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FOUNDATION CHEMISTRY II

CHM096

CHAPTER 4
ACIDS AND
BASES

TOPICS
4.1

Definitions Acids and Bases

4.2

Strength of Acids and Bases

4.3

pH- A Measure of Acidity

4.4

The Acid-Base Properties of Ions and Salts

4.5

Buffer Solutions

4.6

Acid Base Titration Curve

4.7

Indicators
2

TOPIC
4.1 DEFINITIONS OF ACIDS AND BASES

4.1

Definitions Acids and Bases


Properties of Acids

Sour taste
React with active metals
i.e., Al, Zn, Fe, but not Cu, Ag, or Au

2 Al + 6 HCl

2 AlCl3 + 3 H2

corrosive
React with carbonates, producing CO2
marble, baking soda, chalk, limestone

CaCO3 + 2 HCl CaCl2 + CO2 + H2O


Change color of vegetable dyes
blue litmus turns red
React with bases to form ionic salts

Common Acids

4.1

Definitions Acids and Bases


Structures of Acids

Binary acids have acid hydrogens attached to a


nonmetal atom
HCl, HF

Oxy acids have acid hydrogens attached to an


oxygen atom
H2SO4, HNO3

4.1

Definitions Acids and Bases


Structures of Acids

Carboxylic acids have

COOH group
HC2H3O2, H3C6H5O7
Only the first H in the
formula is acidic
the H is on the
COOH

4.1

Definitions Acids and Bases


Properties of Bases

Also known as alkalis


Taste bitter
alkaloids = plant product that is
alkaline
often poisonous
Solutions feel slippery
Change color of vegetable dyes
different color than acid
red litmus turns blue
React with acids to form ionic salts
neutralization

Common Bases

4.1

Definitions Acids and Bases


Structure of Bases

Most ionic bases contain OH ions


NaOH, Ca(OH)2
Some contain CO32 ions
CaCO3 ,NaHCO3
Molecular bases contain structures that react with H+
mostly amine groups -e.g CH3CH2NH2

4.1

Definitions Acids and Bases


Arrhenius Theory

An acid is a substance that, when dissolved in water,


increases the concentration of hydrogen ions.
A base is a substance that, when dissolved in water,
increases the concentration of hydroxide ions.

11

4.1

Definitions Acids and Bases


Arrhenius Theory

NaOH dissociates in water,


HCl ionizes in water,
producing H+ and Cl ions producing Na+ and OH ions
12

4.1

Definitions Acids and Bases


Arrhenius Theory

Hydronium Ion
The H+ ions produced by the acid are so reactive they
cannot exist in water
H+ ions are protons!!

Instead, they react with water molecules to produce


complex ions, mainly hydronium ion, H3O+

H+ + H2 O H3 O +

13

4.1

Definitions Acids and Bases


Arrhenius Theory

Arrhenius Acid-Base Reaction


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-O-H

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)

14

4.1

Definitions Acids and Bases


Arrhenius Theory

Exercise 1
a) Which of the following are Arrhenius acids?
NaHSO4, HI, NaH, H3PO3
a) Which of the following are Arrhenius bases?
H3AsO4, HClO, KOH, H2NNH2

15

4.1

Definitions Acids and Bases


Arrhenius Theory

Limitations of Arrhenius Acid-Base Theory

Does not explain why molecular substances, such as


NH3, dissolve in water to form basic solutions even
though they do not contain OH ions
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
Does not explain why molecular substances, such as
CO2, dissolve in water to form acidic solutions even
though they do not contain H+ ions
Does not explain acidbase reactions that take place in
non-aqueous solution or in the absence of water
16

4.1

Definitions Acids and Bases


Brnsted-Lowry Theory

In a Brnsted-Lowry acidbase reaction,


a proton (H+) is transferred
An acid is a proton donor, must have a removable
(acidic) proton.
A base is a proton acceptor, must have a pair of
nonbonding electrons.
In a Brnsted-Lowry acid-base reaction, the acid
molecule gives an H+ to the base molecule
HA + :B :A + HB+
17

4.1

Definitions Acids and Bases


Brnsted-Lowry Theory

Brnsted-Lowry Acid
Brnsted-Lowry acids are H+ donors

any material that has H can potentially be a Brnsted-Lowry acid

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

18

4.1

Definitions Acids and Bases


Brnsted-Lowry Theory

Brnsted-Lowry Bases
Brnsted-Lowry bases are H+ acceptors

any material that has atoms with lone pairs can potentially be a
Brnsted-Lowry 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

19

4.1

Definitions Acids and Bases


Brnsted-Lowry Theory

Amphoteric Substances
Amphoteric substances can act as either an acid or a
base
because they have both a transferable H and an atom with
lone pair electrons

Water acts as base, accepting H+ from HCl


HCl(aq) + H2O(l) Cl(aq) + H3O+(aq)
Water acts as acid, donating H+ to NH3
NH3(aq) + H2O(l) NH4+(aq) + OH(aq)
Therefore, water is amphoteric

20

4.1

Definitions Acids and Bases


Brnsted-Lowry Theory

Brnsted-Lowry Acid-Base Reactions


One of the advantages of Brnsted-Lowry theory is that
it allows reactions to be reversible
HA + :B :A + HB+
The original base has an extra H+ after the reaction, so it
will act as an acid in the reverse process
And the original acid has a lone pair of electrons after
the reaction so it will act as a base in the reverse
process
:A + HB+ HA + :B

21

4.1

Definitions Acids and Bases


Brnsted-Lowry Theory

Conjugate Acids and Bases


The term conjugate comes from the Latin word
conjugare, meaning to join together.
Reactions between acids and bases always yield their
conjugate bases and acids.

For the reaction: HA + :B :A + HB+


:A is the conjugate base of HA
HB+ is the conjugate acid of :B

22

4.1

Definitions Acids and Bases


Brnsted-Lowry Theory

Conjugate Acids and Bases

23

4.1

Definitions Acids and Bases


Brnsted-Lowry Theory

Conjugate Acids and Bases


H2O and HO constitute an
acid/conjugate base pair

NH3 and NH4+ constitute a


base/conjugate acid pair

24

4.1

Definitions Acids and Bases


Example 1

Write the formula for the conjugate acid of the following

H2O

H3O+

NH3

NH4+

CO32

HCO3

H2PO41

H3PO4
25

4.1

Definitions Acids and Bases


Example 2

Write the formula for the conjugate base of the following

H2O

HO

NH3

NH2

CO32

because CO32 does not have an H,


it cannot be an acid

H2PO41

HPO42
26

4.1

Definitions Acids and Bases


Exercise 2

Identify the Brnsted-Lowry acids and bases, and their


conjugates, in the reaction
a.

HSO4(aq) + HCO3(aq) SO42(aq) +

b.

HCO3 (aq) + H2O

H2CO3 (aq) +

H2CO3(aq)

HO (aq)

27

4.1

Definitions Acids and Bases


Exercise 3

Write the equations for the following species react with


water and label the conjugate acid and base
a) H2PO4-

b) HClO2
c) CH3NH2
d) C6H5NH3+

28

4.1

Definitions Acids and Bases


Conclusion

Comparing Arrhenius and Brnsted-Lowry Theory


Arrhenius theory
HCl(aq) H+(aq) + Cl(aq)
HF(aq) H+(aq) + F(aq)

BrnstedLowry theory
HCl(aq) + H2O(l) Cl(aq) + H3O+(aq)
HF(aq) + H2O(l) F(aq) + H3O+(aq)

NaOH(aq) Na+(aq) + OH(aq)

NaOH(aq) Na+(aq) + OH(aq)

NH4OH(aq) NH4+(aq) +
OH(aq)

NH3(aq) + H2O(l) NH4+(aq) +


OH(aq)

29

4.1

Definitions Acids and Bases


Lewis Acids-Bases Theory

Lewis AcidBase theory focuses on transferring an


electron pair
lone pair bond
Does NOT require H atoms

The electron donor is called the Lewis Base


electron rich, therefore nucleophile (Nu- )

The electron acceptor is called the Lewis Acid


electron deficient, therefore electrophile (E+)

30

4.1

Definitions Acids and Bases


Lewis Acids-Bases Theory

Lewis Acid
Lewis acids are defined as electron-pair acceptors.
Atoms with an empty valence orbital can be Lewis
acids.

31

4.1

Definitions Acids and Bases


Lewis Acids-Bases Theory

Lewis Bases
Lewis bases are defined as electron-pair donors.

Anything that could be a Brnsted-Lowry base is a


Lewis base.

32

4.1

Definitions Acids and Bases


Lewis Acids-Bases Theory

Lewis Bases
Anions are better Lewis Bases than neutral atoms or
molecules
N: < N:
Generally, the more electronegative an atom, the less
willing it is to be a Lewis Base
O: < S:

33

4.1

Definitions Acids and Bases


Lewis Acids-Bases Theory

Lewis Acids-Bases Reaction


The base donates a pair of electrons to the acid
Generally results in a dative bond forming
H3N: + BF3 H3NBF3
No H transfer

The product that forms is called an adduct


Arrhenius and Brnsted-Lowry acidbase reactions are
also Lewis acidbase reactions

34

4.1

Definitions Acids and Bases


Lewis Acids-Bases Theory

Molecules as Lewis Acids


Lewis Acids with Electron-Deficient Atoms

35

4.1

Definitions Acids and Bases


Lewis Acids-Bases Theory

Molecules as Lewis Acids


Lewis Acids with Polar Multiple Bonds

H O H

O H
S
H O O

Acid

Base

Adduct
36

4.1

Definitions Acids and Bases


Lewis Acids-Bases Theory

Metal Cations as Lewis Acids


M2+ + 6H2O
+
Lewis
Acid

M(H2O)6 2+ (aq)

6
Lewis
Base
Adduct

Lone electron pairs on the O atoms of water form


covalently bonds to the positively charged ion
37

4.1

Definitions Acids and Bases


Lewis Acids-Bases Theory

Metal Cations as Lewis Acids


Ag+(aq) + 2 :NH3(aq) Ag(NH3)2+(aq)
Lewis
Acid

Lewis
Base

Adduct

Ag+ ion acts as a Lewis acid when it dissolves in water:


Ammonia is a stronger Lewis base than water because it
displaces H2O from a hydrated ion when aqueous NH3 is
added.
38

4.1

Definitions Acids and Bases


Example 4

Identify the Lewis Acid and Lewis Base in Each Reaction

Lewis
Base

Lewis
Acid

Lewis
Base

Lewis
Acid

39

4.1

Definitions Acids and Bases


Exercise 4

Identify the Lewis Acid and Lewis Base in Each Reaction

a) H+ + OH-

H2O

b) Cl- + BCl3

BCl4-

c) K+ + 6H2O

K(H2O)6 +

40

TOPIC
4.2 STRENGTH OF ACIDS AND BASES

41

4.2

Strength of Acids and Bases


Strong or Weak

A strong acid is a strong electrolyte


practically all the acid molecules ionize,
A strong base is a strong electrolyte
practically all the base molecules form OH ions,
either through dissociation or reaction with water,
A weak acid is a weak electrolyte
only a small percentage of the molecules ionize,
A weak base is a weak electrolyte
only a small percentage of the base molecules form
OH ions, either through dissociation or reaction with
water,
42

4.2

Strength of Acids and Bases


Strong Acid

Strong acids are


completely dissociated in
water.

