nitrous acid is:
− +
HNO (aq) + H O(l) ⇌ NO (aq) + H O (aq).
2 2 2 3
Since 10 −pH
= [H O
3
+
] , we find that 10
−2.09
= 8.1 × 10
−3
M , so that percent ionization (Equation 16.6.1) is:
−3
8.1 × 10
× 100 = 6.5%
0.125
Remember, the logarithm 2.09 indicates a hydronium ion concentration with only two significant figures.
 Exercise 16.6.1
Calculate the percent ionization of a 0.10 M solution of acetic acid with a pH of 2.89.
Answer
1.3% ionized
We can rank the strengths of bases by their tendency to form hydroxide ions in aqueous solution. The reaction of a Brønsted-Lowry
base with water is given by:
+ −
B(aq) + H O(l) ⇌ HB (aq) + OH (aq)
2
Water is the acid that reacts with the base, HB is the conjugate acid of the base B , and the hydroxide ion is the conjugate base of
+
water. A strong base yields 100% (or very nearly so) of OH− and HB+ when it reacts with water; Figure 16.6.1 lists several strong
bases. A weak base yields a small proportion of hydroxide ions. Soluble ionic hydroxides such as NaOH are considered strong
bases because they dissociate completely when dissolved in water.
As we did with acids, we can measure the relative strengths of bases by measuring their base-ionization constant (Kb) in aqueous
solutions. In solutions of the same concentration, stronger bases ionize to a greater extent, and so yield higher hydroxide ion
concentrations than do weaker bases. A stronger base has a larger ionization constant than does a weaker base. For the reaction of a
base, B :
+ −
B(aq) + H O(l) ⇌ HB (aq) + OH (aq),
2
we write the equation for the ionization constant as:

+ −
[ HB ][ OH ]
Kb =
[B]
where the concentrations are those at equilibrium. Again, we do not see water in the equation because water is the solvent and has
an activity of 1. The chemical reactions and ionization constants of the three bases shown are:
− − −11
NO2 (aq) + H O(l) ⇌ HNO (aq) + OH (aq) Kb = 2.17 × 10
2 2
− − −10
CH CO (aq) + H O(l) ⇌ CH CO H(aq) + OH (aq) Kb = 5.6 × 10
3 2 2 3 2
+ − −5
NH (aq) + H O(l) ⇌ NH (aq) + OH (aq) Kb = 1.8 × 10
3 2 4
A table of ionization constants of weak bases appears in Table E2. As with acids, percent ionization can be measured for basic
solutions, but will vary depending on the base ionization constant and the initial concentration of the solution.
Consider the ionization reactions for a conjugate acid-base pair, HA − A : −
+ −
2 3
+ −
[H O ][ A ]
with K a =
3
.
[HA]
− −
A (aq) + H O(l) ⇌ OH (aq) + HA(aq)
2
[HA][OH]
with K b =
−
.
[A ]
Adding these two chemical equations yields the equation for the autoionization for water:
− + − −
HA(aq) + H O(l) + A (aq) + H O(l) ⇌ H O (aq) + A (aq) + OH (aq) + HA(aq)
2 2 3
+ −
2 H O(l) ⇌ H O (aq) + OH (aq)
2 3
As shown in the previous chapter on equilibrium, the K expression for a chemical equation derived from adding two or more other
equations is the mathematical product of the other equations’ K expressions. Multiplying the mass-action expressions together and
cancelling common terms, we see that:
+ − −
[H O ][ A ] [HA][ OH ]
3 + −
Ka × Kb = × = [H O ][ OH ] = Kw
− 3
[HA] [A ]
For example, the acid ionization constant of acetic acid (CH3COOH) is 1.8 × 10−5, and the base ionization constant of its conjugate
base, acetate ion (CH COO ), is 5.6 × 10−10. The product of these two constants is indeed equal to K :
3
−
w
−5 −10 −14
Ka × Kb = (1.8 × 10 ) × (5.6 × 10 ) = 1.0 × 10 = Kw
The extent to which an acid, HA, donates protons to water molecules depends on the strength of the conjugate base, A , of the −
acid. If A is a strong base, any protons that are donated to water molecules are recaptured by A . Thus there is relatively little
− −
A
−
and H O in solution, and the acid, HA, is weak. If A is a weak base, water binds the protons more strongly, and the
3
+ −
solution contains primarily A and H O —the acid is strong. Strong acids form very weak conjugate bases, and weak acids form
−
3
+
stronger conjugate bases (Figure 16.6.2).
Figure 16.6.2 : This diagram shows the relative strengths of conjugate acid-base pairs, as indicated by their ionization constants in
aqueous solution.
Figure 16.6.3 lists a series of acids and bases in order of the decreasing strengths of the acids and the corresponding increasing
strengths of the bases. The acid and base in a given row are conjugate to each other.
The first six acids in Figure 16.6.3 are the most common strong acids. These acids are completely dissociated in aqueous solution.
The conjugate bases of these acids are weaker bases than water. When one of these acids dissolves in water, their protons are
completely transferred to water, the stronger base.
Those acids that lie between the hydronium ion and water in Figure 16.6.3 form conjugate bases that can compete with water for
possession of a proton. Both hydronium ions and nonionized acid molecules are present in equilibrium in a solution of one of these
acids. Compounds that are weaker acids than water (those found below water in the column of acids) in Figure 16.6.3 exhibit no
observable acidic behavior when dissolved in water. Their conjugate bases are stronger than the hydroxide ion, and if any conjugate
base were formed, it would react with water to re-form the acid.
Figure 16.6.3 : The chart shows the relative strengths of conjugate acid-base pairs.
The extent to which a base forms hydroxide ion in aqueous solution depends on the strength of the base relative to that of the
hydroxide ion, as shown in the last column in Figure 16.6.3. A strong base, such as one of those lying below hydroxide ion, accepts
protons from water to yield 100% of the conjugate acid and hydroxide ion. Those bases lying between water and hydroxide ion
accept protons from water, but a mixture of the hydroxide ion and the base results. Bases that are weaker than water (those that lie
above water in the column of bases) show no observable basic behavior in aqueous solution.
 Example 16.6.2: The Product Ka × Kb = Kw
Use the K for the nitrite ion, NO , to calculate the K for its conjugate acid.
b
−
2 a
Solution
Kb for NO is given in this section as 2.17 × 10−11. The conjugate acid of
−
2
NO2
−
is HNO2; Ka for HNO2 can be calculated
using the relationship:
−14
Ka × Kb = 1.0 × 10 = Kw
Solving for Ka, we get:
Kw
Ka =
Kb
−14
1.0 × 10
=
−11
2.17 × 10
−4
= 4.6 × 10
This answer can be verified by finding the Ka for HNO2 in Table E1
 Exercise 16.6.2
We can determine the relative acid strengths of NH and HCN by comparing their ionization constants. The ionization
+
4
constant of HCN is given in Table E1 as 4.9 × 10−10. The ionization constant of NH is not listed, but the ionization constant
+
4
of its conjugate base, NH , is listed as 1.8 × 10−5. Determine the ionization constant of NH , and decide which is the stronger
3
+
4
acid, HCN or NH . +
4
Answer
NH
+
4
is the slightly stronger acid (Ka for NH = 5.6 × 10−10).
+
4
The Ionization of Weak Acids and Weak Bases

Many acids and bases are weak; that is, they do not ionize fully in aqueous solution. A solution of a weak acid in water is a mixture
of the nonionized acid, hydronium ion, and the conjugate base of the acid, with the nonionized acid present in the greatest
concentration. Thus, a weak acid increases the hydronium ion concentration in an aqueous solution (but not as much as the same
amount of a strong acid).
Acetic acid (CH 3
CO H
2
) is a weak acid. When we add acetic acid to water, it ionizes to a small extent according to the equation:
+ −
CH CO H(aq) + H O(l) ⇌ H O (aq) + CH CO2 (aq)
3 2 2 3 3
giving an equilibrium mixture with most of the acid present in the nonionized (molecular) form. This equilibrium, like other
equilibria, is dynamic; acetic acid molecules donate hydrogen ions to water molecules and form hydronium ions and acetate ions at
the same rate that hydronium ions donate hydrogen ions to acetate ions to reform acetic acid molecules and water molecules. We
can tell by measuring the pH of an aqueous solution of known concentration that only a fraction of the weak acid is ionized at any
moment (Figure 16.6.4). The remaining weak acid is present in the nonionized form.
For acetic acid, at equilibrium:
+ −
[H O ][ CH CO ]
3 3 2 −5
Ka = = 1.8 × 10
[ CH CO H]
3 2
Figure 16.6.4 : pH paper indicates that a 0.l-M solution of HCl (beaker on left) has a pH of 1. The acid is fully ionized and [H O ]
+
= 0.1 M. A 0.1-M solution of CH3CO2H (beaker on right) has a pH of 3 ( [H O ] = 0.001 M) because the weak acid CH3CO2H is
3
+
only partially ionized. In this solution, [H O ] < [CH CO H] . (credit: modification of work by Sahar Atwa)
3
+
3 2
This image shows two bottles containing clear colorless solutions. Each bottle contains a single p H indicator strip. The strip in the
bottle on the left is red, and a similar red strip is placed on a filter paper circle in front of the bottle on surface on which the bottles
are resting. Similarly, the second bottle on the right contains and orange strip and an orange strip is placed in front of it on a filter
paper circle. Between the two bottles is a pack of p Hydrion papers with a p H color scale on its cover.
Table 16.6.1 : Ionization Constants of Some Weak Acids
Ionization Reaction Ka at 25 °C
HSO
−
4
+H O ⇌ H O
2 3
+
+ SO
2−
4
1.2 × 10−2
HF + H O ⇌ H O
2 3
+
+F
−
3.5 × 10−4
HNO
2
+H O ⇌ H O
2 3
+
+ NO
−
2
4.6 × 10−4
HNCO + H O ⇌ H O
2 3
+
+ NCO
−
2 × 10−4
HCO H + H O ⇌ H O
2 2 3
+
+ HCO
−
2
1.8 × 10−4
CH CO H + H O ⇌ H O
3 2 2 3
+
+ CH CO
3
−
2
1.8 × 10−5
HCIO + H O ⇌ H O
2 3
+
+ CIO
−
2.9 × 10−8
HBrO + H O ⇌ H O
2 3
+
+ BrO
−
2.8 × 10−9
HCN + H O ⇌ H O
2 3
+
+ CN
−
4.9 × 10−10
Table 16.6.1 gives the ionization constants for several weak acids; additional ionization constants can be found in Table E1.
At equilibrium, a solution of a weak base in water is a mixture of the nonionized base, the conjugate acid of the weak base, and
hydroxide ion with the nonionized base present in the greatest concentration. Thus, a weak base increases the hydroxide ion
concentration in an aqueous solution (but not as much as the same amount of a strong base).
For example, a solution of the weak base trimethylamine, (CH3)3N, in water reacts according to the equation:
+ −
(CH ) N(aq) + H O(l) ⇌ (CH ) NH (aq) + OH (aq)
3 3 2 3 3
This gives an equilibrium mixture with most of the base present as the nonionized amine. This equilibrium is analogous to that
described for weak acids.
We can confirm by measuring the pH of an aqueous solution of a weak base of known concentration that only a fraction of the base
reacts with water (Figure 14.4.5). The remaining weak base is present as the unreacted form. The equilibrium constant for the
ionization of a weak base, K , is called the ionization constant of the weak base, and is equal to the reaction quotient when the
b
reaction is at equilibrium. For trimethylamine, at equilibrium:

