Chapter 15

Acids and Bases

Definitions of Acids and Bases
• Arrhenius definition
– Based on H+ and OH-

• Brønsted–Lowry definition
– Based on reactions in which an H+ is transferred

• Lewis definition
– Based on reactions in which an electron pair is transferred
Arrhenius Theory
• Swedish Chemist Svante Arrhenius (1880s)
• Acids: produce H+ ions in aqueous solution.

HCl(aq) → H+(aq) + Cl−(aq)

 Hydronium Ion

• The H+ ions produced by the acid are so reactive they cannot

exist in water.

• Instead, they react with water molecules to produce complex

ions, mainly hydronium ion, H3O+.
H+ + H2O → H3O+
Arrhenius Theory
• Bases: produce OH− ions in aqueous solution.

NaOH(aq) → Na+(aq) + OH(aq)

Arrhenius Acid–Base Reactions

• The H+ from the acid combines with the OH− from the
base to make a molecule of H2O.
– It is often helpful to think of H2O as H—OH.

• The cation from the base combines with the anion from
the acid to make a salt.

acid + base → salt + water

HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)

 Problems with Arrhenius Theory

• It does not explain why molecular substances, such as NH3,

dissolve in water to form basic solutions, even though they
do not contain OH– ions.

• It does not explain how some ionic compounds, such as

Na2CO3 or Na2O, dissolve in water to form basic solutions,
even though they do not contain OH– ions.

• It does not explain why molecular substances, such as CO2,

dissolve in water to form acidic solutions, even though they
do not contain H+ ions.
Brønsted–Lowry Theory
Any reaction involving H+ (proton) that transfers from one
molecule to another is an acid–base reaction, regardless of
whether it occurs in aqueous solution or if there is OH−
present.

• The acid is an H+ donor.

• The base is an H+ acceptor.

• When HCl dissolves in water, the HCl is the acid because

HCl transfers an H+ to H2O, forming H3O+ ions.
– Water acts as base, accepting H+.

HCl(aq) + H2O(l) → Cl–(aq) + H3O+(aq)

acid base
• When NH3 dissolves in water, the NH3(aq) is the base
because NH3 accepts an H+ from H2O, forming OH–(aq).
– Water acts as acid, donating H+.

NH3(aq) + H2O(l)  NH4+(aq) + OH–(aq)

base acid
Conjugate Acid–Base Pairs
• In a Brønsted-–Lowry acid–base reaction,
– the original base becomes an acid in the reverse reaction.
– the original acid becomes a base in the reverse process.

• Each reactant and the product it becomes is called a

conjugate pair.
Conjugate Pairs

A base accepts a proton and becomes a conjugate acid.

An acid donates a proton and becomes a conjugate base.

Arrow Conventions

• Chemists commonly use two kinds of

arrows in reactions to indicate the degree of
completion of the reactions.

• A single arrow indicates that all the reactant

molecules are converted to product
molecules at the end.

• A double arrow indicates the reaction stops

when only some of the reactant molecules
have been converted into products.
–  in these notes
Acid Strength & Acid Ionization Constant (Ka)

Arrow Conventions
• Chemists commonly use two kinds of
arrows in reactions to indicate the degree of
completion of the reactions.

• A single arrow indicates that all the reactant

molecules are converted to product
molecules at the end.

• A double arrow indicates the reaction stops

when only some of the reactant molecules
have been converted into products.
 Strong Acids
• Strong acids donate practically all their H+.
✓ 100% ionized in water
✓ Strong electrolyte
Examples of Strong Acids
Weak Acids
• Weak acids donate a small fraction of their H+.
Examples of Weak Acids
 Strengths of Acids and Bases

• Commonly, acid or base strength is measured by

determining the equilibrium constant of a
substance’s reaction with water.

HAcid + H2O  Acid− + H3O+

Base + H2O  HBase+ + OH−

• When the equilibrium position lies toward the

products, the stronger the acid or base.
• Acid strength is measured by the equilibrium constant
when it reacts with H2O.

• The equilibrium constant for this reaction is called the acid

ionization constant, Ka.
– larger Ka = stronger acid
Table 15.5
The position of equilibrium depends on the strength
of attraction between the base form and the H+.

Stronger attraction means weaker acid or stronger

base.

The stronger an acid is at donating H, the weaker

the conjugate base is at accepting H.
 Autoionization of Water
• Water is amphoteric; it can act either as an acid or a base.

• About 2 out of every 1 billion water molecules form ions

through a process called autoionization.
H2O  H+ + OH–
H2O + H2O  H3O+ + OH–

• All aqueous solutions contain both H3O+ and OH–.

– The concentration of H3O+ and OH– are equal in water.

– [H3O+] = [OH–] = 10−7 M at 25 °C
Ion Product of Water ( Kw)
• The product of the H3O+ and OH– concentrations is always
the same number called the ion product constant of water
and has the symbol Kw.

• [H3O+] × [OH–] = Kw = 1.00 × 10−14 at 25 °C

– If you measure one of the concentrations, you can calculate
the other.

• As [H3O+] increases the [OH–] must decrease so the product

stays constant - Inversely proportional
 Acidic and Basic Solutions

All aqueous solutions contain both H3O+ and OH– ions.

