Unit 4 Acids Bases Afnd Salts PDF

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Acids,BasesandSalts
Acids,BasesandSalts
(H bd Unit4
(Hebden
U it 4 page109182)
109 182)
Acids,BasesandSalts
Hebden Unit4(page109182)
We will cover the following topics:

1. Definition of Acids and Bases
2. Bronsted-Lowry Acids and Bases
CHEM0012LectureNotes
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Acids,BasesandSalts
Arrhenius Definition of Acids and Bases

An acid is a substance that reacts with water to produce
p
hydronium ions, H3O+.
A base is a substance that produces hydroxide ions, OH-,in water.
Hydroxide ion
OH-
When an acid and base reacts, an ionic compound is produced as

one of the products. We call ionic compounds salts.
Acids,BasesandSalts
Arrhenius Theory of Acid and Bases

Support for the Arrhenius concept comes from measurements of
H of neutralization of any strong acid and base. Consider the
following reactions:
NaOH(aq) + HCl(aq) NaCl(aq) + H2O()
H = -56 kJ/mol
LiOH(aq) + HBr(aq) LiBr(aq) + H2O()
H = -56 kJ/mol
If we write the net ionic equation for both of these reactions we

see that they are the same
H+(aq) + OH-(aq) H2O()
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Acids,BasesandSalts
Monoprotic and Polyprotic acids

1. Monoprotic acids capable off ionizing 1 H+ ion per molecule
of acid.
Strong acid = 100% dissociation into ions
Example:
HCl (aq) + H2O () H3O+ (aq) + Cl- (aq)
CH3COOH (aq) + H2O () H3O+ (aq) + CH3COO- (aq)
Weak acid = partial dissociation into ions
Acids,BasesandSalts
Monoprotic and Polyprotic acids

2. Polyprotic
yp
acids capable
p
of ionizing
g more than one H+ ion p
per
molecule of acid.
Example of a Diprotic acid:
H2SO4 (aq) + H2O () H3O+ (aq) + HSO4- (aq)
HSO4- (aq) + H2O () H3O+ (aq) + SO42- (aq)
Example of a Triprotic acid:
H3PO4 (aq) + H2O () H3O+ (aq) + H2PO4 - (aq)
H2PO4 - (aq) + H2O () H3O+ (aq) + HPO42- (aq)
Youshouldbe
abletowrite
aciddissociation
reactions.
Payattentionto
thechargeson
alltheions,and
balancethe
reactions.
HPO4 2- (aq) + H2O () H3O+ (aq) + PO43- (aq)

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Acids,BasesandSalts
Monoprotic and Polyprotic bases

1. Monoprotic bases capable off ionizing 1 OH
O - ion per molecule
of base.
Strong base = 100% dissociation into ions
Example:
NaOH (aq) Na+ (aq) + OH- (aq)
Nitrogen
g compounds
p
are bases because they
y dissolve in water
to produce OH ions.
NH3 (aq) + H2O () NH4+ (aq) + OH- (aq)
CH3NH2 (aq) + H2O () CH3NH3+ (aq) + OH- (aq)
Weak base = partial dissociation into ions
Acids,BasesandSalts
Monoprotic and Polyprotic bases

2. Polyprotic bases capable off ionizing more than one OH
O - ion
per molecule of base.
Example:
Youshouldbe
Ca(OH)2 (aq) Ca2+ (aq) + 2 OH- (aq)
Al(OH)3 (aq) Al3+ (aq) + 3 OH- (aq)
abletowrite
base
dissociation
reactions.
Payattentionto
thechargeson
alltheions,and
balancethe
reactions.
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Acids,BasesandSalts
In general,
1 Ioni
1.
Ionization
ation of an acid in water
ater
HA (aq) + H2O () H3O+ (aq) + A- (aq)
2. Ionization of a base in water
B (aq)
( ) + H2O () BH+ (aq)
( ) + OH- (aq)
( )
or
B(OH)x (aq) Bx+ (aq) + x OH- (aq)
Acids,BasesandSalts
Brnsted-Lowry Acids and Bases

