Acid-Base Equlibria

William L Masterton
Cecile N. Hurley
http://academic.cengage.com/chemistry/masterton
Chapter 13
Acids and Bases
Edward J. Neth • University of Connecticut

Outline
1. Brønsted-Lowry acid-base model
2. The ion product of water
3. pH and pOH
4. Weak acids and their equilibrium constants
5. Weak bases and their equilibrium constants
6. Acid-base properties of salt solutions
Review from Chapter 4
• The Arrhenius definition of acid and base
• Acids produce H+ in water
• Bases produce OH- in water
• H+ from acids combines with OH- from bases to
produce water in a reaction called a neutralization
Brønsted-Lowry Acid-Base Model
• Brønsted-Lowry
• Johannes Brønsted (1879-1947)
• Thomas Lowry (1874-1936)
• Brønsted-Lowry model focuses on the reaction that
takes place between acid and base, rather than on
the independent nature of the acid or base, as the
Arrhenius model does
• Acids donate H+ to bases
• Bases accept H+ from acids
The Nature of H+
• The H+ ion is the medium of exchange in a
Brønsted-Lowry reaction
• H+ can also be called a proton
• Acid-base reactions involve proton exchange
Conjugate Pairs
• The species that forms when a proton is removed
from an acid is called the conjugate base of the
acid
• If the acid is HB, the conjugate base is B-
• The only difference between the members of a
conjugate acid-base pair is the position of the proton
• A species that can either accept or donate a proton
is called amphiprotic
• Consider water:
• OH-  H2O  H3O+
Remove H+ Add H+
Examples of Conjugate Acid-Base Pairs
Conjugate Conjugate
Acid Base
HF F-
HSO4- SO42-
NH4+ NH3
The Hydronium Ion
• Another way to write the H+ ion is as H3O+
• H3O+ is the hydronium ion
• H+ exists in water as hydronium ion, since H+ itself
would not be stable in water
• Depending on the reason for writing the reaction,
either H+ or H3O+ can be used, and
interchangeably
• The only difference is the inclusion or exclusion of
the H2O molecule
Example 13.1
The Ion Product of Water
• Water can react with itself in a reaction called
autoionization
• Water can react with itself in an acid-base reaction:
• H2O + H2O ⇌ H3O+ (aq) + OH- (aq)
• An alternate way to write the reaction is:
• H2O ⇌ H+ (aq) + OH- (aq)
Equilibrium and the Auto-Ionization of Water
• H2O ⇌ H+ (aq) + OH- (aq)

• Recall that concentrations can be used to write
equilibrium constant expressions
• K for this reaction is [H+][OH-]
• This K is called the ion product constant of
water, Kw
• Kw = [H+][OH-]
• At 25 °C, Kw = 1.0 X 10-14
Concentrations of H+ and OH- in pure water
• In pure water, [H+] = [OH-] = 1.0 X 10-14
• [H+] = 1.0 X 10-7
• [OH-] = 1.0 X 10-7
• When the two concentrations are equal, the
solution is said to be neutral
• If [H+] > 1.0 X 10-7, then [OH-] < 1.0 x 10-7 and the
solution is acidic
• If [OH-] > 1.0 X 10-7, then [H+] < 1.0 x 10-7 and the
solution is basic
Figure 13.1
pH
• Defining equation for pH
pH   log[H  ]
[H  ]  anti log(  pH )  10  pH
• The higher the pH, the less acidic the solution

• The lower the pH, the more acidic the solution
Figure 13.2
pOH
• Defining equation for pH

pOH   log[OH ]
 pOH
[OH ]  antilog[ pOH]  10
• The higher the pOH, the more basic the solution

• The lower the pOH, the more acidic the solution
Relationship between pH and pOH
  14
[H ][OH ]  1.0 x10
pH  pOH  14
Example 13.2
Example 13.2, (Cont’d)
pH and Blood
• From the previous example, it is seen that the [H+] in
blood is very small, about 4.0 X 10-8 M
• Small changes in [H+] can have dramatic
physiological effects
• Many biological reactions depend on [H+]
• An increase in [H+] from 4.0 X 10-8 to 4.0 X 10-7 can
increase the a reaction rate by a power of 10
• Small increases in [H+] can lead to acidosis;
small decreases in [H+] can lead to alkalosis
• Effective control of many physiological
reactions depends on pH control
pH of Strong Acids
• Recall from Chapter 4 that some acids are strong
• HCl, HBr, HI, HClO4, HNO3, H2SO4
• These completely ionize in water
• [H+] is equal to the [H+] of the acid
• A 0.10 M solution of HCl has [H+] = 0.10, so the
pH of the solution is 1.0
Figure 13.3
pH of Strong Bases
• Recall as well that some bases are strong:
• LiOH, NaOH, KOH, Ca(OH)2, Sr(OH)2, Ba(OH)2
• These bases ionize completely to OH-
• pOH is dependent on the concentration of the strong
base
• For an 0.10 M solution of NaOH,
• [Na+] = [OH-] = 0.10
• pOH = 1.0
• pH = 13.0
Example 13.1
Measuring pH
• pH can be measured with a pH meter
• Translates [H+] into an electrical signal
• Signal is shown on an analog or digital meter
calibrated in pH units
Figure 13.4
pH Indicators
• Universal indicator
• Mixture of substances that change color
depending on the concentration of H+
• Less accurate than pH meter
• Depending on the indicator used, can display pH
over a narrow or wide range of [H+]
• Some plants can act as pH indicators
• Color of some flowers in plants is dependent on
the pH of the soil in which the plant is grown
Figure 13.5
Figure 13.6
Weak Acid Equilibrium Constants
• Weak acids ionize only partially
• Prototype reaction
• HB (aq) + H2O ⇌ H3O+ (aq) + B- (aq)
• Two types of species that behave as weak acids
1. Molecules with an ionizable hydrogen atom
• HNO2 (aq) + H2O ⇌ H3O+ (aq) + NO2- (aq)
2. Cations
• NH4+ (aq) + H2O ⇌ H3O+ (aq) + NH3 (aq)
Metal Cations as Acids
• Many metal cations act as weak acids in water
solution as well
• Zn(H2O)42+ (aq) + H2O ⇌ H3O+ (aq) Zn(H2O)3(OH)+ (aq)
• The bond that forms between the oxygen and the
metal ion weakens the O-H bond
• H+ is more easily ionized as a result of the
weakened bond
Equilibrium Constants for Weak Acids
• HB (aq) + H2O  H3O+ (aq) + B- (aq)
• Ka is the acid equilibrium constant
• Simplifying the above to HB (aq)  H+ (aq) + B- (aq)
 