• Neutral solutions have equal [H3O+] and [OH–].

– [H3O+] = [OH–] = 1.00 × 10−7

• Acidic solutions have a larger [H3O+] than [OH–].

– [H3O+] > 1.00 × 10−7; [OH–] < 1.00 × 10−7

• Basic solutions have a larger [OH–] than [H3O+].

– [H3O+] < 1.00 × 10−7; [OH–] > 1.00 × 10−7
 Measuring Acidity: pH
• The acidity or basicity of a solution
is often expressed as pH.

• pH = −log10[H3O+]
✓ pHwater = −log[10−7] = 7
✓ Need to know the [H3O+] concentration
to find pH

• pH < 7 is acidic;
• pH > 7 is basic.
• pH = 7 is neutral.
The pH Scale: A Way to Quantify Acidity and
Basicity
• The lower the pH, the more acidic the solution; the higher
the pH, the more basic the solution.

• Normal range of pH is 0 to 14.

 pOH
• Another way of expressing the acidity/basicity of a solution is
pOH.

• pOH = −log[OH−], [OH−] = 10−pOH

✓ pOHwater = −log[10−7] = 7
✓ Need to know the [OH−] concentration to find pOH

• pOH < 7 is basic;

• pOH > 7 is acidic;
• pOH = 7 is neutral.
• pH + pOH = 14.0 at 25 °C.
Relationship between pH and pOH

• pH + pOH = 14.00 at 25 °C.

– You can use pOH to find the pH of a solution.

[H3O+ ][OH− ] = K w = 1.0  10−14

( ( )) ( )
− log [H3O+ ][OH− ] = − log 1.0  10−14

( ( )) ( ( ))
− log [H3
O ]+
+ − log [OH− ] = 14.00

pH + pOH = 14.00
Example 15.3 Calculating pH from [H3O+] or [OH−]
Calculate the pH of each solution at 25 °C and indicate whether the solution is acidic or basic.
a. [H3O+] = 1.8 × 10−4 M b. [OH−] = 1.3 × 10−2 M

b. First use Kw to find [H3O+] from [OH−].

Then substitute [H3O+] into the pH expression to find pH.
Since pH > 7, this solution is basic.
1- Calculate [H+] for each of the following solutions, and indicate
whether the solution is acidic, basic, or neutral:
(a) [OH-] = 7.3 * 10-10 M
(b) [OH-] = 0.015 M
(c) a solution in which [H+] is 10 times greater than [OH-].
Answer:
A) [H+]=10-14/7.3*10-10=1.4*10-5 M, Acidic
B) [H+]=10-14/0.015=6.67*10-13M, basic
C) [H+]= 10*sqrt(10-14/10)=3.16*10-7M, Acidic
2- Calculate the concentration of an aqueous solution of NaOH
that has a pH of 12.70.
Answer:
pOH=14-12.7=1.3
[OH-]= 10-1.3=0.05M=conc. of NaOH
 Strong Bases

• The stronger the base, the

more willing it is to accept H.
✓ Use water as the standard
acid.

• For ionic bases, practically all

units are dissociated into OH–
or accept H+.
✓ Strong electrolyte
✓ Multi-OH strong bases
completely dissociated
 Weak Bases

• In weak bases, only a small

fraction of molecules accept H+.
✓ Weak electrolyte
✓ Most of the weak base molecules
do not take H from water.
✓ Much less than 1% ionization
in water

• [HO–] << [weak base]

• Finding the pH of a weak base
solution is similar to finding the pH
of a weak acid.
 Base Ionization Constant, Kb

• Base strength is measured by the size of the

equilibrium constant when it reacts with H2O
:Base + H2O  OH− + H:Base+

• The equilibrium constant is called the base

ionization constant, Kb.
– Larger Kb = stronger base
Common Weak Bases

Table 15.8 page 721

 Polyprotic Acids
Ionization in H2SO4

• The ionization constants for H2SO4 are as follows:

H2SO4 + H2O → HSO4− + H3O+ strong
HSO4− + H2O  SO42− + H3O+ Ka2 = 1.2 × 10−2

• For most sulfuric acid solutions, the second ionization is

significant and must be accounted for.

• Because the first ionization is complete, use the given [H2SO4]

= [HSO4−]initial = [H3O+]initial.
a 0.100 m H2C6H6O6 solution contains an H3O+ concentration o
2.8 * 10-3 m from the first step.
The amount of H3O+
contributed by the second step is only 1.6 * 10-12 m, which is
insignificant compared to the amount produced by the first step.
 Lewis Acid–Base Theory
• Lewis acid–base theory focuses on transferring an electron pair.

• Does NOT require H atoms

• The electron donor is called the Lewis base.

– Electron rich; therefore nucleophile

• The electron acceptor is called the Lewis acid.

– Electron deficient; therefore electrophile
 Structure of Amines

• The Lewis base has electrons it is willing to give away to or

share with another atom.

• The Lewis base must have a lone pair of electrons on it that it

can donate.
The Lewis base donates an electron pair to the Lewis
acid, resulting in covalent bond formation

H3N: + BF3 → H3N─BF3 (an adduct)

Lewis base Lewis acid

Boron in BF3 has an empty 2p orbital and an incomplete

octet