When ne
neutralization
trali ation reaction occ
occurs
rs in aq
aqueous
eo s
solution, Arrhenius definition of acid and base
works well.
HCl (aq) + NH3 (aq) NH4Cl (aq) + H2O()
Hydrochloric ammonia ammonium
acid
(base)
chloride
Recallthat
ArrheniusDefinitionof
AcidandBase
Anacid asasubstance
thatreactswithwater
toproduceH3O+.
Abase thatreacts
withwatertoproduce
OH.
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Acids,BasesandSalts

This same ne
neutralization
trali ation reaction can occ
occurr when
hen it is not in an
aqueous medium. Therefore, Arrheniuss definition of an acid and
a base is too restrictive.
Example: Neutralization reaction of reactants in gas phase
HCl (g) + NH3 (g) NH4Cl (s)
Hydrogen ammonia smoke containing
chloride
gas
tiny crystals
gas
of ammonium chloride
We need a broader definition!

11
Acids,BasesandSalts

What is in common bet
between
een the gaseo
gaseous
s and aq
aqueous
eo s reactions?
1. Both involve a transfer of a H+ from one reactant to another.
In solution, HCl is completely ionized and the H+ ion is
transferred from HCl to NH3.
NH3 (aq) + H3O+ (aq) + Cl- (aq) NH4+ (aq) + Cl- (aq) + H2O ()
In gas phase,
NH3 (g) + HCl (g) NH4+Cl- (s)
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Acids,BasesandSalts

View
Vie acid
acid-base
base reactions as simply
simpl the transfer of H+ (protons)
from one species to another.
Brnsted-Lowry Acids and Bases Definitions
Acid is a proton donor.
Base is a proton acceptor
acceptor.
HCl (g) + NH3 (g) NH4+ Cl- (s)
This species donates
a proton to NH3,
therefore, it is an acid.
This species accepts

a proton, therefore,
it is a base.CHEM0012LectureNotes
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Acids,BasesandSalts

In general
general,
HA
H+ donor
ACID
B BH+
H+ acceptor
BASE
H+ donor
ACID
AH+ acceptor
BASE
CONJUGATE ACID-BASE PAIRS

Two species that differ by H+ are called a conjugate pair.
There is a whole table ofCHEM0012LectureNotes
Brnsted-Lowry Acids and Bases.14
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Acids,BasesandSalts
WEAK
W
STRONG
G
15
STRONG
WEAK
Stren
ngth of acid
Strength of base
Acids,BasesandSalts
Brnsted-Lowry Conjugate Acids-Bases Pairs

Acid
H2O
NH4+
HCO3H3O+
N2H4
H3O+
NH3
H2CO3
HPO42-
-H+
+H+
Base
OHNH3
CO32H2O
N2H3H2O
NH2HCO3PO43-
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Acids,BasesandSalts
We will cover the following topics:

1. Amphiprotic Substance
2. Amphoteric Compounds
17
Acids,BasesandSalts
A substance that can act either as a p
proton acceptor
p or a p
proton
donor.
All amphiprotic substances contain a hydrogen atom.
Example 1 Water, H2O
H2O () + HCl (aq) H3O+ (aq) + Cl- (aq)
base
acid
H2O () + NH3 (aq) NH4+ (aq) + OH- (aq)
acid
base
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Acids,BasesandSalts
proton acceptor
p or a p
proton
donor.
Example 2 Bicarbonate, HCO3Youshould
beableto
writethese
equations.
HCO3- (aq) + H3O+ (aq) H2CO3 (aq) + H2O ()

base
acid
HCO3- (aq) + OH- (aq) CO32- (aq) + H2O ()
acid
base
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Acids,BasesandSalts
proton acceptor
p or a p
proton
donor.
Example 3 hydrogen sulfate ion, HSO4Youshould
beableto
writethese
equations.
HSO4- (aq) + H3O+ (aq) H2SO4 (aq) + H2O ()