[H ][B ]
Ka 
[HB ]
• Ka values are related to the weak acid strength

• The smaller Ka is, the weaker the acid is
Table 13.2
pKa
• pKa = -logKa
• The smaller pKa is, the stronger the acid
• pKa follows the trend for pH
Example 13.4
Example 13.5
Percent Ionization
• The percent ionization of a weak acid is defined as
[H  ]equilibrium
%ionization   100%
[HB ]initial
• For the calculation in example 13.5, the percent

ionization is about 12 %
• Note that the percent ionization depends on the
molarity of the weak acid
Figure 13.8 - % Ionization and Concentration
Example 13.6
Calculating [H+] in a Water Solution of a Weak
Acid
• We can use the process for calculating equilibrium
pressure for gaseous reactions that we looked at in
Chapter 12 to calculate the equilibrium concentration
of [H+] for a weak acid
• The relationship between [HB], [H+] and [B-] is given
in the equilibrium expression itself
Algebra Review – Quadratic Equations
• Recall that for a quadratic equation in the form
2
ax  bx  c  0
• The roots are
2
 b  b  4ac
x
2a
Example 13.7
Approximations Used in Calculations
• The value of Ka is usually
known no more accurately
than about ±5%
• When solving for the
unknowns used to work the 2
x
equilibrium problem, for the Ka 
expression ax
• Where a is the initial

concentration of weak acid, x
you can neglect x in the if  0.05, then
a
denominator if doing so
does not introduce an error ax a
of more than 5%, i.e.,
Approximations and Percent Ionization
• When
x [H  ]eq

a [HB ]o
• Multiplying by 100% will give the percent ionization:

x [H  ]eq
%  100%
a [HB ]o
• If the percent ionization is 5% or less, you may make
the approximation.
• If the percent ionization is greater than 5%, the
quadratic formula or the successive approximation
method is required
Example 13.8
Polyprotic Weak Acids
• Acids containing more than one ionizable hydrogen
are called polyprotic
• The anion formed in one step produces another
H+ in a successive ionization step
• The equilibrium constant becomes smaller with
each successive step
Triprotic Acid
• Phosphoric acid
• H3PO4 (aq) ⇌ H+ (aq) + H2PO4- (aq)
Ka1
• H2PO4- (aq) ⇌ H+ (aq) + HPO42- (aq) Ka2
• HPO42- (aq) ⇌ H+ (aq) + PO43- (aq) Ka3
• Ka1 > Ka2 > Ka3

• With each successive step, the acid becomes
progressively weaker
Table 13.3
Example 13.9
Weak Bases and their Equilibrium Constants
• Types of weak bases

• Molecules
• Ammonia, NH3, and amines
• NH3 (aq) + H2O ⇌ NH4+ (aq) + OH- (aq)
• Anions
• Anions derived from weak acids are weak bases
• I- (aq) + H2O ⇌ HI (aq) + OH- (aq)
Example 13.10
Weak Base Equilibrium Constant
• NH3 (aq) + H2O  NH4+ (aq) + OH- (aq)
• The base equilibrium constant, Kb is

[NH 4 ][OH  ]
Kb 
[NH 3 ]
• For a generic weak base where

• B (aq) + H2O  HB+ (aq) + OH- (aq)
[HB  ][OH  ]
Kb 
[B ]
Kb by the Numbers
• As Kb becomes larger, base strength increases
• As with acids and Ka, we can define a pKb:
• pKb = -logKb
• As pKb becomes smaller, base strength increases
Calculation of [OH-] in a Weak Base Solution
• The process of calculating the [OH-] in a weak base

solution is the same as the process for calculating
[H+] in a weak acid solution
Example 13.11

Acid-Base Equlibria

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William L Masterton

Edward J. Neth • University of Connecticut

• H2O ⇌ H+ (aq) + OH- (aq)

• The higher the pH, the less acidic the solution

• The higher the pOH, the more basic the solution

• Ka values are related to the weak acid strength

• The percent ionization of a weak acid is defined as

• For the calculation in example 13.5, the percent

• The roots are

• Where a is the initial

• Multiplying by 100% will give the percent ionization:

• Ka1 > Ka2 > Ka3

• Types of weak bases

• For a generic weak base where

• The process of calculating the [OH-] in a weak base

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