+ −
[ (CH ) NH ][ OH ]
3 3
Kb =
[ (CH ) N]
3 3
Figure 16.6.5 : pH paper indicates that a 0.1-M solution of NH3 (left) is weakly basic. The solution has a pOH of 3 ([OH−] = 0.001
M) because the weak base NH3 only partially reacts with water. A 0.1-M solution of NaOH (right) has a pOH of 1 because NaOH
is a strong base (credit: modification of work by Sahar Atwa).
The ionization constants of several weak bases are given in Table 16.6.2 and Table E2.
Table 16.6.2 : Ionization Constants of Some Weak Bases
Ionization Reaction Kb at 25 °C
(CH ) NH + H O ⇌ (CH ) NH
3 2 2 3 2
+
2
+ OH
−
5.9 × 10−4
CH NH
3 2
+ H O ⇌ CH NH
2 3
+
3
+ OH
−
4.4 × 10−4
(CH ) N + H O ⇌ (CH ) NH
3 3 2 3 3
+
+ OH
−
6.3 × 10−5
NH
3
+ H O ⇌ NH
2
+
4
+ OH
−
1.8 × 10−5
C H NH
6 5 2
+ H O ⇌ C N NH
2 6 5
+
3
+ OH
−
4.3 × 10−10
 Example 16.6.3: Determination of Ka from Equilibrium Concentrations

Acetic acid is the principal ingredient in vinegar; that's why it tastes sour. At equilibrium, a solution contains [CH3CO2H] =
0.0787 M and [H O ] = [CH CO ] = 0.00118 M. What is the value of K for acetic acid?
3
+
3
−
2 a
Vinegar is a solution of acetic acid, a weak acid. (credit: modification of work by “HomeSpot HQ”/Flickr)
Solution
We are asked to calculate an equilibrium constant from equilibrium concentrations. At equilibrium, the value of the equilibrium
constant is equal to the reaction quotient for the reaction:
+ −
CH CO H(aq) + H O(l) ⇌ H O (aq) + CH CO2 (aq)
3 2 2 3 3
+ −
[H O ][ CH CO ]
3 3 2
Ka =
[ CH CO H]
3 2
(0.00118)(0.00118)
=
0.0787
−5
= 1.77 × 10
 Exercise 16.6.3
What is the equilibrium constant for the ionization of the HSO ion, the weak acid used in some household cleansers:
−
− + 2−
HSO 4 (aq) + H O(l) ⇌ H O (aq) + SO 4 (aq)
2 3
In one mixture of NaHSO4 and Na2SO4 at equilibrium, [H 3

O
+
] = 0.027 M; [HSO −
4
] = 0.29 M ; and [SO 2−
4
] = 0.13 M .
Answer
Ka for HSO −
4
= 1.2 × ×10
−2
 Example 16.6.4: Determination of Kb from Equilibrium Concentrations
Caffeine, C8H10N4O2 is a weak base. What is the value of Kb for caffeine if a solution at equilibrium has [C8H10N4O2] = 0.050
M, [C H N O H ] = 5.0 × 10−3 M, and [OH−] = 2.5 × 10−3 M?
8 10 4 2
+
Solution
At equilibrium, the value of the equilibrium constant is equal to the reaction quotient for the reaction:
+ −
C H N O (aq) + H O(l) ⇌ C H N O H (aq) + OH (aq)
8 10 4 2 2 8 10 4 2
so
+ − −3 −3
[C H N O H ][ OH ] (5.0 × 10 )(2.5 × 10 )
8 10 4 2 −4
Kb = = = 2.5 × 10
[C H N O ] 0.050
8 10 4 2
 Exercise 16.6.4
What is the equilibrium constant for the ionization of the HPO 2−
4
ion, a weak base:
2− − −
HPO4 (aq) + H O(l) ⇌ H PO4 (aq) + OH (aq)
2 2
In a solution containing a mixture of NaH 2

PO
4
and Na 2
HPO
4
at equilibrium with:
− −6
[ OH ] = 1.3 × 10 M
[ H PO
2
−
4
]=0 ⋅ 042 M and
[ HPO
2 −
4
]=0 ⋅ 341 M .
Answer
Kb for HPO 2−
4
= 1.6 × 10
−7
 Example 16.6.5: Determination of Ka or Kb from pH

The pH of a 0.0516-M solution of nitrous acid, HNO , is 2.34. What is its K ? 2 a
+ −
HNO (aq) + H O(l) ⇌ H O (aq) + NO (aq)
2 2 3 2
Solution
We determine an equilibrium constant starting with the initial concentrations of HNO2, H O , and NO as well as one of the
3
+ −
final concentrations, the concentration of hydronium ion at equilibrium. (Remember that pH is simply another way to express
the concentration of hydronium ion.)
We can solve this problem with the following steps in which x is a change in concentration of a species in the reaction:
We can summarize the various concentrations and changes as shown here. Because water is the solvent, it has a fixed activity
equal to 1. Any small amount of water produced or used up during the reaction will not change water's role as the solvent, so
the value of its activity remains equal to 1 throughout the reaction.
To get the various values in the ICE (Initial, Change, Equilibrium) table, we first calculate [H O
3
+
, the equilibrium
]
concentration of H O , from the pH:

3
+
+ −2.34
[H O ] = 10 = 0.0046 M
3
The change in concentration of H O , x

3
+
, is the difference between the equilibrium concentration of H3O+, which we
+
[ H3 O ]
determined from the pH, and the initial concentration, [H O ] . The initial concentration of H O is its concentration in pure
3
+
i 3
+
water, which is so much less than the final concentration that we approximate it as zero (~0).
The change in concentration of NO is equal to the change in concentration of [H O ]. For each 1 mol of H O that forms,
−
2 3
+
3
+
1 mol of NO forms. The equilibrium concentration of HNO2 is equal to its initial concentration plus the change in its
−
2
concentration.
Now we can fill in the ICE table with the concentrations at equilibrium, as shown here:
Finally, we calculate the value of the equilibrium constant using the data in the table:
+ −
[H O ][ NO ] (0.0046)(0.0046)
3 2 −4
Ka = = = 4.5 × 10
[ HNO ] (0.0470)
2
 Exercise 16.6.5
The pH of a solution of household ammonia, a 0.950-M solution of NH3, is 11.612. What is Kb for NH3.
Answer
−5
Kb = 1.8 × 10
 Example 16.6.6: Equilibrium Concentrations in a Solution of a Weak Acid
Formic acid, HCO2H, is the irritant that causes the body’s reaction to ant stings.
The pain of an ant’s sting is caused by formic acid. (credit: John Tann)
What is the concentration of hydronium ion and the pH in a 0.534-M solution of formic acid?
+ − −4
HCO H(aq) + H O(l) ⇌ H O (aq) + HCO (aq) Ka = 1.8 × 10
2 2 3 2
Solution
1. Determine x and equilibrium concentrations. The equilibrium expression is:
+ −
HCO H(aq) + H O(l) ⇌ H O (aq) + HCO (aq)
2 2 3 2
Because water is the solvent, it has a fixed activity equal to 1. Any small amount of water produced or used up during the
reaction will not change water's role as the solvent, so the value of its activity remains equal to 1 throughout the reaction so we
do not need to consider it when setting up the ICE table.
The table shows initial concentrations (concentrations before the acid ionizes), changes in concentration, and equilibrium
concentrations follows (the data given in the problem appear in color):
2. Solve for x and the equilibrium concentrations. At equilibrium:

+ −
[H O ][ HCO ]
−4 3 2
Ka = 1.8 × 10 =
[ HCO H]
2
(x)(x)
−4
= = 1.8 × 10
0.534 − x
Now solve for x. Because the initial concentration of acid is reasonably large and K is very small, we assume that a
x << 0.534, which permits us to simplify the denominator term as (0.534 − x) = 0.534. This gives:
2
−4
x
Ka = 1.8 × 10 =
0.534
Solve for x as follows:

2 −4
x = 0.534 × (1.8 × 10 )
−5
= 9.6 × 10
−−−−−−− −
−5
x = √ 9.6 × 10
−3
= 9.8 × 10
To check the assumption that x is small compared to 0.534, we calculate:

−3
x 9.8 × 10
=
0.534 0.534
−2
= 1.8 × 10 (1.8% of 0.534)
x is less than 5% of the initial concentration; the assumption is valid.

We find the equilibrium concentration of hydronium ion in this formic acid solution from its initial concentration and the change in
that concentration as indicated in the last line of the table:
+ −3
[H O ] = 0 + x = 0 + 9.8 × 10 M.
3
−3
= 9.8 × 10 M
The pH of the solution can be found by taking the negative log of the [H 3
O
+
, so:
]
−3
pH = − log(9.8 × 10 ) = 2.01
 Exercise 16.6.6: acetic acid

Only a small fraction of a weak acid ionizes in aqueous solution. What is the percent ionization of acetic acid in a 0.100-M
solution of acetic acid, CH3CO2H?
+ − −5
CH CO H(aq) + H O(l) ⇌ H O (aq) + CH CO (aq) Ka = 1.8 × 10
3 2 2 3 3 2
Hint
Determine [CH 3
−
CO2 ] at equilibrium.) Recall that the percent ionization is the fraction of acetic acid that is ionized × 100,
−
[ CH CO ]
3 2
or × 100 .
[ CH CO H]
3 2 initial
Answer
percent ionization = 1.3%
The following example shows that the concentration of products produced by the ionization of a weak base can be determined by
the same series of steps used with a weak acid.
 Example 16.6.7: Equilibrium Concentrations in a Solution of a Weak Base

Find the concentration of hydroxide ion in a 0.25-M solution of trimethylamine, a weak base:
+ − −5
(CH ) N(aq) + H O(l) ⇌ (CH ) NH (aq) + OH (aq) Kb = 6.3 × 10
3 3 2 3 3
Solution This problem requires that we calculate an equilibrium concentration by determining concentration changes as the
ionization of a base goes to equilibrium. The solution is approached in the same way as that for the ionization of formic acid in
Example 16.6.6. The reactants and products will be different and the numbers will be different, but the logic will be the same:
1. Determine x and equilibrium concentrations. The table shows the changes and concentrations:
2. Solve for x and the equilibrium concentrations. At equilibrium:

+ −
[ (CH ) NH ][ OH ] (x)(x)
3 3 −5
Kb = = 6.3 × 10
[ (CH ) N] 0.25 − x =
3 3
If we assume that x is small relative to 0.25, then we can replace (0.25 − x) in the preceding equation with 0.25. Solving the
simplified equation gives:
−3
x = 4.0 × 10
This change is less than 5% of the initial concentration (0.25), so the assumption is justified.
Recall that, for this computation, x is equal to the equilibrium concentration of hydroxide ion in the solution (see earlier
tabulation):
− −3
([ OH ] = 0 + x = x = 4.0 × 10 M
−3
= 4.0 × 10 M
Then calculate pOH as follows:

−3
pOH = − log(4.3 × 10 ) = 2.40
Using the relation introduced in the previous section of this chapter:
pH + pOH = pKw = 14.00
permits the computation of pH:
pH = 14.00 − pOH = 14.00 − 2.37 = 11.60
Check the work. A check of our arithmetic shows that K b = 6.3 × 10

−5
.
 Exercise 16.6.7
a. Show that the calculation in Step 2 of this example gives an x of 4.3 × 10−3 and the calculation in Step 3 shows Kb = 6.3 ×
10−5.
b. Find the concentration of hydroxide ion in a 0.0325-M solution of ammonia, a weak base with a Kb of 1.76 × 10−5.
+
[ NH ]
Calculate the percent ionization of ammonia, the fraction ionized × 100, or 4
× 100%
[ NH ]
3
Answer a
7.56 × 10
−4
M , 2.33%
Answer b
2.33%
Some weak acids and weak bases ionize to such an extent that the simplifying assumption that x is small relative to the initial
concentration of the acid or base is inappropriate. As we solve for the equilibrium concentrations in such cases, we will see that we
cannot neglect the change in the initial concentration of the acid or base, and we must solve the equilibrium equations by using the
quadratic equation.
 Example 16.6.8: Equilibrium Concentrations in a Solution of a Weak Acid
Sodium bisulfate, NaHSO4, is used in some household cleansers because it contains the HSO
−
4
ion, a weak acid. What is the
pH of a 0.50-M solution of HSO ? −
− + 2− −2
HSO 4 (aq) + H O(l) ⇌ H O (aq) + SO 4 (aq) Ka = 1.2 × 10
2 3
Solution
We need to determine the equilibrium concentration of the hydronium ion that results from the ionization of HSO so that we −
4
can use [H O ] to determine the pH. As in the previous examples, we can approach the solution by the following steps:
3
+
1. Determine x and equilibrium concentrations. This table shows the changes and concentrations:
2. Solve for x and the concentrations.

