Chapter14: Acids & Bases

Chapter 14. Acids & Bases Arrhenius Definition of Acid & Base

Arrhenius Acid: Substance that dissociates to form

hydrogen ions (H+) in solution:

HA(aq) → H+(aq) + A–(aq)

Arrhenius Base: Substance that dissociates in, or

reacts with water to form hydroxide ions (OH–):

MOH(aq) → M+(aq) + OH–(aq)

Bronsted-Lowry Definition of Acid & Base Conjugate Acid-Base Pairs for Acid

• Brønsted–Lowry Acid: Substance that can donate H+

• Brønsted–Lowry Base: Substance that can accept H+

• Chemical species with formulas that differ by one

proton are known as conjugate acid–base pairs.

Relative Strengths of Acids &

Strong versus Weak Acid
Conjugate Bases

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 Chapter14: Acids & Bases

Conjugate Acid-Base Pairs for Base Identifying the Conjugate Acid

In the reaction:
NH4+(aq) + NO2-(aq) ↔ HNO2(aq) + NH3(aq)
What is the conjugate acid of NO2-(aq)?
A. NO2-(aq)
B. HNO2(aq)
C. NH3(aq)

Water as Acid or Base Equilibrium Constant for H2O

Dissociation

• Water can act as an acid or as a base. • Equilibrium constant for H2O dissociation is known
as the ion product constant for water.
H2O(l) → H+(aq) + OH–(aq)

• This dissociation is the autoionization of water. Kw = Kc = [H+][OH–] = 1.0 x 10–14

• If we know either [H+] or [OH–], then we can

determine the other quantity.

• H2O(l) + H2O(l) → H3O+(aq) + OH–(aq)

Using Equilibrium Constant for H2O to Definition of pH

Determine H+ Concentration

• The concentration of OH– ions in a household • pH of a solution is the negative logarithm of the
ammonia cleaning solution is 0.0025 M. What is hydrogen ion concentration (in mol/L).

the concentration of H+ ions? pH = –log [H+]

A. 2.5 x 10-3 M pH + pOH = 14
B. 4.0 x 10-10 M
Acidic solutions: [H+] > 1.0 x 10–7 M, pH < 7.00
C. 4.0 x 10-12 M Basic solutions: [H+] < 1.0 x 10–7 M, pH > 7.00

D. 2.5 x 10-12 M Neutral solutions: [H+] = 1.0 x 10–7 M, pH = 7.00

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 Chapter14: Acids & Bases

Demonstration: pH of Common
Household Items
Many Household
Items Span
Entire pH Range

Calculating the H+ Concentration of Determining the pH of Blood

Orange Juice
The OH– ion concentration of a blood
pH = –log [H+] sample is 2.5 x 10–7 M.
pH + pOH = 14 What is the pH of the blood?
The pH of a certain orange juice is 3.33. pH = –log [H+]; [H+][OH–] = 1.0 x 10–14
Calculate the H+ ion concentration.
A. 6.6
Is orange juice acidic?
B. 7.4
C. 8.1
D. 8.7

Proton is Always Transferred

Strong vs. Weak Acids & Bases
to the Stronger Base
Strong acids and bases: are strong Direction of reaction to reach equilibrium is proton
transfer from the stronger acid to the stronger base
electrolytes that are assumed to ionize to give the weaker acid and the weaker base.
completely in water.
Stronger acid + stronger base →
Weak acids and bases: are weak weaker acid + weaker base
electrolytes that ionize only to a limited
Example:
extent in water.
HNO2(aq) + CN–(aq) → HCN(aq) + NO2–(aq)

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Determining the Direction of Reaction Acid Ionization Constant

Which direction will this reaction go if Acid Ionization Constant: the equilibrium constant
proton transfer is from the stronger acid to for the ionization of an acid.
the stronger base?
HA(aq) + H2O(l) → H3O+(aq) + A–(aq)
HF(aq) + NH3(aq) ↔ F–(aq) + NH4+(aq)
A. Left to Right Or simply: HA(aq) → H+(aq) + A–(aq)

B. Right to Left [H+ ][A − ]

Ka =
C. Equally Balanced [HA]