base
acid
HSO4- (aq) + OH- (aq) SO42- (aq) + H2O ()
acid
base
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Acids,BasesandSalts
2. Amphoteric Substance
A compound
p
that can react as either an acid or a base.
Ampho- is Greek, it means both.
Metals have amphoteric oxides. (eg ZnO, Al(OH)3)
Example 1 Zinc oxide, ZnO
Reacts with acid: ZnO(aq) + 2H3O+(aq) Zn2+(aq) + 3H2O()
acts as a base
Reacts with base:
ZnO (aq) + 2 OH- (aq) + H2O () [Zn(OH)4]2- (aq)
acts as an acid
zincate ion
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Acids,BasesandSalts
A compound
p
Example 2 Water, H2O
Reacts with acid: H2O () + HCl (aq) H3O+ (aq) + Cl- (aq)
acts as a base
Reacts with base: H2O () + NH3 (aq) NH4+ (aq) + OH- (aq)
acts as an acid
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Acids,BasesandSalts
A compound
p
Example 3 Aluminum hydroxide, Al(OH)3
Reacts with acid:
Al(OH)3 (aq) + 3HCl (aq) AlCl3 (aq) + 3 H2O ()
acts as a base
Reacts with base:
Al(OH)3 (aq) + OH- (aq) [Al(OH)4] - (aq)
acts as an acid CHEM0012LectureNotes
aluminate ion
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Acids,BasesandSalts
Strong acids
An acid which dissociates 100% into its ions in a water solution.
Strong acid = 100% dissociation into ions
HCl (aq) + H2O () H3O+ (aq) + Cl- (aq)

The [H+] (or [H3O+]) concentration of a 0.10 M HCl solution is
0.10 M.
For monoprotic strong acids [acid] = [H+]
A common notation to express [H+] is pH, where
pH = -log [H+] = -log 0.10 = 1.00
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Acids,BasesandSalts
Recall the pH scale
pH = - log [H+]
10-10 M
0.1 M
0.01 M 0.001 M
10-9 M
10-11 M
For an increase in 1 pH unit, the solutions [H+] decreases 10x.

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Acids,BasesandSalts
Ka
Strong acids
These are strong acids

acids.
Dissociation is a single arrow to produce ions.
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Acids,BasesandSalts
Weak acids
An acid which dissociates less than100% into its ions in a water
Weak acid = < 100% dissociation into ions
ions.
solution
solution.
Use double arrows to indicate this.
CH3COOH (aq) + H2O ()
H3O+ (aq) + CH3COO- (aq)
The [H+] (or [H3O+]) concentration of a 0.10 M CH3COOH

solution is LESS THAN 0.10 M.
Therefore,
pH >1.00
In weak acids [acid]
[H ]
+
27
Acids,BasesandSalts
Weak acids
An acid which dissociates less than100% into its ions in a water
solution
solution.
HA (aq) + H2O (l)
H3O+ (aq) + A- (aq)
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Acids,BasesandSalts
Ka
Weak acids
.
.
.
These are weak acids except

the bottom two.
These last two are too weak to act as acids in water.

Note the single arrows pointing backward because the
forward dissociation never occurs.
29
Acids,BasesandSalts
Illustration of Strong and

Weak Acids
Graphic representation
of the behavior of acids
of different strengths in
aqueous solution.
(a) A strong acid.
(b) A weak
k acid.
id
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Acids,BasesandSalts
Illustration of Strong and Weak Acids
(a)
(b)
(a) A strong acid HA is completely ionized in water.

(b) A weak acid HB exists mostly as undissociated HB
molecules in water.
Note that the water molecules
are not shown in this figure.
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Acids,BasesandSalts
Strong bases
A base which dissociates 100% into its ions in a water solution.
Strong base = 100% dissociation into ions
NaOH (aq) Na+ (aq) + OH- (aq)

The [OH-] concentration of a 0.10 M NaOH solution is 0.10 M.
For NaOH, [base] = [OH-]
A common notation to express [OH-] is pOH, where
pOH = -log [OH-] = -log 0.10 = 1.00
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Acids,BasesandSalts
pH and pOH scales

[H+] > [OH-]
NEUTRAL
[H+] = [OH-]
[OH-] > [H+]
basic
acidic
Convert between pH and pOH:
pH + pOH = 14 at 25C
33
Acids,BasesandSalts
Strong bases
These are strong bases.