As we begin solving for x, we will find this is more complicated than in previous examples. As we discuss these complications
we should not lose track of the fact that it is still the purpose of this step to determine the value of x.
At equilibrium:
+ 2−
[H O ][ SO 4 ] (x)(x)
−2 3
Ka = 1.2 × 10 = =
−
[ HSO ] 0.50 − x
4
If we assume that x is small and approximate (0.50 − x) as 0.50, we find:

−2
x = 7.7 × 10
When we check the assumption, we confirm:

x ?
≤ 0.05
−
[HSO ]i
4
which for this system is
−2
x 7.7 × 10
= = 0.15(15%)
0.50 0.50
The value of x is not less than 5% of 0.50, so the assumption is not valid. We need the quadratic formula to find x.
The equation:
(x)(x)
−2
Ka = 1.2 × 10 =
0.50 − x
gives
−3 −2 2+
6.0 × 10 − 1.2 × 10 x =x
or
2+ −2 −3
x + 1.2 × 10 x − 6.0 × 10 =0
This equation can be solved using the quadratic formula. For an equation of the form
2+
ax + bx + c = 0,
x is given by the quadratic equation:

− −−−−− −−
2+
−b ± √ b − 4ac
x =
2a
In this problem, a = 1 , b = 1.2 × 10 −3

, and c = −6.0 × 10 −3
.
Solving for x gives a negative root (which cannot be correct since concentration cannot be negative) and a positive root:
−2
x = 7.2 × 10
Now determine the hydronium ion concentration and the pH:

+ −2
[H O ] = 0 + x = 0 + 7.2 × 10 M
3
−2
= 7.2 × 10 M
The pH of this solution is:

+ −2
pH = −log[ H3 O ] = −log7.2 × 10 = 1.14
 Exercise 16.6.8
a. Show that the quadratic formula gives x = 7.2 × 10 . −2
b. Calculate the pH in a 0.010-M solution of caffeine, a weak base:

+ − −4
C H N O (aq) + H O(l) ⇌ C H N O H (aq) + OH (aq) Kb = 2.5 × 10
8 10 4 2 2 8 10 4 2
Hint
It will be necessary to convert [OH−] to [H 3
O
+
] or pOH to pH toward the end of the calculation.
Answer
pH 11.16
The Relative Strengths of Strong Acids and Bases

Strong acids, such as HCl, HBr , and HI , all exhibit the same strength in water. The water molecule is such a strong base compared
to the conjugate bases Cl−, Br−, and I− that ionization of these strong acids is essentially complete in aqueous solutions. In solvents
less basic than water, we find HCl, HBr , and HI differ markedly in their tendency to give up a proton to the solvent. For example,
when dissolved in ethanol (a weaker base than water), the extent of ionization increases in the order HCl < HBr < HI , and so HI
is demonstrated to be the strongest of these acids. The inability to discern differences in strength among strong acids dissolved in
water is known as the leveling effect of water.
Water also exerts a leveling effect on the strengths of strong bases. For example, the oxide ion, O2−, and the amide ion, NH , are −
2
such strong bases that they react completely with water:

2− − −
O (aq) + H O(l) ⟶ OH (aq) + OH (aq)
2
− −
NH (aq) + H O(l) ⟶ NH (aq) + OH (aq)
2 2 3
Thus, O2− and NH appear to have the same base strength in water; they both give a 100% yield of hydroxide ion.
−
2
In the absence of any leveling effect, the acid strength of binary compounds of hydrogen with nonmetals (A) increases as the H-A
bond strength decreases down a group in the periodic table. For group 17, the order of increasing acidity is
HF < HCl < HBr < HI . Likewise, for group 16, the order of increasing acid strength is H2O < H2S < H2Se < H2Te. Across a
row in the periodic table, the acid strength of binary hydrogen compounds increases with increasing electronegativity of the
nonmetal atom because the polarity of the H-A bond increases. Thus, the order of increasing acidity (for removal of one proton)
across the second row is CH < NH < H O < HF ; across the third row, it is SiH < PH < H S < HCl (see Figure 16.6.6).
4 3 2 4 3 2
Figure 16.6.6 : As you move from left to right and down the periodic table, the acid strength increases. As you move from right to
left and up, the base strength increases.
This diagram has two rows and four columns. Red arrows point left across the bottom of the figure and down at the right side and
are labeled “Increasing acid strength.” Blue arrows point left across the bottom and up at the right side of the figure and are labeled
“Increasing base strength.” The first column is labeled 14 at the top and two white squares are beneath it. The first has the number
6 in the upper left corner and the formula C H subscript 4 in the center along with designation Neither acid nor base. The second
square contains the number 14 in the upper left corner, the formula C H subscript 4 at the center and the designation Neither acid
nor base. The second column is labeled 15 at the top and two blue squares are beneath it. The first has the number 7 in the upper
left corner and the formula N H subscript 3 in the center along with the designation Weak base and K subscript b equals 1.8 times
10 superscript negative 5. The second square contains the number 15 in the upper left corner, the formula P H subscript 3 at the
center and the designation Very weak base and K subscript b equals 4 times 10 superscript negative 28. The third column is labeled
16 at the top and two squares are beneath it. The first is shaded tan and has the number 8 in the upper left corner and the formula H
subscript 2 O in the center along with the designation neutral. The second square is shaded pink, contains the number 16 in the
upper left corner, the formula H subscript 2 S at the center and the designation Weak acid and K subscript a equals 9.5 times 10
superscript negative 8. The fourth column is labeled 17 at the top and two squares are beneath it. The first is shaded pink, has the
number 9 in the upper left corner and the formula H F in the center along with the designation Weak acid and K subscript a equals
6.8 times 10 superscript negative 4. The second square is shaded a deeper pink, contains the number 17 in the upper left corner, the
formula H C l at the center, and the designation Strong acid.
Compounds containing oxygen and one or more hydroxyl (OH) groups can be acidic, basic, or amphoteric, depending on the
position in the periodic table of the central atom E, the atom bonded to the hydroxyl group. Such compounds have the general
formula OnE(OH)m, and include sulfuric acid, O S(OH) , sulfurous acid, OS(OH) , nitric acid, O NOH , perchloric acid,
2 2 2 2
O ClOH, aluminum hydroxide, Al(OH) , calcium hydroxide, Ca(OH) , and potassium hydroxide, KOH :
3 3 2
A diagram is shown that includes a central atom designated with the letter E. Single bonds extend above, below, left, and right of
the E. An O atom is bonded to the right of the E, and an arrow points to the bond labeling it, “Bond a.” An H atom is single bonded
to the right of the O atom. An arrow pointing to this bond connects it to the label, “Bond b.”
If the central atom, E, has a low electronegativity, its attraction for electrons is low. Little tendency exists for the central atom to
form a strong covalent bond with the oxygen atom, and bond a between the element and oxygen is more readily broken than bond b
between oxygen and hydrogen. Hence bond a is ionic, hydroxide ions are released to the solution, and the material behaves as a
base—this is the case with Ca(OH)2 and KOH. Lower electronegativity is characteristic of the more metallic elements; hence, the
metallic elements form ionic hydroxides that are by definition basic compounds.
If, on the other hand, the atom E has a relatively high electronegativity, it strongly attracts the electrons it shares with the oxygen
atom, making bond a relatively strongly covalent. The oxygen-hydrogen bond, bond b, is thereby weakened because electrons are
displaced toward E. Bond b is polar and readily releases hydrogen ions to the solution, so the material behaves as an acid. High
electronegativities are characteristic of the more nonmetallic elements. Thus, nonmetallic elements form covalent compounds
containing acidic −OH groups that are called oxyacids.
Increasing the oxidation number of the central atom E also increases the acidity of an oxyacid because this increases the attraction
of E for the electrons it shares with oxygen and thereby weakens the O-H bond. Sulfuric acid, H2SO4, or O2S(OH)2 (with a sulfur
oxidation number of +6), is more acidic than sulfurous acid, H2SO3, or OS(OH)2 (with a sulfur oxidation number of +4). Likewise
nitric acid, HNO3, or O2NOH (N oxidation number = +5), is more acidic than nitrous acid, HNO2, or ONOH (N oxidation number
= +3). In each of these pairs, the oxidation number of the central atom is larger for the stronger acid (Figure 16.6.7).
Figure 16.6.7 : As the oxidation number of the central atom E increases, the acidity also increases.
A diagram is shown that includes four structural formulas for acids. A red, right pointing arrow is placed beneath the structures
which is labeled “Increasing acid strength.” At the top left, the structure of Nitrous acid is provided. It includes an H atom to which
an O atom with two unshared electron pairs is connected with a single bond to the right. A single bond extends to the right and
slightly below to a N atom with one unshared electron pair. A double bond extends up and to the right from this N atom to an O
atom which has two unshared electron pairs. To the upper right is a structure for Nitric acid. This structure differs from the previous
structure in that the N atom is directly to the right of the first O atom and a second O atom with three unshared electron pairs is
connected with a single bond below and to the right of the N atom which has no unshared electron pairs. At the lower left, an O
atom with two unshared electron pairs is double bonded to its right to an S atom with a single unshared electron pair. An O atom
with two unshared electron pairs is bonded above and an H atom is single bonded to this O atom. To the right of the S atom is a
single bond to another O atom with two unshared electron pairs to which an H atom is single bonded. This structure is labeled
“Sulfurous acid.” A similar structure which is labeled “Sulfuric acid” is placed in the lower right region of the figure. This structure
differs in that an H atom is single bonded to the left of the first O atom, leaving it with two unshared electron pairs and a fourth O
atom with two unshared electron pairs is double bonded beneath the S atom, leaving it with no unshared electron pairs.
Hydroxy compounds of elements with intermediate electronegativities and relatively high oxidation numbers (for example,
elements near the diagonal line separating the metals from the nonmetals in the periodic table) are usually amphoteric. This means
that the hydroxy compounds act as acids when they react with strong bases and as bases when they react with strong acids. The
amphoterism of aluminum hydroxide, which commonly exists as the hydrate Al(H O) (OH) , is reflected in its solubility in both
2 3 3
strong acids and strong bases. In strong bases, the relatively insoluble hydrated aluminum hydroxide, Al(H O) (OH) , is 2 3 3
converted into the soluble ion, [Al(H O) (OH) ] , by reaction with hydroxide ion:
2 2 4
−
− −
[Al (H O) (OH) ](aq) + OH (aq) ⇌ H O(l) + [Al (H O) (OH) ] (aq)
2 3 3 2 2 2 4
In this reaction, a proton is transferred from one of the aluminum-bound H2O molecules to a hydroxide ion in solution. The
Al(H O) (OH)
2 3
compound thus acts as an acid under these conditions. On the other hand, when dissolved in strong acids, it is
3
3+
converted to the soluble ion [Al(H O) ] by reaction with hydronium ion:
2 6
+ 3+
3H O (aq) + Al (H O) (OH) (aq) ⇌ Al (H O) (aq) + 3 H O(l)
3 2 3 3 2 6 2
In this case, protons are transferred from hydronium ions in solution to Al(H 2
O) (OH)
3 3
, and the compound functions as a base.
Summary
The strengths of Brønsted-Lowry acids and bases in aqueous solutions can be determined by their acid or base ionization constants.
Stronger acids form weaker conjugate bases, and weaker acids form stronger conjugate bases. Thus strong acids are completely
ionized in aqueous solution because their conjugate bases are weaker bases than water. Weak acids are only partially ionized
because their conjugate bases are strong enough to compete successfully with water for possession of protons. Strong bases react
with water to quantitatively form hydroxide ions. Weak bases give only small amounts of hydroxide ion. The strengths of the
binary acids increase from left to right across a period of the periodic table (CH4 < NH3 < H2O < HF), and they increase down a
group (HF < HCl < HBr < HI). The strengths of oxyacids that contain the same central element increase as the oxidation number of
the element increases (H2SO3 < H2SO4). The strengths of oxyacids also increase as the electronegativity of the central element
increases [H2SeO4 < H2SO4].
Key Equations
+ −
[H O ][ A ]
3
Ka =
[HA]
+ −
[ HB ][ OH ]
Kb =
[B]
−14
Ka × Kb = 1.0 × 10 = Kw (at room temperature)
+
[H O ]
3 eq
Percent ionization = × 100
[HA]
0
Glossary
acid ionization constant (Ka)
equilibrium constant for the ionization of a weak acid
base ionization constant (Kb)