HCl H+ + Cl
HCl + H2O H3O+ + Cl

Willing to donate H+
100% ionized in water
Strong electrolyte

Their conjugate bases


has a negligible tendency
to be protonated.
[H3O+] = [strong acid]
[X] means the molarity of X

0.10 M HCl = 0.10 M H3O+


43

4.2

Strength of Acids and Bases


Weak Acid

Weak acid only


dissociate partially in
water.
Donate a small fraction of
their H+
Less than 1% ionization to
water

HF H+ + F
HF + H2O H3O+ + F

Their conjugate bases


are weak bases.- slight
ability to remove protons
from water

[H3O+]

<< [weak acid]

0.10 M HF 0.10 M H3O+


44

4.2

Strength of Acids and Bases


Acid Ionization Constant, Ka

Acid strength measured by the size of the equilibrium


constant when reacts with H2O

HA(aq) + H2O() A(aq) + H3O+(aq)


The equilibrium constant for this reaction is called the
acid ionization constant, or acid dissociation
constant, Ka

[H3O+] [A-]
larger Ka = stronger acid Ka =
[HA]

45

4.2

Strength of Acids and Bases


Weak Acids

46

4.2

Strength of Acids and Bases


Negligible Acidity

Substances with negligible acidity do not dissociate in


water. Example CH4, contains H but does not
demonstrate any acidic behavior.
Their conjugate bases are exceedingly strong.

47

4.2

Strength of Acids and Bases


Exercise 5

Arrange in the increasing order of acidic strength


Acids

Acid dissociation constant, Ka

HCN
CH3COOH
HF
HBrO

7.2 x 10-10
1.8 x 10-5
6.7 x 10-4
2.5 x 10-9

48

4.2 Strength of Acids and Bases


Relative Strengths of Acids and Bases
We can think of proton transfer reactions as being
governed by the relative abilities of two bases to
abstract protons

HX (aq) + H2O (l)

H3O+ (aq) + X- (aq)

If H2O (the base in the forward reaction) is a much


stronger base than X- (the conjugate base of HX), then
H2O will abstract the proton from HX to produce H3O+
and XAs a result, the equilibrium will lie to the right. This
describes the behavior of a strong acid in water.
49

4.2

Strength of Acids and Bases

Relative Strengths of Acids and Bases


In any acid-base reaction, the equilibrium will favor the
reaction that moves the proton to the stronger base.

HCl (aq) + H2O (l) H3O+ (aq) + Cl- (aq)


H2O is a much stronger base than Cl-, so the equilibrium
lies so far to the right that K is not measured (K>>1)

50

4.2

Strength of Acids and Bases

Relative Strengths of Acids and Bases


When X- is a stronger base than H2O, the equilibrium will
lie to the left. This situation occurs when HX is a weak
acid

CH3CO2H (aq) + H2O (l) H3O+ (aq) + CH3CO2- (aq)


Acetate is a stronger base than H2O, so the equilibrium
favors the left side (K<1)
Conclusion: in every acid-base reaction the position of
the equilibrium favors transfer of the proton from the
stronger acid to the stronger base to form the weaker
acid and the weaker base
51

4.2

Strength of Acids and Bases

Examples of Strong and Weak Acids

52

4.2

Strength of Acids and Bases

53

4.2

Strength of Acids and Bases


Example 6

HSO4(aq) +

CO3(aq) SO42(aq) +

HCO3- (aq)

For the following proton-transfer reaction, use table to


predict whether the equilibrium lies predominantly to
the left (that is Kc < 1) or to the right (Kc >1)

54

4.2

Strength of Acids and Bases


Answer

CO32- appears lower in the right-hand column in Figure


16.4 and is therefore a stronger base than SO42-. CO32-,
therefore will get the proton preferentially to become
HCO3-, while SO42- will remain mostly unprotonated. The
resulting equilibrium will lie to the right favoring
products (that Kc >1)

55

4.2

Strength of Acids and Bases


Exercise 6

For each the following reactions, use table 16.4 to


predict whether the equilibrium lies predominantly to the
left or to the right
HPO42-(aq) +

H2O (l) H2PO4(aq) +

OH- (aq)

NH4+(aq) + OH (l) NH3 (aq) + H2O (aq)

56

4.2

Strength of Acids and Bases


Strong Bases

Bases react with water to produce hydroxide ion.


The most common soluble strong bases are the ionic
hydroxides of the alkali metal.
Metals from group 1A and 2A

NaOH, KOH completely dissociate into ions in aqueous


solution
0.3M NaOH consists of 0.3 M Na+ and 0.3 M OH57

4.2

Strength of Acids and Bases


Strong Bases

LiOH, RbOH are not commonly encountered in the


laboratory
Ca(OH)2, Sr(OH)2, Ba(OH)2 have limited solubilities
Ionic metal oxides, Na2O and CaO
The O2- reacts with water to form OH-, leaving virtually
no O2- remaining in the solution.
O2- (aq) + H2O (l) 2OH- (aq)
58

4.2

Strength of Acids and Bases


Weak Bases

In weak bases, only a small fraction of molecules accept


Hs
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

59

4.2

Strength of Acids and Bases


Weak Bases
NH3 + H2O NH4+ + OH

60

4.2

Strength of Acids and Bases


Base Ionization Constant, Kb

Base strength measured by the size of the equilibrium


constant when a base B reacts with H2O
:B- + H2O OH + H:B+
The equilibrium constant is called the base ionization
constant, Kb
larger Kb = stronger base

The equilibrium constant


expression for this reaction is

[H:B+] [OH-]
Kb =
[:B-]
61

4.2

Strength of Acids and Bases


Weak Bases

62

4.2 Strength of Acids and Bases


Classifying the Relative Strengths of
Acids and Bases
Strong acids. Two types of strong acids, with examples
that you should memorize, are
The hydrohalic acids, HCl, HBr, and HI
Oxoacids in which the number of O atoms exceeds the number of
ionizable protons by two or more, such as HNO3, H2SO4,and
HClO4; for example, in H2SO4, 4 Os -2Hs = 2

63

4.2 Strength of Acids and Bases


Classifying the Relative Strengths of
Acids and Bases
Weak acids. There are many more weak acids than
strong ones. Four types, with example, are
The hydrohalic acid HF
Those acids in which H is not bonded to O or to halogen, such as
HCN and H2S
Oxoacids in which the number of O atoms, equals or exceeds by
one the number of ionizable protons,such as HClO, HNO2 and H3PO4

Carboxylic acids (general formula RCOOH) such as CH3COOH


64

4.2 Strength of Acids and Bases


Classifying the Relative Strengths of
Acids and Bases
Strong bases. Water-soluble compounds containing O2or OH- ion are strong bases. The cations are usually
those of the most active metals
M2O or MOH, where M = Group 1A (1) metal (Li, Na, K, Rb, Cs)

MO or M(OH)2 where M= Group 2A (2) metal (Ca, Sr, Ba)


[MgO and Mg(OH)2 are only slightly soluble in water, but the soluble
portions dissociates completely]

65

4.2 Strength of Acids and Bases


Classifying the Relative Strengths of
Acids and Bases
Weak bases. Many compounds with an electron-rich
nitrogen atom are weak bases (none are Arrhenius
bases). The common structural features is an N atom that
has a lone electron pair
Ammonia (NH3)
Amines (general formula RNH2, R2NH, or R3N), such as
CH3CH2NH2, (CH3)2NH, (C3H7)3N and C5H5N

66

4.2

Strength of Acids and Bases

Factors Affecting Acid Strength

67

4.2

Strength of Acids and Bases

Factors Affecting Acid Strength


The more polar the H-X bond and /or the weaker the H-X
bond, the more acidic the compound

So acidity increases from left to right across a row and


from top to bottom down a group

68

4.2 Strength of Acids and Bases


Factors Affecting Acid Strength
In oxyacids, in which an OH is bonded to another atom,
Y, the more electronegative Y is, the more acidic the acid

4.2

Strength of Acids and Bases

Factors Affecting Acid Strength

For a series of oxyacids, acidity increases


with the number of oxygens.
70

4.2

Strength of Acids and Bases

Factors Affecting Acid Strength


Resonance in the conjugate bases of carboxylic acids
stabilizes the base and makes the conjugate acid more
acidic

71

4.2

Strength of Acids and Bases


Exercise 7

Classify each of the following compounds as a strong


acid, weak acid, strong base, and weak base
a) H2SeO4
b) (CH3)2CHCOOH
c) KOH
d) (CH3)2CHNH2
72

4.2

Strength of Acids and Bases


Degree of Dissociation ()

Degree of dissociation is the fraction of the original solute


molecules that have dissociated or refer to the amount of solute
dissociated into ions per mole of molecules.
Figure below shows that the percentage dissociation of ethanoic
acid (CH3COOH) increases as the concentration decreases. The
percentage dissociation is defined as below
6.0

% dissociation

% dissociation = [HA] dissociated X 100


[HA] initial

5.0
4.0
3.0
2.0
1.0

0.05

0.10

0.15

Concentration of CH3COOH (M)


73

4.2

Strength of Acids and Bases


Degree of Dissociation ()

The relationship between concentration, the degree of dissociation and the


dissociation constant of a weak acid or a weak base can be derived as
shown below
(a) Consider a 1 dm3 solution of a weak acid HA with a concentration of c
mol dm-3
(b) If the degree of dissociation is , the concentration of undissociated acid
at equilibrium would be c(1-), we thus have
HA (aq) A- (aq) +
H+ (aq)
Initial (mol)
At equilb
Ka = [A-][H+]
[HA]

c(1- )

Ka = [c][c] = Ka = c2
c(1-)
(1-)
The above expression is known as the Ostwald dilution law. It can also be
applied to weak bases
Kb = c2
(1-)
74
=

4.2

Strength of Acids and Bases


Degree of Dissociation ()

For a weak acid , is very small


1 - 1 Ka = 2c
= Ka/c
[H+] = c = cKa/c = Kac

[H+] = c or [H+] = Kac

similar to weak base or [OH-] = c [OH-] = Kbc

The above equation show that the degree of dissociation at a given


temperature depends on the concentration of the given acid or base.