Any substance which dissociates completely to produce OH-, O2-,
or NH2- is a strong base
base.
Examples: Group 1 hydroxides: LiOH, NaOH, KOH, RbOH, CsOH
Group 2 hydroxides: Mg(OH)2, Ba(OH)2, Sr(OH)2
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Acids,BasesandSalts
Strong bases
For
For NaOH, [OH-] = [base]
For Ba(OH)2, [OH-] = 2 x [base]
Salts which produce O2- are strong bases.
Example: CaO (s) Ca+2 (aq) + O2- (aq)
O2- (aq) + H2O () 2 OH- (aq)
35
Acids,BasesandSalts
Weak bases
A base which dissociates less than100% into its ions in a water
Weak bases = < 100% dissociation into ions
ions.
solution
solution.
Use double arrows to indicate this.
NH3 (aq) + H2O ()
NH4+ (aq) + OH- (aq)
The [OH-] concentration of a 0.10 M NH3 solution is

LESS THAN 0.10 M.
Therefore,
pOH >1.00
In weak bases [base]
[OH ]
-
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Acids,BasesandSalts
Weak bases
A base which dissociates less than100% into its ions in a water
solution
solution.
B (aq) + H2O ()
BH+ (aq) + OH- (aq)
37
Acids,BasesandSalts
Ka
Weak bases
Conjugate bases of strong acids are VERY weak bases.

.
.
.
These are weak bases

bases, found
on the right side of the table.
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Acids,BasesandSalts
Amphiprotic Species
Found on both sides off the table (eg
( HSO
SO4-)
Can act as acids or as bases
When found on the left, it is an acid.
Ka
Acid
Strength
increases
HCO3- is a weaker acid than phenol and a stronger acid

than hydrogen peroxide.
39
Acids,BasesandSalts
Amphiprotic Species
Found on both sides off the table (eg
( HSO
SO4-)
Can act as acids or as bases
When found on the right, it is a base.
Ka
Base
Strength
increases
HCO3- is a weaker base than citrate ion and a stronger base

than Al(H2O)5(OH)2+.
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Acids,BasesandSalts
WEAK
W
STRONG
G
41
STRONG
WEAK
Stren
ngth of acid
Strength of base
Acids,BasesandSalts
We will work with the reference table

RELATIVE STRENGTHS OF BRNSTED-LOWRY ACIDS AND BASES
to determine the Acid-Base Equilibria and Relative Strengths of

Acids and Bases.
By examining the relative strengths of the acids on both sides of
the equilibrium, we can determine which side of the equilibrium is
favoured.
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Acids,BasesandSalts
1. When H2CO3 and SO32- are mixed, an equilibrium is set up.

Which side of the equilibrium is favoured?
2 (aq)
H2CO3 (aq)
( ) + SO32( )
Thiscanonly
donateaH+
ion.Itisan
ACID.
HCO3- (aq)
( ) + HSO3- (aq)
( )
Thisioncan
onlyactasa
BASE,accept
aH+ ion.
Asaresult
HCO3 isthe
i th
conjugate
baseof
H2CO3.
HSO3 isthe
conjugate
acidofSO3.
43
Acids,BasesandSalts

H2CO3 (aq) + SO322- (aq)
acid
base
HCO3- (aq) + HSO3- (aq)

conjugate base
conjugate acid
Compare the Ka of the two acids
H2CO3 is a slightly stronger acid than HSO3-.

The equilibrium will favour the products.
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Acids,BasesandSalts

2 (aq)
( ) + SO32( )
H2CO3 (aq)
acid
base
( ) + HSO3- (aq)
( )
HCO3- (aq)
conjugate base
conjugate acid
What is the value of K for this equilibrium?
Since K >1, equilibrium favors products

45
Acids,BasesandSalts
2. When H2PO4- and CO32- are mixed, an equilibrium is set up.

2 (aq)
H2PO4- (aq)
( ) + CO32( )
Thisisan
amphiprotic ion.
Itcandonateor
acceptaH+ ion.
2 (aq)
HCO3- (aq)
( ) + HPO42( )
Thisioncan
onlyactasa
BASE,accept
aH+ ion.
Afterconsidering,
inthismixture,
H2PO4 willactas
anacid.
Asaresult
HCO
CO3 isthe
i h
conjugate
acidof
CO32.
2 isthe
HPO
O42
i h
conjugate
baseof
H2PO4.
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Acids,BasesandSalts
2. When H2PO4- and CO32- are mixed, an equilibrium is set up.