equilibrium constant for the ionization of a weak base
leveling effect of water

any acid stronger than H O , or any base stronger than OH− will react with water to form H O , or OH−, respectively; water
3
+
3
+
acts as a base to make all strong acids appear equally strong, and it acts as an acid to make all strong bases appear equally
strong
oxyacid
compound containing a nonmetal and one or more hydroxyl groups
percent ionization
ratio of the concentration of the ionized acid to the initial acid concentration, times 100
16.6: Weak Acids is shared under a CC BY-NC-SA 3.0 license and was authored, remixed, and/or curated by LibreTexts.
14.3: Relative Strengths of Acids and Bases by OpenStax is licensed CC BY 4.0. Original source:
https://openstax.org/details/books/chemistry-2e.
16.7: Weak Bases
The pH of a solution of a weak base can be calculated in a way which is very similar to that used for a weak acid. Instead of an acid
constant Ka, a base constant Kb must be used. If a weak base B accepts protons from water according to the equation
+ −
B + H 2 O ⇌ BH + OH (16.7.1)
then the base constant is defined by the expression

+ −
BH OH
Kb = (16.7.2)
B
A list of Kb values for selected bases arranged in order of strength is given in the table below. This table is part of our larger
collection of acid-base resources.
Table 16.7.1 : The Base Constants for Some Bases at 25°C. Taken from Hogfelt, E. Perrin, D. D. Stability Constants of Metal Ion Complexes,
1st ed. Oxford; New Pergamon, 1979-1982. International Union of Pure and Applied Chemistry, Commission on Equilibrium. ISBN:
0080209580
Base Formula and Ionization Equation Kb Molecular Shape
Ammonia N H3 + H2 O ⇌ N H
+
4
+ OH
–
1.77 × 10–5
Aniline C6 H5 N H2 + H2 O ⇌ C6 H5 N H
+
3
+ OH
–
3.9 × 10–10
Carbonate ion CO
2–
3
+ H2 O ⇌ HC O
−
3
+ OH
–
2.1 × 10–4
K1 = 1.2 × 10–6
+ –
N2 H4 + H2 O ⇌ N2 H + OH
Hydrazine 5
N2 H
+
5
+ H2 O ⇌ N2 H
6
2+
+ OH
–
K2 = 1.3 × 10–15
Hydride ion H
–
+ H2 O → H2 + O H
–
1.0
Phosphate ion PO
3–
4
+ H2 O ⇌ HP O
2−
4
+ OH
–
5.9 × 10–3
Base Formula and Ionization Equation Kb Molecular Shape
Pyridine C5 H5 N + H2 O ⇌ C5 H5 N H
+
+ OH
–
1.6 × 10–9
To find the pH we follow the same general procedure as in the case of a weak acid. If the stoichiometric concentration of the base is
indicated by cb, the result is entirely analogous to equation 4 in the section on the pH of weak acids; namely,
− 2
[OH ]
Kb = (16.7.3)
−
cb − [ OH ]
Under most circumstances we can make the approximation

–
cb – [OH ] ≈ cb
in which case Equation 16.7.3 reduces to the approximation

–
−−−−
[OH ] ≈ √Kb cb (16.7.4)
which is identical to the expression obtained in the acid case (approximation shown in equation 6 in the section on the pH of weak
acids) except that OH– replaces H3O+ and b replaces a. Once we have found the hydroxide-ion concentration from this
approximation, we can then easily find the pOH, and from it the pH.
 Example 16.7.1: pH using Kb
Using the value for Kb listed in the table, find the pH of 0.100 M NH3.
Solution
It is not a bad idea to guess an approximate pH before embarking on the calculation. Since we have a dilute solution of a weak
base, we expect the solution to be only mildly basic. A pH of 13 or 14 would be too basic, while a pH of 8 or 9 is too close to
neutral. A pH of 10 or 11 seems reasonable. Using Equation 16.7.4 we have
− −−−−
[ OH ] = √Kb cb
−−−−−−−−−−−−−−−−−−−−−−−−−−−− −
−5 −1 −1
= √ 1.8 × 10 mol L × 0.100 mol L
− −−−−−−−−−−−−−−− −
−6 2 −2
= √ 1.8 × 10 mol L
−3 −1
= 1.34 × 10 mol L
Checking the accuracy of the approximation, we find

− −3
[ OH ] 1.34 × 10
= ≈ 1 percent
cb 0.1
The approximation is valid, and we thus proceed to find the pOH.

−
[ OH ]
−3
pOH = −log = −log(1.34 × 10 ) = 2.87
−1
mol L
From which
pH = 14.00– pOH = 14.00– 2.87 = 11.13
This calculated value checks well with our initial guess.

Occasionally we will find that the approximation
–
cb – [OH ] ≈ cb
is not valid, in which case we must use a series of successive approximations similar to that outlined above for acids. The
appropriate formula can be derived from Equation 16.7.3 and reads
−−−−−−−−−−−−−
− −
[OH ] ≈ √ Kb (cb − [OH ])
16.7: Weak Bases is shared under a CC BY-NC-SA 3.0 license and was authored, remixed, and/or curated by LibreTexts.
14.5: The pH of Solutions of Weak Bases by Ed Vitz, John W. Moore, Justin Shorb, Xavier Prat-Resina, Tim Wendorff, & Adam Hahn is
licensed CC BY-NC-SA 4.0.
16.8: Relationship Between Ka and Kb
Learning Objectives
To know the relationship between acid or base strength and the magnitude of K , K , pK , and pK . a b a b
The magnitude of the equilibrium constant for an ionization reaction can be used to determine the relative strengths of acids and
bases. For example, the general equation for the ionization of a weak acid in water, where HA is the parent acid and A− is its
conjugate base, is as follows:
+ −
H A(aq) + H2 O(l) ⇌ H3 O +A (16.8.1)
(aq) (aq)
The equilibrium constant for this dissociation is as follows:

+ −
[ H3 O ][ A ]
K = (16.8.2)
[H A]
The equilibrium constant for this reaction is the acid ionization constant K , also called the acid dissociation constant:
a
+ −
[ H3 O ][ A ]
Ka = (16.8.3)
[H A]
Thus the numerical values of K and K differ by the concentration of water (55.3 M). Again, for simplicity, H O can be written
a 3
+
as H in Equation 16.8.3. Keep in mind, though, that free H does not exist in aqueous solutions and that a proton is transferred
+ +
to H O in all acid ionization reactions to form H O . The larger the K , the stronger the acid and the higher the H
2
3 +
a
+
concentration at equilibrium. Like all equilibrium constants, acid–base ionization constants are actually measured in terms of the
activities of H or OH , thus making them unitless. The values of K for a number of common acids are given in Table 16.8.1.
+ −
a
Table 16.8.1 : Values of K , pK , K , and pK for Selected Acids (H A and Their Conjugate Bases (A )
a a b b
−
Acid HA Ka pKa A
−
Kb pKb
hydroiodic acid HI 2 × 10
9
−9.3 I
−
5.5 × 10
−24
23.26
sulfuric acid (1)* H2 S O4 1 × 10

2
−2.0 HSO
−
4
1 × 10
−16
16.0
nitric acid HN O3 2.3 × 10

1
−1.37 NO
−
3
4.3 × 10
−16
15.37
hydronium ion H3 O
+
1.0 0.00 H2 O 1.0 × 10
−14
14.00
sulfuric acid (2)* HSO

−
4
1.0 × 10
−2
1.99 SO
2−
4
9.8 × 10
−13
12.01
hydrofluoric acid HF 6.3 × 10

−4
3.20 F
−
1.6 × 10
−11
10.80
nitrous acid HN O2 5.6 × 10

−4
3.25 N O2
−
1.8 × 10
−11
10.75
formic acid HC O2 H 1.78 × 10

−4
3.750 HC O2 − 5.6 × 10
−11
10.25
benzoic acid C6 H5 C O2 H 6.3 × 10

−5
4.20 C6 H5 C O
−
2
1.6 × 10
−10
9.80
acetic acid C H3 C O2 H 1.7 × 10

−5
4.76 C H3 C O
−
2
5.8 × 10
−10
9.24
pyridinium ion C5 H5 N H
+
5.9 × 10
−6
5.23 C5 H5 N 1.7 × 10
−9
8.77
hypochlorous acid HOCl 4.0 × 10

−8
7.40 OCl
−
2.5 × 10
−7
6.60
hydrocyanic acid HCN 6.2 × 10

−10
9.21 CN
−
1.6 × 10
−5
4.79
ammonium ion NH
4
+
5.6 × 10
−10
9.25 N H3 1.8 × 10
−5
4.75
water H2 O 1.0 × 10
−14
14.00 OH
−
1.00 0.00
acetylene C2 H2 1 × 10
−26
26.0 HC
−
2
1 × 10
12
−12.0
ammonia N H3 1 × 10
−35
35.0 NH
2
−
1 × 10
21
−21.0
Weak bases react with water to produce the hydroxide ion, as shown in the following general equation, where B is the parent base
and BH+ is its conjugate acid:
+ −
B(aq) + H2 O(l) ⇌ BH + OH (16.8.4)
(aq) (aq)
The equilibrium constant for this reaction is the base ionization constant (Kb), also called the base dissociation constant:
+ −
[BH ][OH ]
Kb = (16.8.5)
[B]
Once again, the concentration does not appear in the equilibrium constant expression.. The larger the K , the stronger the base and b
the higher the OH concentration at equilibrium. The values of K for a number of common weak bases are given in Table
−
b
16.8.2.
Table 16.8.2 : Values of K , pK , K , and pK for Selected Weak Bases (B) and Their Conjugate Acids (BH+)
b b a a
Base B Kb pKb BH
+
Ka pKa
hydroxide ion OH
−
1.0 0.00* H2 O 1.0 × 10
−14
14.00
phosphate ion PO
3−
4
2.1 × 10
−2
1.68 HP O
2−
4
4.8 × 10
−13
12.32
dimethylamine (C H3 )2 N H 5.4 × 10
−4
3.27 (C H3 )2 N H
+
2
1.9 × 10
−11
10.73
methylamine C H3 N H2 4.6 × 10
−4
3.34 C H3 N H
3
+
2.2 × 10
−11
10.66
trimethylamine (C H3 )3 N 6.3 × 10
−5
4.20 (C H3 )3 N H
+
1.6 × 10
−10
9.80
ammonia N H3 1.8 × 10
−5
4.75 NH
4
+
5.6 × 10
−10
9.25
pyridine C5 H5 N 1.7 × 10
−9
8.77 C5 H5 N H
+
5.9 × 10
−6
5.23
aniline C6 H5 N H2 7.4 × 10
−10
9.13 C6 H5 N H
+
3
1.3 × 10
−5
4.87
water H2 O 1.0 × 10
−14
14.00 H3 O
+
1.0
∗
0.00
*As in Table 16.8.1.
There is a simple relationship between the magnitude of K for an acid and K for its conjugate base. Consider, for example, the
a b
ionization of hydrocyanic acid (H C N ) in water to produce an acidic solution, and the reaction of C N with water to produce a −
basic solution:
+ −
H C N(aq) ⇌ H + CN (16.8.6)
(aq) (aq)
− −
CN + H2 O(l) ⇌ OH + H C N(aq) (16.8.7)
(aq) (aq)
The equilibrium constant expression for the ionization of HCN is as follows:

+ −
[H ][C N ]
Ka = (16.8.8)
[H C N ]
The corresponding expression for the reaction of cyanide with water is as follows:
−
[OH ][H C N ]
Kb = (16.8.9)
−
[C N ]
If we add Equations 16.8.6 and 16.8.7, we obtain the following (recall that the equilibrium constant for the sum of two reactions is
the product of the equilibrium constants for the individual reactions):
+ − + −
H C N(aq) ⇌ H + CN Ka = [ H ] [C N ] / [H C N ] (16.8.10)
(aq) (aq)
− − − −
CN + H2 O(l) ⇌ OH + H C N(aq) Kb = [OH ] [H C N ] / [C N ] (16.8.11)
(aq) (aq)
+ − + −
H2 O(l) ⇌ H + OH K = Ka × Kb = [ H ][OH ] (16.8.12)
(aq) (aq)
In this case, the sum of the reactions described by K and K is the equation for the autoionization of water, and the product of the
a b
two equilibrium constants is K : w
Ka Kb = Kw (16.8.13)
Thus if we know either K for an acid or

a Kb for its conjugate base, we can calculate the other equilibrium constant for any
conjugate acid–base pair.
Just as with pH, pOH , and pKw, we can use negative logarithms to avoid exponential notation in writing acid and base ionization
constants, by defining pK as follows:
a
pKa = − log10 Ka (16.8.14)
−pKa
Ka = 10 (16.8.15)
and pK as
b
p Kb = − log Kb (16.8.16)
10
−pKb
Kb = 10 (16.8.17)
Similarly, Equation 16.5.10, which expresses the relationship between K and K , can be written in logarithmic form as follows:
a b
p Ka + p Kb = p Kw (16.8.18)
At 25°C, this becomes

p Ka + p Kb = 14.00 (16.8.19)
The values of pK and pK are given for several common acids and bases in Table 16.5.1 and Table 16.5.2, respectively, and a
a b
more extensive set of data is provided in Tables E1 and E2. Because of the use of negative logarithms, smaller values of pK a
correspond to larger acid ionization constants and hence stronger acids. For example, nitrous acid (H N O ), with a pK of 3.25, is
2 a
about a 1000 times stronger acid than hydrocyanic acid (HCN), with a pK of 9.21. Conversely, smaller values of pK correspond
a b
to larger base ionization constants and hence stronger bases.

The relative strengths of some common acids and their conjugate bases are shown graphically in Figure 16.5. The conjugate acid–
base pairs are listed in order (from top to bottom) of increasing acid strength, which corresponds to decreasing values of pK . This a
order corresponds to decreasing strength of the conjugate base or increasing values of pK . At the bottom left of Figure 16.5.2 are
b
the common strong acids; at the top right are the most common strong bases. Notice the inverse relationship between the
strength of the parent acid and the strength of the conjugate base. Thus the conjugate base of a strong acid is a very weak
base, and the conjugate base of a very weak acid is a strong base.
The conjugate base of a strong acid is a weak base and vice versa.
We can use the relative strengths of acids and bases to predict the direction of an acid–base reaction by following a single rule: an
acid–base equilibrium always favors the side with the weaker acid and base, as indicated by these arrows:
stronger acid + stronger base−⇀

↽ weaker acid + weaker base (16.8.20)
In an acid–base reaction, the proton always reacts with the stronger base.
For example, hydrochloric acid is a strong acid that ionizes essentially completely in dilute aqueous solution to produce H O and 3
+
C l ; only negligible amounts of H C l molecules remain undissociated. Hence the ionization equilibrium lies virtually all the way
−
to the right, as represented by a single arrow:

+ −
H C l(aq) + H2 O(l) →→ H3 O + Cl (16.8.21)
(aq) (aq)
In contrast, acetic acid is a weak acid, and water is a weak base. Consequently, aqueous solutions of acetic acid contain mostly
acetic acid molecules in equilibrium with a small concentration of H O and acetate ions, and the ionization equilibrium lies far to
3
+
the left, as represented by these arrows:

⇀ + −
CH CO H +H O ↽− H O + CH CO (16.8.22)
3 2 (aq) 2 (l) 3 (aq) 3 2 (aq)
Similarly, in the reaction of ammonia with water, the hydroxide ion is a strong base, and ammonia is a weak base, whereas the
ammonium ion is a stronger acid than water. Hence this equilibrium also lies to the left:
⇀ + −
H2 O(l) + N H3(aq) ↽− NH + OH (16.8.23)
4(aq) (aq)
All acid–base equilibria favor the side with the weaker acid and base. Thus the proton is bound to the stronger base.
Example 16.8.1 : Butyrate and Dimethylammonium Ions

a. Calculate K and pK of the butyrate ion (C H C H C H C O ). The pK of butyric acid at 25°C is 4.83. Butyric acid is
b b 3 2 2
−
2 a
responsible for the foul smell of rancid butter.

b. Calculate K and pK of the dimethylammonium ion ((C H ) N H ). The base ionization constant K of dimethylamine
a a 3 2
+
2 b
((C H ) N H) is 5.4 × 10 at 25°C.

3 2
−4
Given: pK and K
a b
Asked for: corresponding K and pK , K and pK b b a a
Strategy:
The constants K and K are related as shown in Equation 16.5.10. The pK and pK for an acid and its conjugate base are
a b a b
related as shown in Equation 16.5.15 and Equation 16.5.16. Use the relationships pK = −log K and K = 10−pK (Equation
16.5.11 and Equation 16.5.13) to convert between K and pK or K and pK . a a b b
Solution:
We are given the pK for butyric acid and asked to calculate the K and the pK for its conjugate base, the butyrate ion.
a b b
Because the pK value cited is for a temperature of 25°C, we can use Equation 16.5.16: pK + pK = pKw = 14.00.
a a b
Substituting the pK and solving for the pK ,

a b
4.83 + p Kb = 14.00 (16.8.24)
p Kb = 14.00 − 4.83 = 9.17 (16.8.25)
Because pK b = − log Kb , K is 10
b
−9.17
= 6.8 × 10
−10
.
In this case, we are given K for a base (dimethylamine) and asked to calculate K and pK for its conjugate acid, the
b a a
dimethylammonium ion. Because the initial quantity given is K rather than pK , we can use Equation 16.5.10: K K = K .
b b a b w
Substituting the values of K and K at 25°C and solving for K ,

b w a
−4 −14
Ka (5.4 × 10 ) = 1.01 × 10 (16.8.26)
−11
Ka = 1.9 × 10 (16.8.27)
Because pK = −loga Ka , we have p Ka = − log(1.9 × 10

−11
) = 10.72 . We could also have converted Kb to pKb to obtain
the same answer:
−4
p Kb = − log(5.4 × 10 ) = 3.27 (16.8.28)
pKa + p Kb = 14.00 (16.8.29)
p Ka = 10.73 (16.8.30)
−pKa −10.73 −11

Ka = 10 = 10 = 1.9 × 10 (16.8.31)
If we are given any one of these four quantities for an acid or a base (K , pK , K , or pK ), we can calculate the other three.
a a b b
Exercise 16.8.1 : Lactic Acid

Lactic acid (C H C H (OH )C O H) is responsible for the pungent taste and smell of sour milk; it is also thought to produce
3 2
soreness in fatigued muscles. Its pK is 3.86 at 25°C. Calculate K for lactic acid and pK and K for the lactate ion.
a a b b
Answer
Ka = 1.4 × 10
−4
for lactic acid;
pKb = 10.14 and K b = 7.2 × 10
−11
for the lactate ion
Summary
Two species that differ by only a proton constitute a conjugate acid–base pair. The magnitude of the equilibrium constant for an
ionization reaction can be used to determine the relative strengths of acids and bases. For an aqueous solution of a weak acid, the
dissociation constant is called the acid ionization constant (Ka). Similarly, the equilibrium constant for the reaction of a weak base
with water is the base ionization constant (Kb). For any conjugate acid–base pair, K K = K . Smaller values of pK correspond
a b w a
to larger acid ionization constants and hence stronger acids. Conversely, smaller values of pK correspond to larger base ionization
b
constants and hence stronger bases. At 25°C, pK + pK = 14.00 . Acid–base reactions always proceed in the direction that
a b
produces the weaker acid–base pair.
Key Takeaways
The Ka and Kb values for a conjugated acid–base pairs are related through the Kw value:
Ka Kb = Kw (16.8.32)
The conjugate base of a strong acid is a very weak base, and the conjugate base of a very weak acid is a strong base.
Key Equations
Acid ionization constant:
+ −
[ H3 O ][ A ]
Ka = (16.8.33)
[H A]
Base ionization constant:

+ −
[BH ][OH ]
Kb = (16.8.34)
[B]
Relationship between K and K of a conjugate acid–base pair:

a b
Ka Kb = Kw (16.8.35)
Definition of pK :a
pKa = − log10 Ka
−pKa
Ka = 10 (16.8.36)
Definition of pK :b
p Kb = − log10 Kb
−pKb
Kb = 10 (16.8.37)
Relationship between pK and pK of a conjugate acid–base pair:

a b
p Ka + p Kb = p Kw (16.8.38)
p Ka + p Kb = 14.00 at 25°C (16.8.39)