As the concentration of a weak acid or weak base decreases, the degree


of dissociation increases.
For example, at 298 K, of 0.100M CH3COOH is 1.34% but 0.0001M
CH3COOH is 13.4%

Thus, is not suitable to measure the strength of acid-base, but Ka or Kb


is suitable because the values of Ka or Kb do not change with
75
concentration at a constant temperature.

4.2

Strength of Acids and Bases


Degree of Dissociation ()

The formula [H+] = c or [H+] = Kac or [OH-] = c [OH-] = Kbc


Is important because the concentration of H+ for weak acid and OH- for
weak base can be calculated if the the value or Ka/Kb is given
Example
a) At 298 K, the degree of dissociation of 0.125M benzoic acid (C6H5COOH)
is 2.20 %. Calculate the dissociation constant, Ka
b) Calculate the degree of dissociation of the 0.1 M of ammonia solution
(Kb for ammonia at 298 K is 1.75 x 10-5)

Solution
a) Ka = c2 = 0.125 (0.022)2 = 6.19 x 10-5
(1-)
1- 0.022

b) [OH-] = Kbc = 1.75 x 10-5 x 0.1 = 1.32 x 10-3


[OH-] = c , thus = [OH-]/c = 1.32 x 10-3 / 0.1 = 0.0132 or 1.32%

76

4.2

Strength of Acids and Bases


Exercise 8

A 250 cm3 solution contains 0.123 mole of HF. Calculate


the degree of dissociation of HF if the Ka HF at 25 oC is
3.53 x 10-4

If the degree of dissociation of C2H5NH2 solution at


25oC is 1.25% and Kb is 5.40 x 10-4. Determine the
concentration of [OH-] produced in that solution

77

4.2

Strength of Acids and Bases

Autoionization of Water and The pH Scale


Water is an extremely weak electrolyte
In pure water, a few molecules act as bases and a few act
as acids.
This is referred to as autoionization. About 2 out of 2
billions of water molecules through this process
All aqueous solutions contain both H3O+ and OH
the concentration of H3O+ and OH are equal in water

[H3O+] = [OH] = 107M @ 25 C


+

H2O (l)

H 2O ( l )

H3O+ (aq)

OH- (aq)

78

4.2 Strength of Acids and Bases


Ion Product Constant of Water
The equilibrium expression for this process is

Kw = [H3O+] [OH-]
This special equilibrium constant is referred to as the
ion-product constant for water,

Kw. At 25C, Kw = 1.0 10-14


As [H3O+] increases, the [OH] must decrease so the
product stays constant
79

4.2

Strength of Acids and Bases


Acidic and Basic Solutions

All aqueous solutions contain both H3O+ and OH ions


Neutral solutions have equal [H3O+] = [OH]
[H3O+] = [OH] = 1.00 x 107

Acidic solutions have a larger [H3O+] > [OH]


[H3O+] > 1.00 x 107; [OH] < 1.00 x 107

Basic solutions have a larger [OH] > [H3O+]


[H3O+] < 1.00 x 107; [OH] > 1.00 x 107

80

4.2

Strength of Acids and Bases


Acidic and Basic Solutions

Complete the table [H+] vs. [OH]


[H+] 100 101

+
H
OH

103

105

+
H
OH

107

+
H

109

1011

H+

OH OH

1013 1014
H+

OH

[OH]

81

4.2

Strength of Acids and Bases


Acidic and Basic Solutions
Complete the table [H+] vs. [OH]
Acid

[H+] 100 101

+
H
OH

103

Base

105

+
H
OH

[OH]1014 1013 1011

109

107

109

+
H

OH
107

1011

1013 1014
H+

H+

OH

OH
105

103

101 100

Even though it may look like it, neither H+ nor OH will


ever be 0
The sizes of the H+ and OH are not to scale
because the divisions are powers of 10 rather than units82

4.2

Strength of Acids and Bases


Acidic and Basic Solutions
Example 7

Calculate the [OH] at 25 C when the [H3O+] = 1.5 x 109


M, and determine if the solution is acidic, basic, or
neutral

83

4.2

Strength of Acids and Bases


Acidic and Basic Solutions
Answer

Given:
Find:
Conceptual Plan:

[H3O+] = 1.5 x 109 M


[OH]
[H3O+]

[OH]

Relationships:

Solution:

Check: the units are correct; the fact that the


[H3O+] < [OH] means the solution is basic
84

4.2

Strength of Acids and Bases


Acidic and Basic Solutions
Exercise 9

Determine the [H3O+] when the [OH] = 2.5 x 107 M

85

TOPIC
4.3 pH- A MEASURE OF ACIDITY

86

4.3

pH A Measure of Acidity

Definition
pH is defined as the
negative base-10 logarithm
of the concentration of
hydronium ion.
pH = -log [H3O+]

87

4.3

pH A Measure of Acidity
Definition

The acidity or basicity of a solution is often expressed as


pH
pH = log[H3O+]
exponent on 10 with a positive sign
pHwater = log[107] = 7
need to know the [H3O+] concentration to find pH

pH < 7 is acidic; pH > 7 is basic, pH = 7 is neutral

[H3O+] = 10pH

88

4.3

pH A Measure of Acidity
Definition

An acidic solution the [H3O+] > 1.0 x 10-7


Example: the pH of an acidic solution in which [H+] =
1.0 x 10-3
pH = -log(1.0 x 10-3) = -(-3.00) = 3.00

Conclusion: the pH decreases as [H+] increases


At 25oC the pH of an acidic solution is less than
7.00
89

4.3

pH A Measure of Acidity

[H3O+] and [OH] in a


Strong Acid or Strong Base Solution
There are two sources of H3O+ in an aqueous solution of
a strong acid the acid and the water
There are two sources of OH in an aqueous solution of
a strong acid the base and the water

For a strong acid or base, the contribution of the water


to the total [H3O+] or [OH] is negligible
the [H3O+]acid shifts the Kw equilibrium so far that [H3O+]water is
too small to be significant
except in very dilute solutions, generally < 1 x 104 M
90

4.3

pH A Measure of Acidity

Finding pH of a Strong Acid or


Strong Base Solution
For a monoprotic strong acid [H3O+] = [HA]
for polyprotic acids, the other ionizations can generally be
ignored
0.10 M HCl HAs [H3O+] = 0.10 M and pH = 1.00

For a strong ionic base, [OH] = (number OH)x[Base]


for molecular bases with multiple lone pairs available, only one
lone pair accepts an H, the other reactions can generally be
ignored
0.10 M Ca(OH)2 Has [OH] = 0.20 M and pH = 13.30
91

4.3

pH A Measure of Acidity
Example 8

Calculate the pH at 25 C when the [OH] = 1.3 x 102 M,


and determine if the solution is acidic, basic, or neutral

92

4.3

pH A Measure of Acidity
Answer

Given:
Find:
Conceptual Plan:

[OH] = 1.3 x 102 M


pH

[OH]

[H3O+]

pH

Relationships:

Solution:

Check: pH is unitless; the fact that the pH > 7


means the solution is basic

93

4.3

pH A Measure of Acidity
Exercise 10

Determine the pH @ 25 C of a solution that has [OH]


= 2.5 x 107 M

94

4.3

pH A Measure of Acidity
Example 9

Determine the [OH] of a solution with a pH of 5.40

95

4.3

pH A Measure of Acidity
Answer

Given:
Find:
Conceptual Plan:

pH = 5.40
[OH], M

pH

[H3O+]

[OH]

Relationships:

Solution:

Check: because the pH < 7, [OH] should be less than 1


x 107; and it is

96

4.3

pH A Measure of Acidity
Exercise 11

Consider two solutions, solution A and solution B. [H+]


in solution A is 500 times greater than in solution B.
What is difference in the pH values of the two
solutions?