H2PO4- (aq) + CO322- (aq)
acid
base
HCO3- (aq) +
conjugate acid
HPO422- (aq)
conjugate base
H2PO4- is a stronger acid than HCO3-.

47
Acids,BasesandSalts
3. When HSO4- and NH3 are mixed, an equilibrium is set up.

HSO4- (aq) +
Thisisan
amphiprotic ion.
Itcandonateor
acceptaH+ ion.
NH3 (aq)
NH4+ (aq)
Thiscanonly
actasa
BASE,accept
aH+ ion.
Afterconsidering,
inthismixture,
HSO4 willactas
anacid.
SO42- (aq)
Asaresult
NH4+ isthe
conjugate
acidofNH3.
SO42 isthe
conjugate
baseof
HSO4.
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Acids,BasesandSalts
3. When HSO4- and NH3 are mixed, an equilibrium is set up.

HSO4- (aq)
( ) + NH3 (aq)
( )
acid
base
NH4+ (aq)
( ) +
conjugate acid
2 (aq)
SO42( )
conjugate base
HSO4- is a stronger acid than NH4+ .

49
Acids,BasesandSalts
4. When HSO4- and H2PO4- are mixed, an equilibrium is set up.

Both HSO4- and H2PO4- are amphiprotic ions
ions.
Which will play the role of an acid? Lets compare their Ka values.
HSO4- is a stronger acid than H2PO4-.

HSO4- will act as an acid donating protons to H2PO4-.
Afterconsidering,inthismixture,HSO4 will
actasanacid.H2PO42 willactasthebase.
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Acids,BasesandSalts

HSO4- (aq) + H2PO4- (aq)

Ka ofHSO4 is
bigger.Ithas
thehigher
tendencyto
d
donateH
t H+.+
Ka ofH2PO4 is
smaller.
Comparatively,
ithasless
tendencyto
y
donateH+.
Afterconsidering,in
thismixture,HSO4
willactasanacid.
H3PO4 (aq) + SO422- (aq)

Asaresult
H3PO4 isthe
conjugate
acidofH2PO4
.
SO42 isthe
conjugate
baseof
HSO4.
51
Acids,BasesandSalts

HSO4- (aq)
( ) + H2PO4- (aq)
( )
acid
base
2 (aq)
H3PO4 (aq)
( ) + SO42( )
conjugate acid conjugate base
HSO4- is a stronger acid than H3PO4 .

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Acids,BasesandSalts
5. When CH3COOH and NH3 are mixed, an equilibrium is set up.

CH3COO- (aq) + NH4+ (aq)
conjugate base conjugate acid
CH3COOH (aq) + NH3 (aq)

acid
base

CH3COOH H+ + CH3COONH4+ H+ + NH3
1.8x10
1
8x10-5
5.6x10-10
CH3COOH is a stronger acid than NH4+.

53
Acids,BasesandSalts
6. Consider an amino acid, an equilibrium is set up between the

amine group, R-NH2, and the carboxylic acid group, R-COOH .
H2NCHRCOOH (aq)
base
acid
+H NCHRCOO3
conjugate acid
(aq)
conjugate base
CH3COOH H+ + CH3COONH4+ H+ + NH3
1.8x10
1
8x10-5
5.6x10-10
CH3COOH is a stronger acid than NH4+.