Stephen Lower, Professor Emeritus (Simon Fraser U.) Chem1 Virtual Textbook
16.8: Relationship Between Ka and Kb is shared under a CC BY-NC-SA 3.0 license and was authored, remixed, and/or curated by LibreTexts.
16.9: Acid-Base Properties of Salt Solutions
To recognize salts that will produce acidic, basic, or neutral solutions in water
To understand the Lewis acidity of small, highly-charged metal ions in water
A neutralization reaction can be defined as the reaction of an acid and a base to produce a salt and water. That is, another cation,
such as N a , replaces the proton on the acid. An example is the reaction of C H C O H, a weak acid, with N aOH , a strong base:
+
3 2
H2 O
C H3 C O2 H(l) + N aOH(s) ⟶ H2 OC H3 C O2 N a(aq) + H2 O(l)
acid base salt water
Depending on the acid–base properties of its component ions, however, a salt can dissolve in water to produce a neutral solution, a
basic solution, or an acidic solution.
When a salt such as N aC l dissolves in water, it produces Na
+
(aq)
and C l −
(aq)
ions. Using a Lewis approach, the Na
+
ion can be
viewed as an acid because it is an electron pair acceptor, although its low charge and relatively large radius make it a very weak
acid. The C l ion is the conjugate base of the strong acid H C l, so it has essentially no basic character. Consequently, dissolving
−
N aC l in water has no effect on the pH of a solution, and the solution remains neutral.
Now let's compare this behavior to the behavior of aqueous solutions of potassium cyanide and sodium acetate. Again, the cations (
K
+
and N a ) have essentially no acidic character, but the anions (C N and C H C O ) are weak bases that can react with water
+ −
3
−
because they are the conjugate bases of the weak acids H C N and acetic acid, respectively.
− ⇀ −
CN + H2 O(l) ↽− H C N(aq) + OH
(aq) (aq)
2 ⇀ −
C H3 C O + H2 O(l) ↽− C H3 C O2 H(aq) + OH
2(aq) (aq)
Neither reaction proceeds very far to the right as written because the formation of the weaker acid–base pair is favored. Both
H C N and acetic acid are stronger acids than water, and hydroxide is a stronger base than either acetate or cyanide, so in both
cases, the equilibrium lies to the left. Nonetheless, each of these reactions generates enough hydroxide ions to produce a basic
solution. For example, the pH of a 0.1 M solution of sodium acetate or potassium cyanide at 25°C is 8.8 or 11.1, respectively.
From Table 16.9.1 and Figure 16.9.1, we can see that C N is a stronger base (pK = 4.79) than acetate (pK = 9.24), which is
−
b b
consistent with KC N producing a more basic solution than sodium acetate at the same concentration.
In contrast, the conjugate acid of a weak base should be a weak acid (Equation 16.9.1). For example, ammonium chloride and
pyridinium chloride are salts produced by reacting ammonia and pyridine, respectively, with H C l. As you already know, the
chloride ion is such a weak base that it does not react with water. In contrast, the cations of the two salts are weak acids that react
with water as follows:
+ ⇀ +
NH + H2 O(l) ↽− H H3(aq) + H3 O (16.9.1)
4(aq) (aq)
+ ⇀ +
C5 H5 N H + H2 O(l) ↽− C5 H5 N H(aq) + H3 O (16.9.2)
(aq) (aq)
Equation 16.9.1 indicates that H O is a stronger acid than either N H or C H N H , and conversely, ammonia and pyridine
3
+ +
4 5 5
+
are both stronger bases than water. The equilibrium will therefore lie far to the left in both cases, favoring the weaker acid–base
pair. The H O concentration produced by the reactions is great enough, however, to decrease the pH of the solution significantly:
3
+
the pH of a 0.10 M solution of ammonium chloride or pyridinium chloride at 25°C is 5.13 or 3.12, respectively. This is consistent
with the information shown in Figure 16.2, indicating that the pyridinium ion is more acidic than the ammonium ion.
What happens with aqueous solutions of a salt such as ammonium acetate, where both the cation and the anion can react separately
with water to produce an acid and a base, respectively? According to Figure 16.10, the ammonium ion will lower the pH, while
according to Equation 16.9.2, the acetate ion will raise the pH. This particular case is unusual, in that the cation is as strong an acid
as the anion is a base (pKa ≈ pKb). Consequently, the two effects cancel, and the solution remains neutral. With salts in which the
cation is a stronger acid than the anion is a base, the final solution has a pH < 7.00. Conversely, if the cation is a weaker acid than
the anion is a base, the final solution has a pH > 7.00.
Solutions of simple salts of metal ions can also be acidic, even though a metal ion cannot donate a proton directly to water to
produce H O . Instead, a metal ion can act as a Lewis acid and interact with water, a Lewis base, by coordinating to a lone pair of
3
+
electrons on the oxygen atom to form a hydrated metal ion (part (a) in Figure 16.9.1). A water molecule coordinated to a metal ion
is more acidic than a free water molecule for two reasons. First, repulsive electrostatic interactions between the positively charged
metal ion and the partially positively charged hydrogen atoms of the coordinated water molecule make it easier for the coordinated
water to lose a proton.
Figure 16.9.1 . With less electron density between the O atoms and the H atoms, the O– H bonds are weaker than in a free H2 O
molecule, making it easier to lose a H ion.

+
Figure 16.9.1 : Effect of a Metal Ion on the Acidity of Water (a) Reaction of the metal ion Al with water to form the hydrated
3+
metal ion is an example of a Lewis acid–base reaction. (b) The positive charge on the aluminum ion attracts electron density from
the oxygen atoms, which shifts electron density away from the O–H bonds. The decrease in electron density weakens the O–H
bonds in the water molecules and makes it easier for them to lose a proton.
On the left is the reaction of Al three plus with six OH2 which produces [AL(H2O)6] three plus. On the right is the molecular
structure of [Al(H2O)6] three plus.
The magnitude of this effect depends on the following two factors (Figure 16.9.2):
1. The charge on the metal ion. A divalent ion (M ) has approximately twice as strong an effect on the electron density in a
2+
coordinated water molecule as a monovalent ion (M ) of the same radius.

+
2. The radius of the metal ion. For metal ions with the same charge, the smaller the ion, the shorter the internuclear distance to the
oxygen atom of the water molecule and the greater the effect of the metal on the electron density distribution in the water
molecule.
Figure 16.9.2 : The Effect of the Charge and Radius of a Metal Ion on the Acidity of a Coordinated Water Molecule. The contours
show the electron density on the O atoms and the H atoms in both a free water molecule (left) and water molecules coordinated to
Na , Mg , and Al ions. These contour maps demonstrate that the smallest, most highly charged metal ion (Al ) causes the
+ 2+ 3+ 3+
greatest decrease in electron density of the O–H bonds of the water molecule. Due to this effect, the acidity of hydrated metal ions
increases as the charge on the metal ion increases and its radius decreases.
Thus aqueous solutions of small, highly charged metal ions, such as Al 3+
and F e , are acidic:
3+
3+ 2+ +
[Al(H2 O)6 ] ⇌ [Al(H2 O)5 (OH )] +H (16.9.3)
(aq) (aq) (aq)
The [Al(H O) ] ion has a pK of 5.0, making it almost as strong an acid as acetic acid. Because of the two factors described
2 6
3+
a
previously, the most important parameter for predicting the effect of a metal ion on the acidity of coordinated water molecules is
the charge-to-radius ratio of the metal ion. A number of pairs of metal ions that lie on a diagonal line in the periodic table, such as
Li
+
and M g or C a and Y , have different sizes and charges, but similar charge-to-radius ratios. As a result, these pairs of
2+ 2+ 3+
metal ions have similar effects on the acidity of coordinated water molecules, and they often exhibit other significant similarities in
chemistry as well.
Solutions of small, highly charged metal ions in water are acidic.

Reactions such as those discussed in this section, in which a salt reacts with water to give an acidic or basic solution, are often
called hydrolysis reactions. Using a separate name for this type of reaction is unfortunate because it suggests that they are somehow
different. In fact, hydrolysis reactions are just acid–base reactions in which the acid is a cation or the base is an anion; they obey the
same principles and rules as all other acid–base reactions.
A hydrolysis reaction is an acid–base reaction.
 Example 16.9.1
Predict whether aqueous solutions of these compounds are acidic, basic, or neutral.
a. KNO 3
b. CrBr cdotH
3 2
O
c. Na SO
2 4
Given: compound
Asked for: acidity or basicity of aqueous solution
Strategy:
A. Assess the acid–base properties of the cation and the anion. If the cation is a weak Lewis acid, it will not affect the pH of
the solution. If the cation is the conjugate acid of a weak base or a relatively highly charged metal cation, however, it will
react with water to produce an acidic solution.
B. f the anion is the conjugate base of a strong acid, it will not affect the pH of the solution. If, however, the anion is the
conjugate base of a weak acid, the solution will be basic.
Solution:
a
A. The K cation has a small positive charge (+1) and a relatively large radius (because it is in the fourth row of the periodic
+
table), so it is a very weak Lewis acid.

B. The N O − anion is the conjugate base of a strong acid, so it has essentially no basic character (Table 16.1). Hence neither
3
the cation nor the anion will react with water to produce H or OH , and the solution will be neutral.
+ −
b.
A. The C r ion is a relatively highly charged metal cation that should behave similarly to the Al
3+ 3+
ion and form the
[C r(H 2O) ] complex, which will behave as a weak acid:
6
3+
3+ −⇀ 2+ +
C r(H2 O)6 ] ↽ C r(H2 O)5 (OH )] +H
(aq) (aq) (aq)
B. The Br anion is a very weak base (it is the conjugate base of the strong acid H Br), so it does not affect the pH of the
−
solution. Hence the solution will be acidic.

c.
A. The N a ion, like the K , is a very weak acid, so it should not affect the acidity of the solution.
+ +
B. In contrast, SO is the conjugate base of H SO , which is a weak acid. Hence the SO
2−
4
−
4
2−
4
ion will react with water as
shown in Figure 16.6 to give a slightly basic solution.
 Exercise 16.9.1
Predict whether aqueous solutions of the following are acidic, basic, or neutral.
a. KI
b. M g(C lO 4 )2
c. N aH S
Answer a
neutral
Answer b
acidic
Answer c
basic (due to the reaction of HS with water to form H
−
2
S and OH )
−
Summary
A salt can dissolve in water to produce a neutral, a basic, or an acidic solution, depending on whether it contains the conjugate base
of a weak acid as the anion (A ), the conjugate acid of a weak base as the cation (BH ), or both. Salts that contain small, highly
− +
charged metal ions produce acidic solutions in water. The reaction of a salt with water to produce an acidic or a basic solution is
called a hydrolysis reaction.
Key Takeaways
Acid–base reactions always contain two conjugate acid–base pairs.
Each acid and each base has an associated ionization constant that corresponds to its acid or base strength.
16.9: Acid-Base Properties of Salt Solutions is shared under a CC BY-NC-SA 3.0 license and was authored, remixed, and/or curated by
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16.10: Acid-Base Behavior and Chemical Structure
To understand how molecular structure affects the strength of an acid or base.
We have seen that the strengths of acids and bases vary over many orders of magnitude. In this section, we explore some of the
structural and electronic factors that control the acidity or basicity of a molecule.
Bond Strengths
In general, the stronger the A– H or B– H bond, the less likely the bond is to break to form H
+ +
ions and thus the less acidic the
substance. This effect can be illustrated using the hydrogen halides:
Relative Acid Strength HF HCl HBr HI
H–X Bond Energy

570 432 366 298
(kJ/mol)
pKa 3.20 −6.1 −8.9 −9.3
The trend in bond energies is due to a steady decrease in overlap between the 1s orbital of hydrogen and the valence orbital of the
halogen atom as the size of the halogen increases. The larger the atom to which H is bonded, the weaker the bond. Thus the bond
between H and a large atom in a given family, such as I or Te, is weaker than the bond between H and a smaller atom in the same
family, such as F or O. As a result, acid strengths of binary hydrides increase as we go down a column of the periodic table. For
example, the order of acidity for the binary hydrides of Group 16 elements is as follows, with pK values in parentheses:
a
H2 O(14.00 = p Kw ) < H2 S(7.05) < H2 Se(3.89) < H2 T e(2.6) (16.10.1)
Stability of the Conjugate Base

Whether we write an acid–base reaction as AH ⇌ A + H or as BH ⇌ B + H , the conjugate base (A or B ) contains
− + + + −
one more lone pair of electrons than the parent acid (AH or BH ). Any factor that stabilizes the lone pair on the conjugate base
+
favors dissociation of H and makes the parent acid a stronger acid. Let’s see how this explains the relative acidity of the binary
+
hydrides of the elements in the second row of the periodic table. The observed order of increasing acidity is the following, with
pKa values in parentheses:
C H4 ( 50) ≪ N H3 ( 36) < H2 O(14.00) < H F (3.20) (16.10.2)
Consider, for example, the compounds at both ends of this series: methane and hydrogen fluoride. The conjugate base of C H is 4
C H , and the conjugate base of H F is F . Because fluorine is much more electronegative than carbon, fluorine can better
− −
3
stabilize the negative charge in the F ion than carbon can stabilize the negative charge in the CH3− ion. Consequently, HF has a
−
greater tendency to dissociate to form H and F than does methane to form H and C H , making HF a much stronger acid
+ − + −
than C H . 4
The same trend is predicted by analyzing the properties of the conjugate acids. For a series of compounds of the general formula
H E , as the electronegativity of E increases, the E–H bond becomes more polar, favoring dissociation to form E and H . Due to− +
both the increasing stability of the conjugate base and the increasing polarization of the E–H bond in the conjugate acid, acid
strengths of binary hydrides increase as we go from left to right across a row of the periodic table.
Acid strengths of binary hydrides increase as we go down a column or from left to right across a row of the periodic table.
 the strongest acid Known: The hydrohelium Cation

The stornger acid, the weaker the covalent bond to a hydrogen atom. So the strongest acid possible is the molecule with the
weakest bond. That is the hydrohelium (1+) cation, HeH , which is a positively charged ion formed by the reaction of a proton
+
with a helium atom in the gas phase. It was first produced in the laboratory in 1925 and is isoelectronic with molecular
hydrogen (\ce{H2}}). It is the strongest known acid, with a proton affinity of 177.8 kJ/mol.
Ball and stick model of the hydrohelium ion. (CC BY-SA 3.0; CCoil).
HeH
+
cannot be prepared in a condensed phase, as it would protonate any anion, molecule or atom with which it were
associated. However it is possible to estimate a hypothetical aqueous acidity using Hess's law:
HHe+(g) → H+(g) + He(g) +178 kJ/mol
HHe+(aq) → HHe+(g) +973 kJ/mol

+ +
H (g) → H (aq) −1530 kJ/mol
He(g) → He(aq) +19 kJ/mol
HHe+(aq) → H+(aq) + He(aq) −360 kJ/mol
A free energy change of dissociation of −360 kJ/mol is equivalent to a pKa of −63.