97

4.3

pH A Measure of Acidity
pOH

Another way of expressing the acidity/basicity of a


solution is pOH
pOH = log[OH],

[OH] = 10pOH
pOHwater = log[107] = 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
98

4.3

pH A Measure of Acidity
pOH

99

4.3

pH A Measure of Acidity

Relationship between pOH and pH


pH + pOH = 14.00
at 25 C
you can use pOH to find pH of a solution

[H3O ][OH ] K w 1.0 1014


] 14.00

log
[H
O
]

log
[OH

log [H3O ][OH ] log 1.0 1014

pH pOH 14.00
100

4.3

pH A Measure of Acidity
Example 10

Calculate the pH at 25 C when the [OH] = 1.3 x 102 M,


and determine if the solution is acidic, basic or neutral

101

4.3

pH A Measure of Acidity
Answer

Given:
Find:
Conceptual Plan:

[OH] = 1.3 x 102 M


pH

[OH]

pOH

pH

Relationships:

Solution:

Check: pH is unitless; since t pH > 7, the solution


is basic
102

4.3

pH A Measure of Acidity
Example 12

Determine the pOH at 25 C of a solution that has


[H3O+] = 2.5 x 109 M

103

4.3

pH A Measure of Acidity
Answer

Given:
Find:
Conceptual Plan:

[H3O+] = 2.5 x 109 M


pOH
[H3O+]

pH

pOH

Relationships:

Solution:

Check: pH is unitless; the fact tHAt the pH < 7


means the solution is acidic

104

4.3

pH A Measure of Acidity
Example 12

Calculate the pH at 25 C of a 0.0015 M Sr(OH)2 solution


and determine if the solution is acidic, basic, or neutral
(Alterative Method)

105

4.3

pH A Measure of Acidity
Answer

[Sr(OH)2] = 1.5 x 103 M

Given:

pH

Find:

[OH]

Conceptual Plan: [Sr(OH) ]


2
Relationships:

[OH]=2[Sr(OH)2]

pOH

pH

pH + pOH = 14.00

Solution:

[OH]
= 2(0.0015)
= 0.0030 M
Check:

pH

= 14.00 2.52 = 11.48

pH is unitless; the fact that the pH > 7


means the solution is basic

106

4.3

pH A Measure of Acidity
Exercise 13

(a) Calculate the pH of a solution formed by mixing 10.0


mL of 0.015 M Ba(OH)2 with 40 mL of 7.5 x 10-3 M
NaOH

(b) Calculate the concentration of an aqueous solution


of Ca(OH)2 that has a pH of 12.05

107

4.3

pH A Measure of Acidity

Finding the pH of a Weak Acid


There are also two sources of H3O+ in an aqueous
solution of a weak acid the acid and the water
However, finding the [H3O+] is complicated by the fact HA
the acid only undergoes partial ionization
Calculating the [H3O+] requires the use of Ka for the
equilibrium :

HA + H2O A + H3O+
108

4.3

pH A Measure of Acidity
Example 13

Find the pH of 0.200 M HNO2(aq) solution @ 25


C, given that Ka for HNO2 = 4.6 x 104

109

4.3

pH A Measure of Acidity
Answer

represent the change


in the concentrations
in terms of x
sum the columns to
find the equilibrium
concentrations in
terms of x
substitute into the
equilibrium constant
expression

[HNO2]

initial
change
equilibrium

0.200

x
0.200 x

[NO2] [H3O+]
0
+x
x

0
+x
x

HNO2 + H2O(l) NO2(aq) + H3O+(aq)

110

4.3

pH A Measure of Acidity
Answer

because Ka is very
small, approximate initial
the [HNO2]eq =
change
[HNO2]init and
solve for x
equilibrium

[HNO2]

[NO2] [H3O+]

0.200

+x

+x

0.200

111

4.3

pH A Measure of Acidity
Answer

Ka for HNO2 = 4.6 x 104


check if the
[HNO2] [NO2] [H3O+]
approximation is
0.200
initial
0
0
valid by seeing if
x
+x
+x
x < 5% of [HNO2]init change
equilibrium
0.200
x
x

x = 9.6 x 103

the approximation is valid

112

4.3

pH A Measure of Acidity
Answer

substitute x
into the
equilibrium
concentration
definitions and
solve

Ka for HNO2 = 4.6 x 104

initial
change
equilibrium

[HNO2] [NO2] [H3O+]


0.200
0
0
x
+x
+x
0.190

0.0096 0.0096

x = 9.6 x 103

113

4.3

pH A Measure of Acidity
Answer

substitute
[H3O+] into the
formula for pH
and solve

initial

change
equilibrium

[HNO2]

[NO2]

[H3O+]

0.200

+x

+x

0.190

0.0096

0.0096

114

4.3

pH A Measure of Acidity

Determining [H3O+] of a Weak Acid from Ka


using the Direct Approach
For a weak acid HA with [HA] = c mol/L

[H3O+] [A-]
Ka =
[HA]
Since [A] = [H3O+]

[HA ] x Ka = [H3O+]
[H3O+] = c x Ka

[H3O+] = c x Ka
115

4.3

pH A Measure of Acidity
Example 14

What is the pH of a 0.012 M solution of nicotinic acid,


HC6H4NO2?
(Ka = 1.4 x 105 at 25 C)
Answer
[HC6H4NO2 ] = 0.012 M = c
[H3O+] = c x Ka
[H3O+] = 0.012 x 1.4 x 105 = 4.1 x 104 M
pH = log(4.1 x 104) = 3.39
116

4.3

pH A Measure of Acidity
Example 15

What is the Ka of a weak acid if a 0.100 M solution


has a pH of 4.25?
Answer
use the pH to find the
equilibrium [H3O+]
write the reaction for
the acid with water

Compute Ka

HA + H2O A + H3O+

Ka = [H3O+] / c
= (5.6 x 105)/0.100
= 3.1 x 108
117

4.3

pH A Measure of Acidity
Exercise 14

The acid-dissociation constant Ka of hypochlorous acid,


(HClO), is 3.0 x 10-8. Calculate the concentrations of H3O+
and pH if the initial concentration of HClO is 0.0090 M

118

4.3

pH A Measure of Acidity
Exercise 15

A 0.100 M solution of chloroacetic acid (ClCH2COOH) is


11.0% ionized. Using this information, calculate
[ClCH2COO-], [H+], [ClCH2COOH] , and Ka for
chloroacetic acid.

119

4.3

pH A Measure of Acidity
Exercise 16

How many moles of HF (Ka = 6.8 x 10-4) must be present


in 0.200 L to form a solution with a pH of 3.25?

120

4.3

pH A Measure of Acidity
pK

Another way of expressing the strength of a weak acid


or weak base is pK
pKa = log(Ka), Ka = 10pKa
The stronger the acid, the smaller the pKa
larger Ka = smaller pKa because it is the log

pKb = log(Kb), Kb = 10pKb

The stronger the base, the smaller the pKb


larger Kb = smaller pKb

121

4.3

pH A Measure of Acidity
Example 16

a) HF has Ka = 3.5 x 104. Calculate the pKa.


pKa = logKa = log(3.5 x 104) = 3.455
b) The pKb of ethylamine, C2H5NH2 = 3.25. What is its
Kb value?
pKb = 3.25 Kb = 10pKb = 103.25
= 5.62 x 104

122

4.3

pH A Measure of Acidity
Example 17

Find the pH of 0.100 M NH3(aq)

123

4.3

pH A Measure of Acidity
Answer

Kb for NH3 = 1.76 x 105

determine the value


of Kb from Table 15.8
because Kb is very
small, approximate
the [NH3]eq = [NH3]init
and solve for x

initial
change

equilibrium

[NH3]

[NH4+]

[OH]

0.100

+x

+x

0.100

124

4.3

pH A Measure of Acidity
Answer

From previous calculation, obtained: x = 1.33 x 103

125

4.3

pH A Measure of Acidity
Answer

Alterative method:
use the [OH] to
find the pOH
use pOH to find
pH

126

4.3

pH A Measure of Acidity
Example 18

Find the pH of a 0.0015 M morphine solution,


Kb = 1.6 x 106 using direct approximation
method

127

4.3

pH A Measure of Acidity
Answer

B + H2O BH+ + OH
Taking [B] = c, and [BH+] = [OH]

Kb =

[BH+][OH]

[OH]
=

[B]

[OH] = (c x Kb) = (0.0015 x 1.6 x 106 )


= 4.9 x 105
pOH = log(4.9 x 105) = 4.31
pH = 14 pOH = 14 4.31
= 9.69

128

4.3

pH A Measure of Acidity
Answer

Kb for morphine = 1.6 x 106


use the [OH] to
find the pOH
use pOH to find
pH

initial
change
equilibrium

[B]

[BH+]

[OH]

0.0015

+x

+x

0.0015

4.9E5

4.9E5

129

4.3

pH A Measure of Acidity

Relationship between Ka of an Acid and Kb of Its


Conjugate Base
Many reference books only give tables of Ka
values because Kb values can be found from them
when you add
equations, you
multiply the
Ks

At 25 oC, Kw = 1 x 10 14
130

4.3

pH A Measure of Acidity
Exercise 17

Find the pH of a 0.075 M ethylamine solution,


(C2H5NH2, Kb = 1.6 x 106)

131

4.3

pH A Measure of Acidity
Exercise 18

Codeine (C18H21NO3) is a weak organic base. A 5.0 x 10-3


M solution of codeine has a pH of 9.95.
a) Calculate the value of Kb for this substance.
b) Determine the degree of dissociation
c) What is the pKb for this base?

132

4.3

pH A Measure of Acidity
Exercise 19

A 0.035 M of Ephedrine (C10H15ON) has a pH of 11.33.


(a). Write the chemical equation and the Kb expression
for the ionization of ephedrine in aqueous solution.
(b). Calculate the equilibrium concentrations for all
species
(c). Calculate pKb for ephedrine

133

TOPIC
4.4 THE ACID-BASE PROPERTIES
OF IONS AND SALTS

134

4.4 The Acid-base Properties of Ions


and Salts
Salt Hydrolysis
Salts are water-soluble ionic compounds
Basic salts
Salts that contain the cation of a strong base and an anion that is the
conjugate base of a weak acid are basic
NaF solutions are basic
Na+ is the cation of the strong base NaOH

F is the conjugate base of the weak acid HF. F sligthly


hydrolyse in water to give OH
F(aq) + H2O(l) HF(aq) + OH(aq)
135

4.4 The Acid-base Properties of Ions


and Salts
Salt Hydrolysis

Acidic Salts
Salts that contain cations that are the conjugate acid of a weak base
and an anion of a strong acid are acidic
NH4Cl solutions are acidic
NH4+ is the conjugate acid of the weak base NH3

NH4+ under goes hydrolysis to produce slight excess of H+


NH4+ (aq) + H2O(l) NH4 OH(aq) + H+(aq)
Cl is the anion of the strong acid HCl. No hydrolysis.
Neutral Salts
Salts that contain cations that are the conjugate acid of a strong
base and an anion of a strong acid are neutral. Examples: NaBr,
KNO3
136

4.4 The Acid-base Properties of Ions


and Salts

Salt Hydrolysis
Example 19
Use the table to determine if the given anion is basic or
neutral
a)

NO3

the conjugate base of a


strong acid, HNO3,
therefore neutral
b)

