Acid-Base Titrations

Introduction to Acids and

Bases
Chapter 8
There are three (3) definitions of acids and bases: 1. Arrhenius, 2.
Bronsted-Lowry and 3. Lewis.

Name Acids Base

Definition Example Definition Example
Arrhenius An H-containing HCl An OH-containing KOH
compound that HNO3 compound that NaOH
increases H+ HBr increases OH-
concentration in HF concentration in
water Acetic acid water
Bronsted- Proton donor Terminal Proton acceptor NH3
Lowry alkynes
Lewis Electron pair Fe3+ and other Electron pair donor
acceptor transition
metal cations
There are three (3) definitions of acids and bases: 1. Arrhenius, 2.
Bronsted-Lowry and 3. Lewis.

base acid acid base

conjugate conjugate
base acid
acid base

Conjugate acid-base pairs differ by only one proton.

There are three (3) definitions of acids and bases: 1. Arrhenius, 2.
Bronsted-Lowry and 3. Lewis.

Arrhenius
Arrhenius
Bases:
Acids:
LiOH,
HCl, H2SO4
Mg(OH)2

Bronsted Bases: Bronsted Acids:

H2O, NH3, HS- H2O, HS-, H2PO4-

Lewis Bases: Lewis Acids:

Any species with a Any species that
lone pair accepts electron
pairs. (H+ CO2, Mn+)
 Acids and Bases undergo neutralization reactions.

NaOH + HCl  NaCl + H2O

Na+ + OH– + H+ + Cl–  Na+ + Cl– + H2O
H+ + OH–  H2O
Acids and Base strengths are defined by how much H3O+ or OH- is
produced by a given concentration

Strong Acid Weak Acid

Acids and Base strengths are defined by how much H3O+ or OH- is
produced by a given concentration

Ionized acid concentration at equilibrium

percent ionization = x 100%
Initial concentration of acid

For a monoprotic acid HA

[H+]eq
Percent ionization = x 100% [HA]0 = initial concentration
[HA]0
 Weak acids and bases are in equilibrium with their original
species.

CH3COOH + H2O H3O+ +CH3COO–

Kc 
H O CH COO 
3

3


Kc << 1
H2OCH3COOH 

KcH2O 
 3  3
H O 
CH COO

CH3COOH 

Ka 
 3  3
H O 
CH COO


CH3COOH 
 Weak acids and bases are in equilibrium with their original
species.

NH3 + H2O NH4+ +OH–

Kc 
 NH4


 
OH 
Kc << 1
H 2ONH3 

KcH O 
NH OH  4
 


2
NH3 

Kb 

NH4


 
OH 

NH3 
Ka and Kb tells us something about the relative acid/base
strengths
Ka and Kb tells us something about the relative acid/base
strengths
Water can act both as an acid and a base (AUTOIONIZATION)

Kc 
H O OH 
3
 
The ion-product constant
H 2O (Kw) is the product of the
2
concentration of H3O+ and
KcH2O  H3O OH 
 
2
OH– ions at a particular
temperature
Kw  H3O 
OH 

At 250C
Kw = [H3O+][OH-] = 1.0 x 10-14
The p-scale conveniently handles a wide range of concentrations


pH   log[ H 3O ]

pOH   log[ OH ]
pKw   log Kw pKa   log Ka
Solving weak acid ionization problems:
1. Identify the major species that can affect the pH.
• In most cases, you can ignore the autoionization of
water. [H3O+] from water is negligible in comparison
to [H3O+] from the weak acid.
• Ignore [OH-] because it is determined by [H+].
2. Use ICE to express the equilibrium concentrations in
terms of single unknown x.
3. Write Ka in terms of equilibrium concentrations. Solve
for x by the approximation method. If approximation is
not valid, solve for x exactly.
4. Calculate concentrations of all species and/or pH of the
solution.
 Exercises
 What is the pH of a 0.5 M HF solution (at 25°C, Ka = 7.1
x 10-4)?

 What is the pH of a 0.05 M HF solution?

 What is the pH of a 0.122 M monoprotic acid whose Ka

is 5.7 x 10-4?
 Complete the following table:

Parameter An NaOH A 0.30 M

solution HNO3
pH 9.52
pOH
[H3O+]
[OH-]
 Complete the following table:

Parameter An NaOH A 0.30 M

solution HNO3
pH 9.52 0.52
pOH 4.48 13.48
[H3O+] 3.0 x 10-10M 0.30 M
[OH-] 3.3 x 10-5 M 3.3 x 10-14
M
 Exercises
 What is the pH, [H3O+], [OH-] of 7.52 x 10-4 M CsOH?

 What is the pOH, [H3O+], [OH-] of 1.59 x10-3 M HClO4?

 What is the [H3O+], [OH-] and pOH in a solution with a

pH of 2.77

 What is the [H3O+], [OH-] and pH in a solution with a

pOH of 11.27
 Exercises
 Chloroacetic acid has a pKa of 2.87. What are [H3O+],
pH, [ClCH2COOH], [ClCH2COO-] in 1.05 M
[ClCH2COOH]

 A 0.735 M of weak acid is 12.5% dissociated. Calculate

[H3O+], pH, [OH-], pOH of solution. Calculate Ka of
acid
Buffers
Chapter 9
Buffers solutions are solutions that resist changes in pH
Buffers contain appreciable amounts of a weak acid and its
conjugate base

HA/A–

NH4Cl/NH3 HBr/KBr
H3PO4/NaH2P H3IO3/Li2HIO3
O4 NaOH/Na2O
NH4SH/Na2S
HCOOH/HCO
OK
Buffers contain appreciable amounts of a weak acid and its
conjugate base

What do we mean by appreciable?