It has been suggested that HeH should occur naturally in the interstellar medium, but it has not yet been detected.
+
Inductive Effects
Atoms or groups of atoms in a molecule other than those to which H is bonded can induce a change in the distribution of electrons
within the molecule. This is called an inductive effect, and, much like the coordination of water to a metal ion, it can have a major
effect on the acidity or basicity of the molecule. For example, the hypohalous acids (general formula HOX, with X representing a
halogen) all have a hydrogen atom bonded to an oxygen atom. In aqueous solution, they all produce the following equilibrium:
+ −
H OX(aq) ⇌ H + OX (aq) (16.10.3)
(aq)
The acidities of these acids vary by about three orders of magnitude, however, due to the difference in electronegativity of the
halogen atoms:
HOX Electronegativity of X pKa
HOCl 3.0 7.40
HOBr 2.8 8.55
HOI 2.5 10.5
As the electronegativity of X increases, the distribution of electron density within the molecule changes: the electrons are drawn
more strongly toward the halogen atom and, in turn, away from the H in the O–H bond, thus weakening the O–H bond and
allowing dissociation of hydrogen as H .+
The acidity of oxoacids, with the general formula H OXO (with n = 0−3), depends strongly on the number of terminal oxygen
n
atoms attached to the central atom X. As shown in Figure 16.10.1, the K values of the oxoacids of chlorine increase by a factor
a
of about 10 to 10 with each oxygen as successive oxygen atoms are added. The increase in acid strength with increasing number
4 6
of terminal oxygen atoms is due to both an inductive effect and increased stabilization of the conjugate base.
Any inductive effect that withdraws electron density from an O–H bond increases the
acidity of the compound.
Because oxygen is the second most electronegative element, adding terminal oxygen atoms causes electrons to be drawn away
from the O–H bond, making it weaker and thereby increasing the strength of the acid. The colors in Figure 16.10.1 show how the
electrostatic potential, a measure of the strength of the interaction of a point charge at any place on the surface of the molecule,
changes as the number of terminal oxygen atoms increases. In Figure 16.10.1 and Figure 16.10.2, blue corresponds to low electron
densities, while red corresponds to high electron densities. The oxygen atom in the O–H unit becomes steadily less red from H C lO
to H C lO (also written as H OC lO , while the H atom becomes steadily bluer, indicating that the electron density on the O–H
4 3
unit decreases as the number of terminal oxygen atoms increases. The decrease in electron density in the O–H bond weakens it,
making it easier to lose hydrogen as H ions, thereby increasing the strength of the acid.
+
Figure 16.10.1: The Relationship between the Acid Strengths of the Oxoacids of Chlorine and the Electron Density on the O–H
Unit. These electrostatic potential maps show how the electron density on the O–H unit decreases as the number of terminal
oxygen atoms increases. Blue corresponds to low electron densities, whereas red corresponds to high electron densities. Source:
Chlorine oxoacids pKa values from J. R. Bowser, Inorganic Chemistry (Pacific Grove, CA: Brooks-Cole,1993).
At least as important, however, is the effect of delocalization of the negative charge in the conjugate base. As shown in Figure
16.10.2, the number of resonance structures that can be written for the oxoanions of chlorine increases as the number of terminal
oxygen atoms increases, allowing the single negative charge to be delocalized over successively more oxygen atoms.
Electron delocalization in the conjugate base increases acid strength.

The electrostatic potential plots in Figure 16.10.2 demonstrate that the electron density on the terminal oxygen atoms decreases
steadily as their number increases. The oxygen atom in ClO− is red, indicating that it is electron rich, and the color of oxygen
progressively changes to green in C lO , indicating that the oxygen atoms are becoming steadily less electron rich through the
+
4
series. For example, in the perchlorate ion (C lO ), the single negative charge is delocalized over all four oxygen atoms, whereas in
−
4
the hypochlorite ion (OC l ), the negative charge is largely localized on a single oxygen atom (Figure 16.10.2). As a result, the
−
perchlorate ion has no localized negative charge to which a proton can bind. Consequently, the perchlorate anion has a much lower
affinity for a proton than does the hypochlorite ion, and perchloric acid is one of the strongest acids known.
As the number of terminal oxygen atoms increases, the number of resonance structures that can be written for the oxoanions of
chlorine also increases, and the single negative charge is delocalized over more oxygen atoms. As these electrostatic potential plots
demonstrate, the electron density on the terminal oxygen atoms decreases steadily as their number increases. As the electron
density on the oxygen atoms decreases, so does their affinity for a proton, making the anion less basic. As a result, the parent
oxoacid is more acidic.
Similar inductive effects are also responsible for the trend in the acidities of oxoacids that have the same number of oxygen atoms
as we go across a row of the periodic table from left to right. For example, H P O is a weak acid, H SO is a strong acid, and
3 4 2 4
H C lO is one of the strongest acids known. The number of terminal oxygen atoms increases steadily across the row, consistent
4
with the observed increase in acidity. In addition, the electronegativity of the central atom increases steadily from P to S to C l,
which causes electrons to be drawn from oxygen to the central atom, weakening the O– H bond and increasing the strength of the
oxoacid.
Careful inspection of the data in Table 16.10.1 shows two apparent anomalies: carbonic acid and phosphorous acid. If carbonic
acid (H C O ) were a discrete molecule with the structure (HO) C=O, it would have a single terminal oxygen atom and should
2 3 2
be comparable in acid strength to phosphoric acid (H P O ), for which pKa1 = 2.16. Instead, the tabulated value of pK for
3 4 a1
carbonic acid is 6.35, making it about 10,000 times weaker than expected. As we shall see, however, H C O is only a minor
2 3
component of the aqueous solutions of C O that are referred to as carbonic acid. Similarly, if phosphorous acid (H P O ) actually
2 3 3
had the structure (H O) P , it would have no terminal oxygen atoms attached to phosphorous. It would therefore be expected to be
3
about as strong an acid as H OC l (pKa = 7.40). In fact, the pK for phosphorous acid is 1.30, and the structure of phosphorous
a1
acid is (HO) P(=O)H with one H atom directly bonded to P and one P=O bond. Thus the pKa1 for phosphorous acid is similar
2
to that of other oxoacids with one terminal oxygen atom, such as H P O . Fortunately, phosphorous acid is the only common
3 4
oxoacid in which a hydrogen atom is bonded to the central atom rather than oxygen.
Table 16.10.1: Values of pKa for Selected Polyprotic Acids and Bases
Polyprotic Acids Formula pKa1 pKa2 pKa3
carbonic acid* “H 2 C O3 ” 6.35 10.33
citric acid 3.13

H O2 CCH − 2C(OH)(C O2 H)C H2 C O2 H 4.76 6.40
malonic acid HO − 2CC H2 C O2 H 2.85 5.70
oxalic acid H O2 CC O2 H 1.25 3.81
phosphoric acid H3 P O4 2.16 7.21 12.32
phosphorous acid H3 P O3 1.3 6.70
succinic acid H O2 CC H2 C H2 C O2 H 4.21 5.64
sulfuric acid H2 S O4 −2.0 1.99
sulfurous acid* “H 2 S O3 ” 1.85 7.21
Polyprotic Bases Formula pKb1 pKb2
ethylenediamine H2 N (C H2 )2 N H2 4.08 7.14
piperazine HN (C H2 C H2 )2 N H 4.27 8.67
propylenediamine H2 N (C H2 )3 N H2 3.45 5.12
*H C O and H S O are at best minor components of aqueous solutions of

2 3 2 3 CO2(g) and SO
2(g) , respectively, but such solutions are commonly
referred to as containing carbonic acid and sulfurous acid, respectively.
Inductive effects are also observed in organic molecules that contain electronegative substituents. The magnitude of the electron-
withdrawing effect depends on both the nature and the number of halogen substituents, as shown by the pKa values for several
acetic acid derivatives:
p Ka C H3 C O2 H 4.76 < C H2 C lC O2 H 2.87 < C H C l2 C O2 H 1.35 < C C l3 C O2 H 0.66 < C F3 C O2 H 0.52
As you might expect, fluorine, which is more electronegative than chlorine, causes a larger effect than chlorine, and the effect of
three halogens is greater than the effect of two or one. Notice from these data that inductive effects can be quite large. For instance,
replacing the – CH group of acetic acid by a – CF group results in about a 10,000-fold increase in acidity!
3 3
 Example 16.10.1
Arrange the compounds of each series in order of increasing acid or base strength.
a. sulfuric acid [H SO , or (H O) SO ], fluorosulfonic acid (F SO
2 4 2 2 3H , or F SO 2 OH ), and sulfurous acid [H 2 S O3 , or
(H O) SO ] 2
b. ammonia (N H ), trifluoramine (N F ), and hydroxylamine (N H

3 3 2 OH )
The structures are shown here.
Given: series of compounds
Asked for: relative acid or base strengths
Strategy:
Use relative bond strengths, the stability of the conjugate base, and inductive effects to arrange the compounds in order of
increasing tendency to ionize in aqueous solution.
Solution:
Although both sulfuric acid and sulfurous acid have two –OH groups, the sulfur atom in sulfuric acid is bonded to two terminal
oxygen atoms versus one in sulfurous acid. Because oxygen is highly electronegative, sulfuric acid is the stronger acid because
the negative charge on the anion is stabilized by the additional oxygen atom. In comparing sulfuric acid and fluorosulfonic
acid, we note that fluorine is more electronegative than oxygen. Thus replacing an –OH by –F will remove more electron
density from the central S atom, which will, in turn, remove electron density from the S–OH bond and the O–H bond. Because
its O–H bond is weaker, F SO H is a stronger acid than sulfuric acid. The predicted order of acid strengths given here is
3
confirmed by the measured pKa values for these acids:
−2
pKaH2 S O3 1.85 < H2 S O < F S O3 H − 10
4
The structures of both trifluoramine and hydroxylamine are similar to that of ammonia. In trifluoramine, all of the hydrogen
atoms in NH3 are replaced by fluorine atoms, whereas in hydroxylamine, one hydrogen atom is replaced by OH. Replacing the
three hydrogen atoms by fluorine will withdraw electron density from N, making the lone electron pair on N less available to
bond to an H ion. Thus N F is predicted to be a much weaker base than N H . Similarly, because oxygen is more
+
3 3
electronegative than hydrogen, replacing one hydrogen atom in N H by OH will make the amine less basic. Because oxygen
3
is less electronegative than fluorine and only one hydrogen atom is replaced, however, the effect will be smaller. The predicted
order of increasing base strength shown here is confirmed by the measured pK values: b
p Kb N F3 — << N H2 OH 8.06 < N H3 4.75
Trifluoramine is such a weak base that it does not react with aqueous solutions of strong acids. Hence its base ionization
constant has never been measured.
 Exercise 16.10.1
Arrange the compounds of each series in order of

a. decreasing acid strength: H P O , C H P O H , and H C lO .
3 4 3 3 2 3
b. increasing base strength: C H S , OH , and C F S .