NO2
the conjugate base of a
weak acid, HNO2
therefore basic

137

4.4 The Acid-base Properties of Ions


and Salts
Salt Hydrolysis
Example 20

Find the pH of 0.100 M NaCHO2(aq) solution

138

4.4 The Acid-base Properties of Ions


and Salts
Salt Hydrolysis
Na+ is the cation of a
strong base pH
neutral. The CHO2
is the anion of a
weak acid pH basic
write the reaction for
the anion with water
construct an ICE
table for the reaction

Answer

CHO2 + H2O HCHO2 + OH


initial

[CHO2]

[HCHO2]

[OH]

0.100

change

equilibrium

enter the initial


concentrations
assuming the [OH]
from water is 0
139

4.4 The Acid-base Properties of Ions


and Salts
represent the change
in the concentrations
in terms of x
sum the columns to
find the equilibrium
concentrations in
terms of x

Salt Hydrolysis
Answer
[CHO2] [HCHO2] [OH]
initial

0.100

change
equilibrium

Calculate the value of


Kb from the value of Ka
of the weak acid from
Table 15.5
substitute into the
equilibrium constant
expression

140

4.4 The Acid-base Properties of Ions


and Salts
Salt Hydrolysis
Answer

because Kb is very
small, approximate
the [CHO2]eq =
[CHO2]init and solve
for x

initial
change
equilibrium

[CHO2]

[HCHO2]

[OH]

0.100

+x

+x

0.100

Kb for CHO2 = 5.6 x 1011

141

4.4 The Acid-base Properties of Ions


and Salts

Salt Hydrolysis
Answer
Kb for CHO2 = 5.6 x 1011

check if the
approximation is
valid by seeing if x
< 5% of [CHO2]init

initial
change
equilibrium

[CHO2]

[HCHO2]

[OH]

0.100

+x

+x

0.100

x = 2.4 x 106

the approximation is valid

142

4.4 The Acid-base Properties of Ions


and Salts

Salt Hydrolysis
Answer
Kb for CHO2 = 5.6 x 1011

substitute x into
the equilibrium
concentration
definitions and
solve

initial
change

[CHO2]

[HCHO2]

[OH]

0.100

+x

+x

equilibrium

143

4.4 The Acid-base Properties of Ions


and Salts
use the [OH] to
find the [H3O+]
using Kw
substitute [H3O+]
into the formula
for pH and solve

Salt Hydrolysis
Answer
Kb for CHO2 = 5.6 x 1011

initial

change
equilibrium

[CHO2]

[HCHO2]

[OH]

0.100

+x

+x

0.100

2.4E-6

2.4E-6

144

4.4 The Acid-base Properties of Ions


and Salts

Salt Hydrolysis
Answer
Kb for CHO2 = 5.6 x 1011

use the [OH] to


find the pOH
use pOH to find
pH

initial
change

equilibrium

[CHO2]

[HCHO2]

[OH]

0.100

+x

+x

0.100

2.4E6

2.4E6

145

4.4 The Acid-base Properties of Ions


and Salts
check by
substituting the
equilibrium
concentrations
back into the
equilibrium
constant
expression and
comparing the
calculated Kb to
the given Kb

Salt Hydrolysis
Answer

[CHO2] [HCHO2]
0.100
initial
cHAnge
x
equilibrium 0.100

[OH]

+x

+x

2.4E6

2.4E6

Kb for CHO2 = 5.6 x 1011

though not exact, the


answer is reasonably
close

146

4.4 The Acid-base Properties of Ions


and Salts

Na+ is the cation of


a strong base pOH
neutral. Because
pOH is < 7, the
solution is basic. A
is basic.

Salt Hydrolysis
Example 21

If a 0.0015 M NaA solution has a pOH


of 5.45, what is the Ka of HA?

A + H2O HA + OH

write the reaction


for the anion with
water
construct an ICE
table for the
reaction

initial

enter the initial


concentrations
assuming the [OH]
from water is 0

equilibrium

[A]

[HA]

[OH]

0.100

change

147

4.4 The Acid-base Properties of Ions


and Salts
use the pOH to
find the [OH]

Salt Hydrolysis
Answer

use [OH] to fill


in other items

[A]

[HA]

[OH]

0.15
0
0
initial
3.6E6 +3.6E6 +3.6E6
cHAnge
0.15
3.6E-6
3.6E-6
equilibrium

148

4.4 The Acid-base Properties of Ions


and Salts
Salt Hydrolysis
Answer

calculate the
value of Kb of A

initial
change
equilibrium

[A]

[HA]

[OH]

0.15

3.6E6

+3.6E6

+3.6E6

0.15

3.6E-6

3.6E-6

149

4.4 The Acid-base Properties of Ions


and Salts
Salt Hydrolysis
Answer

use Kb of A to
find Ka of HA

initial
change

equilibrium

[A]

[HA]

[OH]

0.15

3.6E6

+3.6E6

+3.6E6

0.15

3.6E-6

3.6E-6

Kb 8.39 1011

150

4.4 The Acid-base Properties of Ions


and Salts
Exercise 20

An unknown salt is either KBr, NH4Cl, KCN, or K2CO3. If


a 0.100 M solution of the salt is neutral, what is the
identity of the salt?
Calculate the pH of a 0.050 M solution of sodium
butyrate. (pKa CH3CH2CH2COONa = 4.84)

151

4.4 The Acid-base Properties of Ions


and Salts
Polyatomic Cations as Weak Acids

Some cations can be thought of as the conjugate acid of


a weak base
others are the counter-ions of a strong base

Therefore, some cations can potentially be acidic. They


undergo hydrolysis
MH+(aq) + H2O(l) MOH(aq) + H3O+(aq)

The stronger the base is, the weaker the conjugate acid is
a cation that is the counter-ion of a strong base is pH neutral
a cation that is the conjugate acid of a weak base is acidic

NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq)


because NH3 is a weak base, the position of this equilibrium
favors the right
152

4.4 The Acid-base Properties of Ions


and Salts
Metal Cations as Weak Acids

Cations of small, highly charged metals are weakly


acidic
alkali metal cations and alkali earth metal cations are pH neutral
cations are hydrated
Al(H2O)63+(aq) + H2O(l) Al(H2O)5(OH)2+ (aq) + H3O+(aq)

153

4.4 The Acid-base Properties of Ions


and Salts
Example 22

Determine if the given cation is acidic or neutral


a)

b)

c)

C5H5NH+
the conjugate acid of the weak base pyridine, C5H5N
therefore acidic
Ca2+
the counter-ion of the strong base Ca(OH)2,
therefore neutral
Cr3+
a highly charged metal ion, therefore acidic
154

4.4 The Acid-base Properties of Ions


and Salts
Classifying Salt Solutions as Acidic, Basic, or Neutral
If the salt cation is the counter-ion of a strong base and
the anion is the conjugate base of a strong acid, it will
form a neutral solution
NaCl

Ca(NO3)2

KBr

If the salt cation is the counter-ion of a strong base and


the anion is the conjugate base of a weak acid, it will
form a basic solution
NaF

Ca(C2H3O2)2

KNO2

155

4.4 The Acid-base Properties of Ions


and Salts
Classifying Salt Solutions as Acidic, Basic, or Neutral
If the salt cation is the conjugate acid of a weak base
and the anion is the conjugate base of a strong acid, it
will form an acidic solution
NH4Cl

If the salt cation is a highly charged metal ion and the


anion is the conjugate base of a strong acid, it will
form an acidic solution
Al(NO3)3

156

4.4 The Acid-base Properties of Ions


and Salts
Classifying Salt Solutions as Acidic, Basic, or Neutral
If the salt cation is the conjugate acid of a weak base
and the anion is the conjugate base of a weak acid,
the pH of the solution depends on the relative
strengths of the acid and base
NH4F because HF is a stronger acid than NH4+, Ka of NH4+ is
larger than Kb of the F; therefore the solution will be acidic

157

4.4 The Acid-base Properties of Ions


and Salts
Example 23
Determine whether a solution of the following salts is
acidic, basic, or neutral
a)

b)

c)

SrCl2
Sr2+ is the counter-ion of a strong base, pH neutral
Cl is the conjugate base of a strong acid, pH neutral
solution will be pH neutral
AlCl3
Al3+ is a small, highly charged metal ion, weak acid
Cl is the conjugate base of a strong acid, pH neutral
solution will be acidic
CH3NH3NO3
CH3NH3+ is the conjugate acid of a weak base, acidic
NO3 is the conjugate base of a strong acid, pH neutral solution
will be acidic
158

4.4 The Acid-base Properties of Ions


and Salts
Answer
d)

e)

NaCHO2
Na+ is the counter-ion of a strong base, pH neutral
CHO2 is the conjugate base of a weak acid, basic
solution will be basic
NH4F
NH4+ is the conjugate acid of a weak base, acidic
F is the conjugate base of a weak acid, basic
Ka(NH4+) > Kb(F); solution will be acidic

159

4.4 The Acid-base Properties of Ions


and Salts
Example 24
Determine whether a solution of the following salts is
acidic, basic, or neutral

KNO3
CoCl3

Ba(HCO3)2
CH3NH3NO3
160

4.4 The Acid-base Properties of Ions


and Salts
Answer
K+ is the counter-ion of a strong base, pH neutral

KNO3

CoCl3

Ba(HCO3)2

CH3NH3NO3

NO3 is the counter-ion of a strong acid, pH neutral


the solution is pH neutral
Co3+ is a highly charged cation, pH acidic
Cl is the counter-ion of a strong acid, pH neutral
the solution is pH acidic
Ba2+ is the counter-ion of a strong base, pH neutral
HCO3 is the conjugate of a weak acid, pH basic
the solution is pH basic
CH3NH3+ is the conjugate of a weak base, pH acidic

NO3 is the counter-ion of a strong acid, pH neutral


the solution is pH acidic
161

TOPIC
4.5 BUFFER SOLUTIONS

162

4.5 Buffer Solutions


Buffers
Buffers are solutions of a weak conjugate acid-base pair.
They are practically resist changes in pH when an acid or base is
added even strong acid or base.
They act by neutralizing acid or base that is added to the buffered
solution
Acidic buffers are made by mixing a solution of a weak acid with a
solution of a salt containing its conjugate base anion
Mixing acetic acid, HC2H3O2 with sodium acetate, NaC2H3O2
Basic buffers are prepared by mixing a solution of a weak base
with a solution of a salt containing its conjugate acid cation
Mixing aqueous NH3 with ammonium chloride solution NH4Cl