The equilibrium will favour the products
(i.e. a double charged
species).
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Acids,BasesandSalts
Direction of Reaction Example

Predict the direction favored in each of the following acid-base
reactions That is
reactions.
is, does the reaction tend to go more in the forward
or in the reverse direction?
a) NH4+ + OH- H2O + NH3
Forward
b) HSO4- + NO3- HNO3 + SO42c) HSO3 + CH3

-
COO-
SO3 + CH3COOH
2-
Reverse
Reverse
d) CH3COOH + Cr(H2O)5(OH)2+ Cr(H2O)63+ + CH3COO-
Reverse
e) HNO2 + ClO4 HClO4 + NO2
Reverse
f)
H2CO3 + CO32- HCO3- + HCO3-
Forward
55
Acids,BasesandSalts
Inaqueoussolutions,H3O+ (aq)&OH (aq)arethe

strongest acids and bases that exist.
strongestacidsandbasesthatexist.
StrongerbasesreactwithwatertoformOH (aq)
O2 (aq)+H2O()OH (aq)+OH (aq)
StrongeracidsreactwithwatertoformH
Stronger
acids react with water to form H3O+ (aq).
HCl (aq)+H2O() H3O+ (aq)+Cl (aq)
ThisisknownastheLeveling Effect
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Acids,BasesandSalts
The Self-Ionization of Water
57
Acids,BasesandSalts
Ion Product of Water

H2O()+ H2O() H3O+(aq) + OH-(aq)
K=
[H3O+][OH-]
[H2O][H2O]
KW= K[H2O][H2O] = [H3O+][OH-] = 1x10-14 at 25C

Consider
HA(aq) + H2O() A-(aq) + H3O+(aq)
Ka
A-(aq) + H2O() HA(aq) + OH-(aq)
Kb
A H 3O
K a K b
HA
HA OH H O OH K
K w K aK b
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Acids,BasesandSalts
pH and pOH
Thepotentialofthehydrogenionwasdefinedin
1909asthenegativeofthelogarithmof[H+].
pH = -log[H3O+]
pOH = -log[OH-]
KW = [H3O+][OH-] = 1.0x10-14 at 25C

-logK
logKW = -log[H
log[H3O+]]-log[OH
log[OH-]]= -log(1
log(1.0x10
0x10-14)
pKW = pH + pOH= -(-14)
pKW = pH + pOH = 14 at 25C
Acids,BasesandSalts
Concentration and pH and pOH Examples at 25C

[H+]
[OH]
pH
pOH
Acidic/Basic
pH=5.52
0.15M
HNO3
0.0100M
Ca(OH)2
1.0x1010 M
Ca(OH)2
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Acids,BasesandSalts
Concentration and pH and pOH Examples at 25C

[H+]
[OH]
pH
pOH
Acidic/Basic
pH=5.52
3.0x106M
3.3x109M
5.52
8.48
Acidic
0.15M
HNO3
0.15 M
6.7x1014M
0.82
13.18
Acidic
0.0100M
Ca(OH)2
5.00x1013M
2.00x102M
12.301
1.699
Basic
1.0x1010 M
Ca(OH)2
1x107M
1x107M
Neutral
Acids,BasesandSalts
Strong Acid and Bases Examples
1. CalculatethepHofasolutionof0.400gof
HIin500.mlofsolution.
2. Calculatethethe massofSr(OH)2 which

mustbedissolvedin600.mlofsolutionto
makeapHof12.00.
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Acids,BasesandSalts
Weak Acid and Bases Examples
1. Butyricacid,HC4H7O2(orCH3CH2CH2COOH)is
usedtomakecompoundsemployedin
artificialflavoringsandsyrups.A0.250M
aqueoussolutionofHC4H7O2isfoundtohave
apHof2.72.DetermineKA forbutyricacid.
2. CalculatethepHofa0.20MsolutionofKF,Kb
forF is1.5x1011.
Acids,BasesandSalts
Hydrolysis
is the reaction between water and the ions contained in
th water
the
t solution.
l ti
Wh
When this
thi occurs, thi
this could
ld result
lt iin
producing an acidic or basic solution.
Spectator ions do NOT undergo hydrolysis. They are:
1. Group 1 (alkali metals): Li+, Na+, K+, Rb+, Cs+, Fr+
2. Group 2 (alkaline-earth metals): Be2+, Mg2+, Ca2+, Ba2+, Sr2+
3. Conjugate bases of strong acids: ClO4-, I-, Br-, Cl-, NO3-
64
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Acids,BasesandSalts
Cation that undergo hydrolysis

NH4+, ammonia
Hydrolysis equation:
NH4+ (aq) + H2O () H3O+ (aq) + NH3 (aq)
65
Acids,BasesandSalts
Hydrated cations that undergo hydrolysis