3
− −
3
−
Answer a
H C lO − 3 > C H3 P O3 H2 > H3 P O4
Answer a
− − −
C F3 S < C H3 S < OH
Summary
Inductive effects and charge delocalization significantly influence the acidity or basicity of a compound. The acid–base strength of
a molecule depends strongly on its structure. The weaker the A–H or B–H+ bond, the more likely it is to dissociate to form an H +
ion. In addition, any factor that stabilizes the lone pair on the conjugate base favors the dissociation of H , making the conjugate
+
acid a stronger acid. Atoms or groups of atoms elsewhere in a molecule can also be important in determining acid or base strength
through an inductive effect, which can weaken an O– H bond and allow hydrogen to be more easily lost as H ions. +
Anonymous
16.10: Acid-Base Behavior and Chemical Structure is shared under a CC BY-NC-SA 3.0 license and was authored, remixed, and/or curated by
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16.8: Molecular Structure and Acid-Base Behavior is licensed CC BY-NC-SA 4.0.
16.11: Lewis Acids and Bases
Make sure you thoroughly understand the following essential ideas which have been presented above. It is especially important
that you know the precise meanings of all the highlighted terms in the context of this topic.
Write the equation for the proton transfer reaction involving a Brønsted-Lowry acid or base, and show how it can be
interpreted as an electron-pair transfer reaction, clearly identifying the donor and acceptor.
Give an example of a Lewis acid-base reaction that does not involve protons.
Write equations illustrating the behavior of a given non-aqueous acid-base system.
The Brønsted-Lowry proton donor-acceptor concept has been one of the most successful theories of Chemistry. But as with any
such theory, it is fair to ask if this is not just a special case of a more general theory that could encompass an even broader range of
chemical science. In 1916, G.N. Lewis of the University of California proposed that the electron pair is the dominant actor in acid-
base chemistry. The Lewis theory did not become very well known until about 1923 (the same year that Brønsted and Lowry
published their work), but since then it has been recognized as a very powerful tool for describing chemical reactions of widely
different kinds and is widely used in organic and inorganic chemistry. According to Lewis,
An acid is a substance that accepts a pair of electrons, and in doing so, forms a covalent bond with the entity that supplies the
electrons.
A base is a substance that donates an unshared pair of electrons to a recipient species with which the electrons can be shared.
In modern chemistry, electron donors are often referred to as nucleophiles, while

acceptors are electrophiles.
Proton-Transfer Reactions Involve Electron-Pair Transfer

Just as any Arrhenius acid is also a Brønsted acid, any Brønsted acid is also a Lewis acid, so the various acid-base concepts are all
"upward compatible". Although we do not really need to think about electron-pair transfers when we deal with ordinary aqueous-
solution acid-base reactions, it is important to understand that it is the opportunity for electron-pair sharing that enables proton
transfer to take place.
This equation for a simple acid-base neutralization shows how the Brønsted and Lewis definitions are really just different views of
the same process. Take special note of the following points:
The arrow shows the movement of a proton from the hydronium ion to the hydroxide ion.
Note carefully that the electron-pairs themselves do not move; they remain attached to their central atoms. The electron pair on
the base is "donated" to the acceptor (the proton) only in the sense that it ends up being shared with the acceptor, rather than
being the exclusive property of the oxygen atom in the hydroxide ion.
Although the hydronium ion is the nominal Lewis acid here, it does not itself accept an electron pair, but acts merely as the
source of the proton that coordinates with the Lewis base.
The point about the electron-pair remaining on the donor species is especially important to bear in mind. For one thing, it
distinguishes a Lewis acid-base reaction from an oxidation-reduction reaction, in which a physical transfer of one or more
electrons from donor to acceptor does occur. The product of a Lewis acid-base reaction is known formally as an "adduct" or
"complex", although we do not ordinarily use these terms for simple proton-transfer reactions such as the one in the above
example. Here, the proton combines with the hydroxide ion to form the "adduct" H2O. The following examples illustrate these
points for some other proton-transfer reactions that you should already be familiar with.
Another example, showing the autoprotolysis of water. Note that the conjugate base is also the adduct.
Ammonia is both a Brønsted and a Lewis base, owing to the unshared electron pair on the nitrogen. The reverse of this reaction
represents the hydrolysis of the ammonium ion.
Because HF is a weak acid, fluoride salts behave as bases in aqueous solution. As a Lewis base, F– accepts a proton from water,
which is transformed into a hydroxide ion.
The bisulfite ion is amphiprotic and can act as an electron donor or acceptor.
Acid-base Reactions without Transferring Protons

The major utility of the Lewis definition is that it extends the concept of acids and bases beyond the realm of proton transfer
reactions. The classic example is the reaction of boron trifluoride with ammonia to form an adduct:
BF + NH → F B−NH (16.11.1)
3 3 3 3
One of the most commonly-encountered kinds of Lewis acid-base reactions occurs when electron-donating ligands form
coordination complexes with transition-metal ions.
Figure 16.11.1: The tin atom in SnCl4 can expand its valence shell by utilizing a pair of d-orbitals, changing its hybridization from
sp3 to sp3d2.
 Exercise 16.11.1
Here are several more examples of Lewis acid-base reactions that cannot be accommodated within the Brønsted or Arrhenius
models. Identify the Lewis acid and Lewis base in each reaction.
a. Al (OH)
3
+ OH
–
→ Al (OH) –
4
b. SnS + S → SnS
2
2 – 2 –
3
c. Cd(CN) + 2 CN– → Cd(CN)

2
2 +
4
+
d. AgCl + 2 NH → Ag(NH ) + Cl–
3 3 2
e. Fe + NO → Fe(NO)
2 + 2 +
2 +
f. Ni + 6 NH → Ni(NH )
2 +
3 3 5
Applications to organic reaction mechanisms

Although organic chemistry is beyond the scope of these lessons, it is instructive to see how electron donors and acceptors play a
role in chemical reactions. The following two diagrams show the mechanisms of two common types of reactions initiated by simple
inorganic Lewis acids:
In each case, the species labeled "Complex" is an intermediate that decomposes into the products, which are conjugates of the
original acid and base pairs. The electric charges indicated in the complexes are formal charges, but those in the products are "real".
In reaction 1, the incomplete octet of the aluminum atom in AlCl serves as a better electron acceptor to the chlorine atom than
3
does the isobutyl part of the base. In reaction 2, the pair of non-bonding electrons on the dimethyl ether coordinates with the
electron-deficient boron atom, leading to a complex that breaks down by releasing a bromide ion.
Non-aqueous Protonic Acid-Base Systems

We ordinarily think of Brønsted-Lowry acid-base reactions as taking place in aqueous solutions, but this need not always be the
case. A more general view encompasses a variety of acid-base solvent systems, of which the water system is only one (Table
16.11.1). Each of these has as its basis an amphiprotic solvent (one capable of undergoing autoprotolysis), in parallel with the
familiar case of water.

The ammonia system is one of the most common non-aqueous system in Chemistry. Liquid ammonia boils at –33° C, and can
conveniently be maintained as a liquid by cooling with dry ice (–77° C). It is a good solvent for substances that also dissolve in
water, such as ionic salts and organic compounds since it is capable of forming hydrogen bonds. However, many other familiar
substances can also serve as the basis of protonic solvent systems as Table 16.11.1 indicates:
Table 16.11.1: Popular Solvent systems
solvent autoprotolysis reaction pKap
water 2 H2O → H3O+ + OH– 14
ammonia 2 NH3 → NH4+ + NH2– 33
acetic acid 2 CH3COOH → CH3COOH2+ + CH3COO– 13
ethanol 2 C2H5OH → C2H5OH2+ + C2H5O– 19
hydrogen peroxide 2 HO-OH → HO-OH2+ + HO-O– 13
hydrofluoric acid 2 HF → H2F+ + F– 10
sulfuric acid 2 H2SO4 → H3SO4+ + HSO4– 3.5
One use of nonaqueous acid-base systems is to examine the relative strengths of the strong acids and bases, whose strengths are
"leveled" by the fact that they are all totally converted into H3O+ or OH– ions in water. By studying them in appropriate non-
aqueous solvents which are poorer acceptors or donors of protons, their relative strengths can be determined.
Figure 16.11.2: Use of non-aqueous solvents allows the study of strong acids that are hindered by the "leveling" of the solvent.
16.11: Lewis Acids and Bases is shared under a CC BY-NC-SA 3.0 license and was authored, remixed, and/or curated by LibreTexts.
10.5: Lewis Acids and Bases by Stephen Lower is licensed CC BY 3.0. Original source:
http://www.chem1.com/acad/webtext/virtualtextbook.html.

Acid-Base Equilibria - Libre Texts

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Acid-Base Equilibria - Libre Texts

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CHAPTER OVERVIEW

16: Acid–Base Equilibria

Chemistry: The Central Science

produce a piercing pain in a wound. give a slippery feel.

taste sour. taste bitter.

have a pH<7. have a pH>7.

produce hydrogen gas when reacted with metals.

produce carbon dioxide when reacted with carbonates.

The Arrhenius Definition of Acids and Bases

adding H2O to the reactants side.

releasing H+ ions into solution. Formation of the hydronium ion equation:

describe acids and bases in an aqueous environment.

 Limitation of the Arrhenius Definition of Acids and Bases

Contributors and Attributions

a proton from acids to form water:

base + proton ⇌ conjugate acid (16.2.8)

\[\ce{F^- +H^+ \rightleftharpoons HF} \label{16.2.3g} \]

the ion-product constant for water (Kw):

times larger than the value at 25 °C.

Conjugate Acid-Base Pairs

A Video Discussing Conjugate Acid-Base Pairs: Conjugate Acid-Base Pairs [youtu.be]

 Example 16.2.1: Ion Concentrations in Pure Water

The ion product of water at 80 °C is 2.4 × 10 −13

and hydroxide ion concentrations.

Self-Ionization of Water (Kw)

 Example 16.2.2: The Inverse Proportionality of [H 3

A solution of carbon dioxide in water has a hydronium ion concentration of 2.0 × 10

Thus, we can calculate the missing equilibrium concentration.

A check of these concentrations confirms that our arithmetic is correct:

 Example 16.2.3: The Acid-Base Behavior of an Amphoteric Substance

Write separate equations representing the reaction of HSO −

Write separate equations representing the reaction of H 2

a. as a base with HBr

ion-product constant for water (Kw)

Contributors and Attributions

Lewis electron-pair acceptor electron-pair donor

Acid–Base Properties of Water

In this reaction, H C l is the acid, and water acts as a base by accepting an H +

In Equation 16.3.2, the hydronium ion is represented by H

The Ion-Product Constant of Liquid Water

The equilibrium constant K for this reaction can be written as follows:

Because a = 1 for a dilute solution, Ka = Keq(1), or Ka = Keq.

law of mass action as the K of water:

Thus, to three significant figures, K w = 1.01 × 10

The Relationship among pH, pOH, and pK w

and the H (H O ) concentration are related as follows:

The constant K can also be expressed using this notation, where pK

Thus at any temperature, pH + pOH = pK , so at 25 °C, where K = 1.0 × 10

A Video Introduction to pH: Introduction to pH [youtu.be]

Asked for: pK , pH, and pOH

The answer is reasonable: K is between 10

Because x is equal to both [H 3O

= 6.15 (to two decimal places)

Relationship among pH, pOH , and pK : w

hydronium and hydroxide ion is always 1.0 × 10 . −14

call the hydronium ion.

At room temperature (25 °C),

Using the properties of logarithms, Equation 16.4.8 can be rewritten as

The pH scale is logarithmic, meaning that an increase or decrease of an integer value

If the concentration of N aOH in a solution is 2.5 × 10 −4

to find the concentration of H3O+, solve for the [H3O+].

b. The equation for pOH is -log [OH-]

A Video Introduction to pH: Introduction to pH [youtu.be]

pOH = − log[ OH ] . In pure water, pH = 7.00 and pOH = 7.00.

Contributors and Attributions

To understand the leveling effect.

The equilibrium constant for this dissociation is as follows:

Again, for simplicity, H 3O

sulfuric acid (1)* H2 S O4 1 × 10

nitric acid HN O3 2.3 × 10

sulfuric acid (2)* HSO

hydrofluoric acid HF 6.3 × 10