163

4.5 Buffer Solutions


Making an Acid Buffers
H2O(l) + HC2H3O2 (aq) C2H3O2-(aq) + H3O+(aq)

164

4.5 Buffer Solutions


Making a Basic Buffers
H2O(l) + NH3 (aq) NH4+(aq) + OH(aq)

165

4.5 Buffer Solutions


How Acid Buffers Work: Base Addition

H2O(l) + HA (aq) A-(aq) + H3O+(aq)


Buffers work by applying Le Chteliers Principle to
weak acid equilibrium
Acid Buffer solutions contain significant amounts of
the weak acid molecules, HA
These molecules neutralize the added base OH(aq)
HA(aq) + OH(aq) A(aq) + H2O(l)
you can also think of the H3O+ combining with the OH to make H2O;
the H3O+ is then replaced by the shifting equilibrium

166

4.5 Buffer Solutions


How Acid Buffers Work: Acid Addition

H2O(l) + HA (aq) A-(aq) + H3O+(aq)


The buffer solution also contains significant amounts
of the conjugate base anion, A
These ions combine with added acid, H+(aq) to make
more HA
H+(aq) + A(aq) HA(aq)

167

4.5 Buffer Solutions


Common Ion Effect

Adding a salt, NaA containing the anion, A(aq) which is


the conjugate base of the acid (the common ion),
shifts the position of equilibrium to the left, lowering

the H3O+ ion concentration


This causes the pH to be higher than the pH of the
acid solution

168

4.5 Buffer Solutions


Common Ion Effect
Consider a solution of acetic acid:

H2O(l) + HC2H3O2 (aq) C2H3O2-(aq) + H3O+(aq)


If acetate ion is added to the solution, Le Chtelier
says the equilibrium will shift to the left.

169

4.5 Buffer Solutions


Example 25
In which of these solutions will HNO2 ionize less than it does in pure
water?
a. 0.1 M KNO3
b. 0.1 M NaCl
c. 0.1 M NaOH
d. 0.1 NaNO2
A formic acid solution has a pH of 3.25. Which of these substances
will raise the pH of the solution upon addition? Explain
a. HCl
b. NaBr
c. NaCHO2
d. KCl
170

4.5 Buffer Solutions


Answer
In which of these solutions will HNO2 ionize less than it does in pure
water?
Answer: The only solution that HNO2 will ionize less in is (d). It is the
only solution that generates a common ion NO2- with nitrous acid
A formic acid solution has a pH of 3.25. Which of these substances
will raise the pH of the solution upon addition? Explain

Answer: Formic acid is HCHO2 which dissociates to H+ and CHO2-.


The only solution that generates a common ion (CHO2-) with
formic acid is (c) NaCHO2

171

4.5 Buffer Solutions


Example 26
What is the pH of a buffer that is 0.100 M HC2H3O2 and
0.100 M NaC2H3O2?
write the reaction
for the acid with
water
construct an ICE
table for the
reaction
enter the initial
concentrations
assuming the
[H3O+] from water
is 0

HC2H3O2 + H2O C2H3O2 + H3O+

initial
change
equilibrium

[HA]

[A]

[H3O+]

0.100

0.100

172

4.5 Buffer Solutions


Answer
represent the change
in the concentrations
in terms of x
sum the columns to
find the equilibrium
concentrations in
terms of x

HC2H3O2 + H2O C2H3O2 + H3O+


initial
change

[HA]

[A]

[H3O+]

0.100

0.100

+x

equilibrium 0.100 x 0.100 + x

+x
x

substitute into the


equilibrium constant
expression

173

4.5 Buffer Solutions


Answer

Ka for HC2H3O2 = 1.8 x 105

determine the value


of Ka
because Ka is very
small, approximate
the [HA]eq = [HA]init
and [A]eq = [A]init ,
then solve for x

initial

change
equilibrium

[HA]

[A]

[H3O+]

0.100

0.100

+x

+x

0.100

0.100

174

4.5 Buffer Solutions


Answer

check if the
approximatio
n is valid by
seeing if x <
5% of
[HC2H3O2]init

Ka for HC2H3O2 = 1.8 x 105

initial
change
equilibrium

[HA]

[A]

[H3O+]

0.100

0.100

+x

+x

0.100

0.100

x = 1.8 x 105

the approximation is valid

175

4.5 Buffer Solutions


Answer

substitute x
into the
equilibrium
concentrati
on
definitions
and solve

initial
change
equilibrium

[HA]

[A]

[H3O+]

0.100

0.100

+x

+x

0.100

0.100

1.8E-5

x = 1.8 x 105

176

4.5 Buffer Solutions


Answer

substitute
[H3O+] into the
formula for pH
and solve

[HA]

[A]

[H3O+]

0.100
initial
x
change
equilibrium 0.100

0.100

+x

+x

0.100

1.8E5

177

4.5 Buffer Solutions


Example 27

What is the pH of a buffer that is 0.14 M HF


(pKa = 3.15) and 0.071 M KF?
write the reaction
for the acid with
water
construct an ICE
table for the
reaction
enter the initial
concentrations
assuming the
[H3O+] from water
is 0

HF + H2O F + H3O+

initial

[HA]

[A]

[H3O+]

0.14

0.071

change
equilibrium

178

4.5 Buffer Solutions


Answer
represent the
change in the
concentrations
in terms of x

sum the
columns to find
the equilibrium
concentrations
in terms of x
substitute into
the equilibrium
constant
expression

HF + H2O F + H3O+
initial
change

equilibrium

[HA]

[A]

[H3O+]

0.14

0.071

x
0.14 x

+x
0.071 + x

+x
x

179

4.5 Buffer Solutions


Answer

Ka for HF = 7.0 x 104


determine the
value of Ka
because Ka is
very small,
approximate the
[HA]eq = [HA]init
and [A]eq =
[A]init solve for x

initial
change
equilibrium

pKa for HF = 3.15

[HA]

[A]

[H3O+]

0.14

0.071

+x

+x

0.012

0.100

180

4.5 Buffer Solutions


Answer

Ka for HF = 7.0 x 104


check if the
approximation
initial
is valid by
seeing if
x change
< 5% of
equilibrium
[HC2H3O2]init

[HA]

[A]

[H3O+]

0.14

0.071

+x

+x

0.14

0.071

x = 1.4 x 103

the approximation is valid

181

4.5 Buffer Solutions


Answer
substitute x
into the
initial
equilibrium
concentration change
definitions
equilibrium
and solve

[HA]

[A]

[H3O+]

0.14

0.071

+x

+x

0.14

0.072

1.4E-3

x = 1.4 x 103

182

4.5 Buffer Solutions


Answer

substitute
[H3O+] into
the formula
for pH and
solve

initial
change
equilibrium

[HA]

[A]

[H3O+]

0.14

0.071

+x

+x

0.14

0.072

1.4E3

183

4.5 Buffer Solutions


Exercise 21

What is the pH of a buffer that is 0.12 M in lactic acid


CH3CH(OH)COOH, and 0.10 M in sodium lactate
CH3CH(OH)COONa. For lactic acid, Ka = 1.4 x 10-4

184

4.5 Buffer Solutions


Henderson-Hasselbalch Equation
Calculating the pH of a buffer solution can be
simplified by using an equation derived from the Ka
expression called the Henderson-Hasselbalch
Equation
The equation calculates the pH of a buffer from the
pKa and initial concentrations of the weak acid and
salt of the conjugate base
as long as the x is small approximation is valid

185

4.5 Buffer Solutions


Deriving the Equation

186

4.5 Buffer Solutions


Example 28

What is the pH of a buffer that is 0.050 M


HC7H5O2 and 0.150 M NaC7H5O2?

187

4.5 Buffer Solutions


Answer
assume the [HA] and
[A] equilibrium
concentrations are the
same as the initial

HC7H5O2 + H2O C7H5O2 + H3O+


Ka for HC7H5O2 = 6.5 x 105

substitute into the


HendersonHasselbalch Equation

check the x is small


approximation

188

4.5 Buffer Solutions


Example 29

What is the pH of a buffer that is 0.14 M HF


(pKa = 3.15) and 0.071 M KF?

189

4.5 Buffer Solutions


Answer
find the pKa from the
given Ka

HF + H2O F + H3O+

assume the [HA]


and [A] equilibrium
concentrations are
the same as the
initial

substitute into the


HendersonHasselbalch
equation
check the x is
small
approximation

190

4.5 Buffer Solutions


Henderson-Hasselbalch Equation for Basic
Buffers

The Henderson-Hasselbalch equation is written for a


chemical reaction with a weak acid reactant and its
conjugate base as a product
The chemical equation of a basic buffer is written with
a weak base as a reactant and its conjugate acid as a
product

B: + H2O H:B+ + OH

To apply the Henderson-Hasselbalch equation, the


chemical equation of the basic buffer must be looked
at like an acid reaction
H:B+ + H2O B: + H3O+

this does not affect the concentrations, just the way we are
191
looking at the reaction

4.5 Buffer Solutions


Relationship between pKa and pKb

Just as there is a relationship between the Ka of


a weak acid and Kb of its conjugate base,
there is also a relationship between the pKa of
a weak acid and the pKb of its conjugate base

Ka Kb = Kw = 1.0 x 1014
log(Ka Kb) = log(Kw) = 14
log(Ka) + log(Kb) = 14
pKa + pKb = 14
192

4.5 Buffer Solutions

Henderson-Hasselbalch Equation for Basic


Buffers

The Henderson-Hasselbalch equation is written


for a chemical reaction with a weak acid reactant
and its conjugate base as a product
The chemical equation of a basic buffer is written
with a weak base as a reactant and its conjugate
acid as a product
B: + H2O H:B+ + OH
We can rewrite the Henderson-Hasselbalch
equation for the chemical equation of the basic
buffer in terms of pOH

4.5 Buffer Solutions


Example 30

What is the pH of a buffer that is 0.50 M NH3


(pKb = 4.75) and 0.20 M NH4Cl?