Diprotic & Polyprotic Acids

Wide Range of Acid Ionization Constants

ACID Ka CONJ. BASE Kb Diprotic and polyprotic acids yield more than one
HF 7.1 x 10 –4 F– 1.4 x 10 –11 hydrogen ion per molecule.
HNO2 4.5 x 10 –4 NO2 – 2.2 x 10 –11
C9H8O4 (aspirin) 3.0 x 10 –4 C9H7O4 – 3.3 x 10 –11
One proton is lost at a time. Conjugate base of first
HCO2H (formic) 1.7 x 10 –4 HCO2 – 5.9 x 10 –11
step is acid of second step.
C6H8O6 (ascorbic) 8.0 x 10 –5 C6H7O6 – 1.3 x 10 –10
C6H5CO2H (benzoic) 6.5 x 10 –5 C6H5CO2 – 1.5 x 10 –10
CH3CO2H (acetic) 1.8 x 10 –5 CH3CO2 – 5.6 x 10 –10 Ionization constants decrease as protons are
HCN 4.9 x 10 –10 CN – 2.0 x 10 –5 removed.
C6H5OH (phenol) 1.3 x 10 –10 C6H5O – 7.7 x 10 –5

Dissociation Constants for Dissociation Constants for

Polyprotic Acids Polyprotic Acids
ACID Ka CONJ. BASE Kb
H2SO4 Very Large HSO4 – Very Small
HSO4– 1.3 x 10 –2 SO4 2– 7.7 x 10 –13
C2 H2 O 4 6.5 x 10 –2 C2HO4– 1.5 x 10 –13
C2HO4– 6.1 x 10 –5 C2O42– 1.6 x 10 –10
H2SO3 1.3 x 10 –2 HSO3 – 7.7 x 10 –13
HSO3– 6.3 x 10 –8 SO3 2– 1.6 x 10 –7
H2CO3 4.2 x 10 –7 HCO3– 2.4 x 10 –8
HCO3– 4.8 x 10 –11 CO3 2– 2.1 x 10 –4
H2 S 9.5 x 10 –8 HS– 1.1 x 10 –7
HS– 1 x 10 –19 S 2– 1 x 10 –5
H3PO4 7.5 x 10 –3 H2PO4– 1.3 x 10 –12
H2PO4– 6.2 x 10 –8 HPO42– 1.6 x 10 –7
HPO42– 4.8 x 10 –13 PO43– 2.1 x 10 –2

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 Chapter14: Acids & Bases

pH and Equilibria for Weak Acids

Demonstration: Acidity of Dry Ice
Determining pH and Concentrations in Solutions
When dry ice is added to a graduated cylinder containing of Weak Acids:
blue liquid (basic water with universal indicator), the dry ice
produces bubbles and fog and turns the solution yellow. 1. Write a balanced equation and equilibrium expression.

2. Identify all species present that may affect pH.

CO2 produces carbonic acid (diprotic acid) in solution.
Dissociation of carbonic acid produces H+ in solution and
3. Major species will be HA, H+, A–. Ignore H2O & OH–.
neutralizes OH-.

CO2(aq) + H2O(l) —> H2CO3(aq) <—> 2H+(aq) + CO32-(aq) 4. Summarize the changes in concentration of HA, H+, A–
using an I.C.E. table.
H+(aq) + OH-(aq) —> H2O(l)

Equilibrium Calculations Solving the Quadratic Equation

• Initial Change Equilibrium Table: Determine the • The Quadratic Equation:

pH of 0.50 M HA solution at 25°C. Ka = 7.1 x 10–4. ax 2 + bx + c = 0

HA (aq) → H +(aq) + A-(aq) • Values are substituted into the below expression and
solved for a positive solution to x.
Initial (M): 0.50 0.00 0.00
Change (M): –x +x +x − b ± b2 − 4ac
x=
Equilib (M): 0.50 – x x x 2a

Simplifying Assumptions
Another Equilibrium Calculation
For weak acid problems, Ka is very small.
Consequently, the amount of dissociated acid, Calculate the pH and the concentrations
x, is negligible relative to the initial of all species present in 0.050 M HF. Ka
concentration. for HF is 3.5 x 10-4.

Under these conditions, can ignore x in terms

involving the initial concentrations.
After solving for x, can go back and verify
assumption.

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Percent Dissociation Decreases as

Percent Dissociation
Concentration Increases
• Percent Dissociation is a measure of the
strength of an acid.
[H+ ]
% Dissociation = × 100%
[HA]
• Stronger acids have higher percent dissociation.

• Percent dissociation of a weak acid decreases as

its concentration increases.