Transition metals have smaller ions and bigger charges
This
Thi attracts
tt t H2O molecules
l
l
3+
Example Fe or iron (III) ions forms
Fe3+ (aq) + 6 H2O () Fe(H2O)63+ (aq)
Hexaaquoiron,oriron(III)ionisaweakacid.
Other hydrated ions are chromium (III) and

aluminum (III) ions
66
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Acids,BasesandSalts
Anions that undergo hydrolysis
.
.
.
Allionsinthissectioncanundergo
hydrolysis.
Anions that are not amphiprotic will act as weak bases in water.
67
Acids,BasesandSalts

Examples of net ionic hydrolysis equations are:
IO3- (aq) + H2O () HIO3 (aq) + OH- (aq)
NO2- (aq) + H2O () HNO2 (aq) + OH- (aq)
CH3COO- (aq)
( ) + H2O () CH3COOH (aq)
( ) + OH- (aq)
( )
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26/02/2012
Acids,BasesandSalts
These2ionsactasSTRONGBases.Theyundergo
100%hydrolysistoformOH ions.
Anions that are not amphiprotic will act as weak bases in water.
69
Acids,BasesandSalts
Anions that do not undergo hydrolysis
These5ionsdoNOTundergohydrolysis.
Theyarespectators.
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Acids,BasesandSalts
Amphiprotic anions that undergo hydrolysis

These anions start with H and have a - charge.
Examples: HSO4-, HSO3-, H2PO4-, HPO42-, HS- etc.
Amphiprotic anions hydrolyze as acids to produce H3O+, but
They also hydrolyze as bases to produce OH-. Compare the
Ka and Kb values to determine the predominant hydrolysis.
Find the Ka of the ion by looking for the ion on the LEFT side of the
acid table.
Find the Kb of the ion by looking for the ion on the RIGHT side of
the acid table. (Kb = Kw/Ka (conjugate acid))
71
Acids,BasesandSalts
1. Is the salt NaCl acidic, basic or neutral in water?

NaCl ((s)) Na+ ((aq)
q) + Cl- ((aq)
q)
Na+ andCl ionsarespectatorions.
Asaresult
Nohydrolysisreactionoccurs.
Solutionisneutral.
72
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Acids,BasesandSalts
2. Is the salt NaF acidic, basic or neutral in water?

What is the net ionic equation?
NaF ((s)) Na+ ((aq)
q) + F- ((aq)
q)
F
Na+ ionsarespectatorions.
ionsarefoundontherightsideoftheacidtable.
Itisaweakbase.
As a result
Asaresult
F undergoeshydrolysisreaction.
(aq)+H2O() HF(aq)+OH (aq)
Solutionisbasic.
73
Acids,BasesandSalts
3. Is the salt NH4NO3 acidic, basic or neutral in water?

NH4NO3 ((s)) NH4+ ((aq)
q) + NO3- ((aq)
q)
NH4+
NO3 ionsarespectatorions.
ionsarefoundontheleftsideoftheacidtable.
Itisaweakacid.
Asaresult
NH4+ undergoeshydrolysisreaction.
NH4+ (aq)+H2O() NH3 (aq)+H3O+ (aq)
Solutionisacidic.
74
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Acids,BasesandSalts
4. Is the salt NaHC2O4 acidic, basic or neutral in water?

NaHC2O4 ((s)) Na+ ((aq)
q) + HC2O4- ((aq)
q)
HC2O4
ionsarefoundontherightandleftsideoftheacidtable.
Itcaneitherbeaweakacidoraweakbase.
Asaresult,compare
Ka andKb valuesofHC2O4.
HC2O4
Ka 6.4x10-5; Kb
1014
-2
5.9x10
1.7x10-13
Ka >Kb.
(aq)+H2O() H2C2O4 (aq)+H3O+ (aq)
Solutionisacidic.
75
Acids,BasesandSalts
5. Is the salt NH4NO2 acidic, basic or neutral in water?