194

4.5 Buffer Solutions


Answer

find the pKa of the


conjugate acid (NH4+)
from the given Kb
assume the [B] and
[HB+] equilibrium
concentrations are the
same as the initial
substitute into the
HendersonHAsselbalch equation
check the x is small
approximation

NH3 + H2O NH4+ + OH

195

4.5 Buffer Solutions


Exercise 22

Find the pH of a buffer that consists of 0.50 M


methylamine (CH3NH2) and 0.60 M CH3NH3Cl (pKb of
CH3NH2 = 3.35)

196

4.5 Buffer Solutions


Buffering Effectiveness
A good buffer should be able to neutralize moderate
amounts of added acid or base
However, there is a limit to how much can be added
before the pH changes significantly

The buffering capacity is the amount of acid or base


a buffer can neutralize
The buffering range is the pH range the buffer can be
effective
The effectiveness of a buffer depends on two factors
(1) the relative amounts of acid and base, and (2) the
absolute concentrations of acid and base
197

4.5 Buffer Solutions


Buffering Capacity

a concentrated
buffer can
neutralize more
added acid or
base than a
dilute buffer

198

4.5 Buffer Solutions


Effectiveness of Buffers

A buffer will be most effective when the


[base]:[acid] = 1
equal concentrations of acid and base
A buffer will be effective when
0.1 < [base]:[acid] < 10
A buffer will be most effective when the [acid]
and the [base] are large

199

4.5 Buffer Solutions


Buffering Range
We have said that a buffer will be effective when
0.1 < [base]:[acid] < 10
Substituting into the Henderson-Hasselbalch equation
we can calculate the maximum and minimum pH at
which the buffer will be effective

Lowest pH

Highest pH

Therefore, the effective pH range of a buffer is pKa 1

When choosing an acid to make a buffer, choose one whose is pKa


closest to the pH of the buffer
200

4.5 Buffer Solutions


Example 31
Which of the following acids would be the best choice
to combine with its sodium salt to make a buffer with
pH 4.25?
Chlorous acid, HClO2

Nitrous acid, HNO2


Formic acid, HCHO2
Hypochlorous acid, HClO

pKa = 1.95

pKa = 3.34
pKa = 3.74
pKa = 7.54

The pKa of HCHO2 is closest to the desired pH of the


buffer, so it would give the most effective buffering range
201

4.5 Buffer Solutions


Answer
What ratio of NaCHO2 : HCHO2 would be required to
make a buffer with pH 4.25?
Formic acid, HCHO2, pKa = 3.74

To make a buffer with pH


4.25, you would use 3.24
times as much NaCHO2 as
HCHO2
202

4.5 Buffer Solutions


Example 32
What ratio of NaC7H5O2 : HC7H5O2 would be required to
make a buffer with pH 3.75?

Benzoic acid, HC7H5O2, pKa = 4.19

to make a buffer with pH


3.75, you would use 0.363
times as much NaC7H5O2 as
203
HC7H5O2

4.5 Buffer Solutions


Buffering Capacity
Buffering capacity is the amount of acid or base that
can be added to a buffer without causing a large
change in pH
The buffering capacity increases with increasing
absolute concentration of the buffer components
As the [base]:[acid] ratio approaches 1, the ability of
the buffer to neutralize both added acid and base
improves
Buffers that need to work mainly with added acid
generally have [base] > [acid]
Buffers that need to work mainly with added base
generally have [acid] > [base]
204

TOPIC
4.6 ACID-BASE TITRATION
CURVE

205

4.6 Acid-base Titration Curve


Titration
In an acid-base titration, a solution of unknown
concentration (titrant) is slowly added to a solution of
known concentration from a burette until the reaction
is complete
when the reaction is complete we have reached
the endpoint of the titration
An indicator may be added to determine the endpoint
an indicator is a chemical that changes color when
the pH changes
When the moles of H3O+ = moles of OH, the titration
has reached its equivalence point
206

4.6 Acid-base Titration Curve


Titration

207

4.6 Acid-base Titration Curve


Titration Curve
A plot of pH vs. amount of added titrant
The inflection point of the curve is the equivalence
point of the titration
Prior to the equivalence point, the known solution in
the flask is in excess, so the pH is closest to its pH
The pH of the equivalence point depends on the pH of
the salt solution
equivalence point of neutral salt, pH = 7
equivalence point of acidic salt, pH < 7
equivalence point of basic salt, pH > 7
Rapid pH change from about pH = 3 to pH = 11
208

4.6 Acid-base Titration Curve


Titration Curve
Unknown Strong Base Added to Strong Acid

209

4.6 Acid-base Titration Curve


Titration Curve for Strong Acid and Strong Base
Titration of 25 mL of 0.100 M HCl with 0.100 M NaOH
Because the solutions
are equal
concentration, and 1:1
stoichiometry, the
equivalence point is at
equal volumes
Before Equivalence
(excess acid)

After Equivalence

(excess base)

Equivalence Point
equal moles of
HCl and NaOH
pH = 7.00

210

4.6 Acid-base Titration Curve


Titration Curve for Strong Acid and Strong Base
Titration of 25 mL of 0.100 M HCl with 0.100 M NaOH
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)
Initial pH = log(0.100) = 1.00
Initial mol of HCl = 0.0250 L x 0.100 mol/L = 2.50 x 103
Before equivalence point
added 5.0 mL NaOH
5.0 x 104 mole NaOH added

4.6 Acid-base Titration Curve


Titration Curve for Strong Acid and Strong Base

mols before
mols change
mols end
molarity, new

HCl

NaCl

NaOH

2.50E-3

5.0E-4

4.6 Acid-base Titration Curve


Titration Curve for Strong Acid and Strong Base
HCl

NaCl

NaOH

mols before

2.50E-3

5.0E-4

mols change

5.0E-4

+5.0E-4

5.0E-4

mols end

2.00E-3

5.0E-4

molarity, new

4.6 Acid-base Titration Curve


Titration Curve for Strong Acid and Strong Base
HCl

NaCl

NaOH

mols before

2.50E-3

5.0E-4

mols change

5.0E-4

+5.0E-4

5.0E-4

mols end

2.00E-3

5.0E-4

molarity, new

0.0667

0.017

4.6 Acid-base Titration Curve


Titration Curve for Strong Acid and Strong Base
pHs after adding 10.0, 15.0 and 20.0 mL of NaOH.
We can calculate pH at each points in the same way
that we calculated the pH at 5 mL point.
Volume (mL)

pH10.0

10.0
15.0
20.0

1.37
1.60
1.95

4.6 Acid-base Titration Curve


Titration Curve for Strong Acid and Strong Base
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(aq)
To reach equivalence, the added moles NaOH = initial
moles of HCl = 2.50 x 103 moles
At equivalence, we have 0.00 mol HCl and 0.00 mol
NaOH left over
Because the NaCl is a neutral salt, the pH at
equivalence = 7.00

4.6 Acid-base Titration Curve


Titration Curve for Strong Acid and Strong Base

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


Initial pH = log(0.100) = 1.00
Initial mol of HCl = 0.0250 L x 0.100 mol/L = 2.50 x 103
At equivalence point
added 25.0 mL NaOH
2.5 x 103 mole NaOH added

4.6 Acid-base Titration Curve


Titration Curve for Strong Acid and Strong Base

HCl

NaCl

NaOH

mols before 2.50E-3


0
2.5E-3
mols change 2.5E-3 +2.5E-3 2.5E-3

mols end

2.5E-3

molarity, new

0.050

4.6 Acid-base Titration Curve


Titration Curve for Strong Acid and Strong Base

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


Initial pH = log(0.100) = 1.00
Initial mol of HCl = 0.0250 L x 0.100 mol/L = 2.50 x 103
After equivalence point

added 30.0 mL NaOH


0.100 mol NaOH
1L
moles added NaOH

L of added NaOH

3.0 x 103 mole NaOH added

4.6 Acid-base Titration Curve


Titration Curve for Strong Acid and Strong Base

mols before
mols change

HCl

NaCl

NaOH

2.50E-3

3.0E-3

2.5E-3 +2.5E-3 2.5E-3

mols end

2.5E-3

5.0E-4

molarity, new

0.045

0.0091

4.6 Acid-base Titration Curve


Titration Curve for Strong Acid and Strong Base
added
30.0
5.0
10.0
25.0
mL
mLNaOH
NaOH
25.0 mL35.0
0.100
M
HCl
0.00050
0.00100
0.00200
0.00150
equivalence
mol point
NaOH
0.00250
HCl
pH = 12.22
11.96
1.18
1.37
7.00
1.00
added 15.0
40.0 mL NaOH
0.00150 mol HCl
0.00100
NaOH
pH = 1.60
12.36
added 20.0
50.0 mL NaOH
0.00250 mol HCl
0.00050
NaOH
pH = 1.95
12.52

4.6 Acid-base Titration Curve


Example 33 Calculate the pH of the solution that
results when 10.0 mL of 0.15 M NaOH is added to 50.0
mL of 0.25 M HNO3
Example 34 Calculate the pH of the solution that
results when 100.0 mL of 0.15 M NaOH is added to
50.0 mL of 0.25 M HNO3

4.6 Acid-base Titration Curve


Answer

HNO3(aq) + NaOH(aq) NaNO3(aq) + H2O(l)


Initial pH = log(0.250) = 0.60
Initial mol of HNO3= 0.0500 L x 0.25 mol/L=1.25 x 102
Before equivalence point added 10.0 mL NaOH

mols before

HNO3

NaNO3

NaOH

1.25E-2

1.5E-3

mols cHAnge 1.5E-3 +1.5E-3 1.5E-3


mols end

1.1E-3

1.5E-3

molarity, new

0.018

0.025

4.6 Acid-base Titration Curve


Answer
HNO3(aq) + NaOH(aq) NaNO3(aq) + H2O(l)
Initial mol of HNO3= 0.0500 L x 0.25 mol/L=1.25 x 102
After equivalence point added 100.0 mL NaOH