Determining the Percent Dissociation Base Ionization Constant

What is the percent dissociation for a 1.0 M
Base Ionization Constant is the equilibrium
weak acid solution with Ka= 1.0 x 10-4? constant for the ionization of a base.
[H+ ]
% Dissociation = × 100% Ionization of weak bases is treated in the same way
[HA]
as the ionization of weak acids.
A. 3.2%
B(aq) + H2O(l) → BH+(aq) + OH–(aq)
B. 0.32%
Calculations follow the same procedure as used for
C. 1.0% weak acids but [OH–] is calculated instead of [H+].

D. 0.10%

Wide Range of Base Ionization Constants Product of Ka and Kb

BASE Kb CONJ. ACID Ka Multiplying out the expressions for Ka and Kb

equals Kw.
C2H5NH2 (ethylamine) 5.6 x 10 –4 C2H5NH3+ 1.8 x 10 –11
C8H10N4O2 (caffeine) 4.1 x 10 –4 C8H11N4O2+ 2.4 x 10 –11
NH3 (ammonia) 1.8 x 10 –5 NH4+ 5.6 x 10 –10 Ka × Kb = Kw = 1.0 x 10-14
C5H5N (pyridine) 1.7 x 10 –9 C5 H6 N+ 5.9 x 10 –6
C6H5NH2 (aniline) 3.8 x 10 –10 C6H5NH3+ 2.6 x 10 –5 Use this expression to solve for acid ionization
NH2CONH2 (urea) 1.5 x 10 –14 NH2CONH3+ 0.67 constant if know base ionization constant or
visa versa.

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Determining Ka from Kb Acid-Base Properties of Salts

CH3NH2(aq) + H2O(l) ↔ CH3NH3+(aq) + OH-(aq) Kb

Salts that produce neutral solutions are those
formed from strong acids and strong bases.
CH3NH3 +(aq) + H2O(l) ↔ H3 O+(aq) + CH3NH2(aq) Ka

Kb for CH3NH2 is 4.4 x 10-4. Calculate Ka for Salts that produce basic solutions are those formed
from weak acids and strong bases.
the methylamine ion, CH3NH3+.
Salts that produce acidic solutions are those formed
A. 7.82 x 10-8 from strong acids and weak bases.
B. 3.9 x 10-9
C. 2.3 x 10-11

Table of Different Salt Behavior Neutral Solutions from Salts Formed

from Strong Acids and Strong Bases

Example: NaCl
Derived from NaOH (strong base)
and HCl (strong acid).
Neither Na+ or Cl- will react with
water and change [H+] or [OH-]

Basic Solutions from Salts Formed Acidic Solutions from Salts Formed
from Weak Acids and Strong Bases from Strong Acids and Weak Bases

Example: NaCN Example: NH4Cl

Derived from NaOH (strong base) Derived from NH3 (weak base) and
and HCN (weak acid). HCl (strong acid).
Na+ will not react with water and Cl- will not react with water and
change [H+] of [OH-] change [H+]
CN- will react with H2O and produce NH4+ will react with H2O and produce
OH- and HCN. → Basic Solution H3O+ and NH3. → Acidic Solution

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Demonstration: Acidic or Basic Determining the pH of a Salt Solution

Solutions from Salts
What is the pH of a 0.15 M solution of
The pH of acidic, basic, and neutral sodium acetate (CH3COONa)? Ka
aqueous solutions of salts is shown with for CH3COOH is 1.8 x 10-5.
ammonium chloride, sodium acetate, and
sodium chloride. A. 7.81
B. 8.32
C. 8.96
D. 9.31

Lewis Definition of Acid & Base Lewis Base Molecules

Electron Pair Donors

• Lewis Acid is an electron-pair acceptor. These are
generally cations or neutral molecules with vacant
valence orbitals, such as Al3+, Cu2+, H+, BF3.

• Lewis Base is an electron-pair donor. These are

generally anions or neutral molecules with available
pairs of electrons, such as H2O, NH3, O2–.

Lewis Acid + Lewis Base Interaction

Factors Affect Acid Strength

Strength of acid depends on its tendency to

ionize.
For general acids of the type H–X:
The stronger the bond, the weaker the acid.
The more polar the bond, the stronger the
acid.

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 Chapter14: Acids & Bases

Stronger Bond Strength → Weaker Acid Larger Electronegativity → Stronger Acid

For binary acids in the same group, H–A bond For binary acids in the same row, H–A polarity
strength decreases with increasing size of A increases with increasing electronegativity of A and
and acidity increases. acidity increases.

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