o A 50-mL solution of 0.25 M Acetic acid.
o A 50-mL solution of 0.25 M Sodium
Acetate
o A solution containing 0.125 M Acetic acid
and 0.125 M Acetate
HA /A– ** If we take the ratio
of base to acid or acid
to base, it should be
within 10% of each
other
+ base + acid
 Buffers work because there are weak acids and weak
bases present to counter-act small amounts of acid/bases.
 The effectivity (and pH) of the buffer is dependent on the
ratio between the weak acid and its conjugate base

Ka 
 3  
H O 
A H O A 
log Ka  log 
3

HA  HA  
 

log Ka  log H O  log

 A 


3
HA
pKa  pH  log
 A  

Henderson- HA
 Hasselbach
Equation: pH  pKa  log
A  

HA

The effectivity (and pH) of the buffer is dependent on the
ratio between the weak acid and its conjugate base

pH  pKa  log
A  

HA
o A 0.25 M Acetic acid buffer with pH 4.74
o A 0.25 M Acetic acid buffer with pH 5.10
o A 0.25 M Acetic acid buffer with pH 4.40

0.1 
A 


 10
** If we take the ratio of
base to acid or acid to
HA base, it should be within
10% of each other
pH  pKa  1
BUFFER RANGE
The effectivity (and pH) of the buffer is dependent on the
ratio between the weak acid and its conjugate base

o A buffer for pH 10.00

o A buffer for pH 4.00
o A buffer for pH 7.00
The closer the pH of the buffer to the pKa the better
 The effectivity (and pH) of the buffer is also dependent on
the total amount of weak acid and conjugate base.

pH  pKa  log
 
A o A 1.00 M Acetic acid buffer
with pH 4.74
HA o A 0.30 M Acetic acid buffer
with pH 4.74
o A 0.10 M Acetic acid buffer
with pH 4.74
o A 0.030 M Acetic acid
buffer with pH 4.74
 Buffer Capacity is the measure of the ability of a buffer
to resist pH Changes

pH  pKa  log
A  

HA
pH  pKa  1

GOOD BUFFER RANGE + appreciable amounts

(High Concentration)…
 Buffers work through a phenomenon known as the common
ion effect

What is the common ion effect?

This effect occurs when a reactant containing a given
ion is added to an equilibrium mixture that already
contains that ion, and the position of equilibrium shifts
away from forming more of it
 Preparation of Buffers

1. Choose the conjugate acid-base pair

2. Calculate the ratio of the buffer component
concentrations
3. Determine the buffer concentration
4. Mix the solution and adjust pH
Buffers can be prepared using a weak acid and the salt of its
conjugate base (or a weak base and the salt of its conjugate
acid).

Example 1
Preparing a pH 10.00 carbonate buffer. How many
grams of Na2CO3 must one add to 1.5 L of freshly
prepared 0.20 M NaHCO3 to make the buffer? Ka of
HCO3- is 4.7 x 10-11
Example 2
Prepare a 50-mL of 0.12 M Acetic acid buffer with
equal concentrations of acetic acid and acetate from
3.00 M acetic acid stock solution and sodium acetate
salt
Buffers can also be prepared by using a weak acid (or
weak base) then add a strong base (or acid) to desired
pH.

5.0 g of CH3COONa is dissolved in 100. mL of

water. How many mL of 0.50 MHCl should be
added to form a buffer with pH 4.90? Will
diluting the final mixture to 500 mL affect the
pH of the buffer? What is affected by dilution?
Acid-Base Titrations
Chapter 10
In an acid-base reaction, the key parameter that changes in the
system is pH.

Example:

A 40.00 mL sample of 0.1000 M HCl solution

was titrated with 0.1000 M NaOH solution.

Calculate the pH when the following volume

of the NaOH is added.
a) 0.00 f) 39.00
b) 10.00 g) 40.00
c) 20.00 h) 41.00
d) 30.00 i) 45.00
e) 35.00 j) 50.00
In an acid-base reaction, pH is monitored through colored
indicators.
Acid-base indicators are usually weak acids (HIn) which have
different color than its conjugate base (In-).

basic
change
occurs over
acidic
~2 pH units
Acid-base indicators are usually weak acids (HIn) which have
different color than its conjugate base (In-).
TITRATION OF A STRONG
ACID BY A STRONG BASE

40 mL of 0.1000 M HCl
 TITRATION OF A WEAK
ACID BY A STRONG BASE

REGION 1: Before
addition (weak acid)

REGION 2: Before
Equivalence point
(buffer)

REGION 3: At
Equivalence point
(weak base)

REGION 4: After
Equivalence point
(strong base)
 TITRATION OF A WEAK
ACID BY A STRONG BASE

EXAMPLE in Book: Titration of 50.00 mL of 0.0200 M MES

(pKa = 6.27) with 0.1000 M NaOH

REGION 1: Before addition (weak acid)

REGION 2: Before Equivalence point (buffer)

REGION 3: At Equivalence point (weak base)

REGION 4: After Equivalence point (strong base)

 TITRATION OF A WEAK
BASE BY A STRONG ACID

REGION 1: Before
addition (weak base)

REGION 2: Before
Equivalence point
(buffer)

REGION 3: At
Equivalence point
(weak acid)

REGION 4: After
Equivalence point
(strong acid)
 TITRATION OF A WEAK
BASE BY A STRONG ACID

Example in Book: Titration of 25.00 mL of 0.08364 M pyridine

(Kb = 1.6 x 10-9) with 0.1067 M HCl.

REGION 1: Before addition (weak base)

REGION 2: Before Equivalence point (buffer)

REGION 3: At Equivalence point (weak acid)

REGION 4: After Equivalence point (strong acid)

 TITRATION OF A
POLYPROTIC SYSTEMS
 TITRATION OF A
POLYPROTIC SYSTEMS