HNO3

NaNO3

NaOH

mols before

1.25E-2

1.5E-2

mols change
cHAnge

1.25E-2 +1.25E-2 1.25E-2

mols end

1.25E-2

0.0025

molarity, new

0.0833

0.017

4.6 Acid-base Titration Curve


Titration of a Strong Base with a Strong Acid

If the titration is run so


that the acid is in the
burette and the base is
in the flask, the titration
curve will be the
reflection of the one
just shown

4.6 Acid-base Titration Curve


Titration of a Weak Acid with a Strong Base
Titrating a weak acid with a strong base results in
differences in the titration curve at the equivalence
point and excess acid region
The initial pH is determined using the Ka of the weak
acid
The pH in the excess acid region is determined as you
would determine the pH of a buffer
The pH at the equivalence point is determined using
the Kb of the conjugate base of the weak acid
The pH after equivalence is dominated by the excess
strong base
the basicity from the conjugate base anion is
negligible

4.6 Acid-base Titration Curve


Titrating Weak Acid with a Strong Base
The initial pH is that of the weak acid solution
calculate like a weak acid equilibrium problem
e.g 15 and 16
Before the equivalence point, the solution becomes a
buffer
Half-neutralization pH = pKa
At equivalence point, pH 9
and rapid change of pH from about pH = 7 to pH = 11

4.6 Acid-base Titration Curve


Titrating Weak Acid with a Strong Base
Titration of 25 mL of 0.100 M HCHO2 with 0.100 M NaOH
HCHO2(aq) + NaOH(aq) NaCHO2(aq) + H2O(aq)
Initial pH
[HCHO2] [CHO2] [H3O+]
initial
change

0.100

0.000

+x

+x

equilibrium 0.100 x

Ka = 1.8 x 104

4.6 Acid-base Titration Curve


Titrating Weak Acid with a Strong Base
HCHO2(aq) + NaOH(aq) NaCHO2 (aq) + H2O(aq)
Initial mol of HCHO2 = 0.0250 L x 0.100 mol/L = 2.50 x 103
Before equivalence
added 5.0 mL NaOH

HA

OH

mols
before

2.50E-3

mols
added

5.0E-4

mols after

2.00E-3 5.0E-4

Titrating Weak Acid with a


Strong Base

25.0
added 30.0
5.0 mL
mLNaOH
NaOH
10.0
initial HCHO2 solution
equivalence
point
0.00200
0.00050
molmL
NaOH
0.00150
HCHO
2xs
added
35.0
NaOH
0.00250 mol HCHO
2
0.00250
mol
CHO
pH
=
3.14
11.96
3.56
2
0.00100
mol NaOH xs
pH = 2.37

[CHO
2 ]init = 0.0500 M
pH = 12.22
[OH ]eq = 1.7 x 106
added
12.5 mL NaOH
pH
= 8.23
added
40.0 mL NaOH
0.00125 mol HCHO2
0.00150 mol NaOH xs
pH = 3.74 = pKa
pH = 12.36
half-neutralization
added 50.0
15.0 mL NaOH
0.00100 mol NaOH
0.00250
HCHO2xs
pH = 12.52
3.92
added 20.0 mL NaOH
0.00050 mol HCHO2
pH = 4.34

4.6 Acid-base Titration Curve


Titrating Weak Acid with a Strong Base
The initial pH is that of the weak acid solution
calculate like a weak acid equilibrium Example 15
& 16

Before the equivalence point, the solution


becomes a buffer
calculate mol HAinit and mol Ainit using reaction
stoichiometry
calculate pH with Henderson-Hasselbalch using
mol HAinit and mol Ainit

Half-neutralization pH = pKa

4.6 Acid-base Titration Curve


Titrating Weak Acid with a Strong Base
At the equivalence point, the mole HA = mol Base, so the
resulting solution has only the conjugate base anion in it
before equilibrium is established
mol A = original mole HA
calculate the volume of added base as you did in Example
4.8
[A]init = mol A/total liters
calculate like a weak base equilibrium problem
e.g., 21

Beyond equivalence point, the OH is in excess


[OH] = mol MOH xs/total liters
[H3O+][OH]=1 x 1014

4.6 Acid-base Titration Curve


Example 35: A 40.0 mL sample of 0.100 M HNO2 is titrated
with 0.200 M KOH. Calculate the volume of KOH at the
equivalence point.

write an equation
for the reaction for
B with HA
use stoichiometry
to determine the
volume of added B

HNO2 + KOH NO2 + H2O

4.6 Acid-base Titration Curve


Example 36 : A 40.0 mL sample of 0.100 M HNO2 is titrated with
0.200 M KOH. Calculate the pH after adding 5.00 mL KOH.
write an
equation for the
HNO2 + KOH NO2 + H2O
reaction for B
with HA

determine the
moles of HAbefore
& moles of
added B
make a
stoichiometry
table and
determine the
moles of HA in
excess and
moles A made

mols before
mols added
mols after

HNO2

NO2

OH

0.00400

0.00100
0.00300

0.00100

4.6 Acid-base Titration Curve


HNO2 + H2O NO2 + H3O+
Table 15.5 Ka = 4.6 x 104
write an
equation for
the reaction of
HA with H2O
determine Ka
and pKa for HA
use the
HendersonHasselbalch
equation to
determine the
pH

HNO2

NO2

OH

mols before

0.00400

mols added

0.00100

0.00300

0.00100

mols after

4.6 Acid-base Titration Curve


Example 37: A 40.0 mL sample of 0.100 M HNO2 is titrated
with 0.200 M KOH. Calculate the pH at the half-equivalence
point.
write an equation
for the reaction for
B with HA

HNO2 + KOH NO2 + H2O

determine the
moles of HAbefore &
moles of added B
make a
stoichiometry
table and
determine the
moles of HA in
excess and moles
A made

at Half-equivalence, moles KOH = mole


HNO2

mols before

mols added
mols after

HNO2

NO2

OH

0.00400

0.00200 0.00200

0.00200
0

4.6 Acid-base Titration Curve


Answer
HNO2 + H2O NO2 + H3O+
write an
equation for the
reaction of HA
with H2O

Table 15.5 Ka = 4.6 x 10-4

determine Ka
and pKa for HA

use the
HendersonHasselbalch
equation to
determine the
pH

HNO2

NO2

OH

mols before

0.00400

mols added

0.00200

0.00200

0.00200

mols after

4.6 Acid-base Titration Curve


Titrating Weak Base with a Strong Acid
At equivalence point, pH 5
Rapid change of pH range between pH = 3 to pH = 7

4.6 Acid-base Titration Curve


Titration Curve of a Weak Base with a Strong Acid

4.6 Acid-base Titration Curve


Example 38 : Titration of 25.0 mL of 0.10 M NH3 with 0.10
M HCl. Calculate the initial pH of the NH3(aq)

4.6 Acid-base Titration Curve


Answer
NH3(aq) + HCl(aq) NH4Cl(aq)
Initial: NH3(aq) + H2O(l) NH4+(aq) + OH(aq)

[HCl] [NH4+]

[NH3]

initial

0.10

cHAnge

+x

+x

equilibrium

0.10x

pKb = 4.75
Kb = 104.75 = 1.8 x 105

4.6 Acid-base Titration Curve


Example 39 :Titration of 25.0 mL of 0.10 M NH3 (pKb =
4.75) with 0.10 M HCl. Calculate the pH of the solution at
equivalence.

4.6 Acid-base Titration Curve


Answer
NH3(aq) + HCl(aq) NH4Cl(aq)
Initial mol of NH3 = 0.0250 L x 0.100 mol/L = 2.50 x 103
At equivalence mol NH3 = mol HCl = 2.50 x 103

NH3

NH4Cl

HCl

mols before

2.50E-3

2.5E-3

mols change

2.5E-3 +2.5E-3 2.5E-3

mols end

2.5E-3

molarity, new

0.050

added 25.0 mL HCl

4.6 Acid-base Titration Curve


Answer
NH3(aq) + HCl(aq) NH4Cl(aq)
at equivalence [NH4Cl] = 0.050 M
NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq)

[NH3]

[NH4+] [H3O+]

initial

0.050

change

+x

+x

equilibrium

0.050x

TOPIC
4.7 INDICATORS

4.7 Indicators
Many dyes change color depending on the pH of the
solution
These dyes are weak acids, establishing an
equilibrium with the H2O and H3O+ in the solution
HInd(aq) + H2O(l) Ind(aq) + H3O+(aq)

The color of the solution depends on the relative


concentrations of Ind:HInd
when Ind:HInd 1, the color will be mix of the colors of Ind
and HInd
when Ind:HInd > 10, the color will be mix of the colors of Ind
when Ind:HInd < 0.1, the color will be mix of the colors of
Hind

4.7 Indicators
Monitoring a Titration with an Indicator
For most titrations, the titration curve shows a very
large change in pH for very small additions of titrant
near the equivalence point
An indicator can therefore be used to determine the
endpoint of the titration if:
pKa of indicator pH at equivalence point
it changes color within the same range as the rapid change in
pH

4.7 Indicators
Acid-Base Indicators

4.7 Indicators
Acid-Base Indicators

4.7 Indicators
Phenolphthalein

4.7 Indicators
Methyl Red

H
C
(CH3)2N

H
C

H
C
C

C
H

(CH3)2N

OH-

CH
C

C
H

H
C

H
C

NaOOC

H
C

C
C
H

N
H

C
H

H3O+
H
C

H
C

C
H

CH
C

NaOOC

C
H

The titration curve of a strong acid with a strong base.

252

4.7 Indicators
Example 40
Which indicator or indicators listed in Table 16.1 would you use for the
acid-base titrations shown in
(a)

4.7 Indicators
Example
(b)

4.7 Indicators
Example
(c)

4.7 Indicators
Answer
(a) Near the equivalence point, the pH of the solution changes
abruptly from 4 to 10. Therefore, all the indicators except thymol
blue, bromophenol blue, and methyl orange are suitable for use in
the titration.
(b) Here the steep portion covers the pH range between 7 and 10;
therefore, the suitable indicators are cresol red and
phenolphthalein.
(c) Here the steep portion of the pH curve covers the pH range
between 3 and 7; therefore, the suitable indicators are
bromophenol blue, methyl orange, methyl red, and chlorophenol
blue.

End of Chapter 3
Please Read Chapter 4

Thank You

Question!
257