Write the net ionic equation.
NH4NO2 ((s)) NH4+ ((aq)
q) + NO2- ((aq)
q)
NH4+ ionsarefoundontheleftsideoftheacidtable.
NO2 ionsarefoundontherightsideoftheacidtable.
Asaresult,compare
Ka ofNH4+ Kb ofNO2.
Ka 5.6x10 ; Kb
-10
Ka >Kb.Solutionisacidic.
1014
-4
4.6x10
2.2x10-11
76
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Acids,BasesandSalts
6. Is the HCO3- ion acidic, basic or neutral in water?

HCO33 ionsarefoundontherightandleftsideoftheacidtable.
ions are found on the right and left side of the acid table
Asaresult,compareKa andKb ofHCO3.
Ka 5.6x10 ; Kb
-10
HCO3
1014
-7
4.3x10
2.3x10-8
Kb >Ka.
(aq)+H2O() H2CO3 (aq)+OH (aq)
Solutionisbasic.
77
Acids,BasesandSalts
Salt Examples
Predict whether the following solutions are acidic or basic?
a)) NaOCl
N OCl
Na+ no hydrolysis,
N
h d l i OCl- is
i conjugate
j
t b
base off HOCl.
HOCl
Therefore solution is basic.
b) KCl
K+ no hydrolysis, Cl- no hydrolysis.

Therefore solution is neutral.
c)) NH4Br
Br- no hydrolysis
y
y
(HBr
(
is strong
g acid)) ,
NH4+ is a weak acid. Therefore solution is acidic.
d) NH4CN Both NH4+ and CN- hydrolyze in aqueous solutions.

Must compare the values of Ka(NH4+) = 5.6x10-10
and Kb(CN-) = 2.0x10-5. Since Kb>Ka the solution is
basic.
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26/02/2012
Acids,BasesandSalts
Acids,BasesandSalts
Is the salt Na2CO3 acidic, basic or neutral in water?

Write the net ionic equation.
Na2CO3 ((s)) 2 Na+ ((aq)
q) + CO32- ((aq)
q)
CO32 ionsarefoundontherightsideoftheacidtable.
Itisaweakbase.
As a result
Asaresult
CO32 undergoeshydrolysisreaction.Thenetionicequationis
CO32 (aq)+H2O() HCO3 (aq)+OH (aq)
Solutionisbasic.
80
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Acids,BasesandSalts
Calculate the pH of 0.30 M Na2CO3.

Step 1: Identify the ions involved
involved.
Na2CO3 (s) 2 Na+ (aq) + CO32- (aq)
Spectatorion
Foundontheright
sideoftheacid
table;undergobase
h d l i
hydrolysis
81
Acids,BasesandSalts

Step 2: Write the net ionic equation for the hydrolysis. Set up
ICE table.
CO32-(aq) + H2O () HCO3- (aq) + OH- (aq)
CO32(aq)+H2O() HCO3 (aq)+OH (aq)
[I]
0.30
[C]
x
[E] 0.30 x
0
+x
x
0
+x
x
Stoichio
metric
ratio
82
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26/02/2012
Acids,BasesandSalts

Step 3: Determine the Kb for the base hydrolysis.
Look up in the acid table the Ka for HCO3-
Kb
Kw
K a (HCO 3 )
1.0 x 10 -14
5.6 x 10
-11
1.786 x 10 -4
83
Acids,BasesandSalts

Step 4: Write the Kb expression for the base hydrolysis.
Kb
[HCO 3 ] [OH - ]
[CO 3 2 ]
84
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26/02/2012
Acids,BasesandSalts

Step 5: Substitute in the equilibrium concentrations
from the ICE table.
CO32(aq)+H2O() HCO3 (aq)+OH (aq)
[I]
0.30
[C]
[E]
Kb
+x
+x
0 30 x
0.30
[HCO 3 ] [OH - ]
[CO 3 2 ]
x2
1.786 x 10 -4
0.30 - x
85
Acids,BasesandSalts

Step 6: Solve for x, where x = [OH-].
Kb
[HCO 3 ] [OH - ]
[CO 3 2 ]
x2
1.786 x 10 - 4
0 30
0.30
x2
1.786 x 10 - 4
0.30 - x
Useassumption0.30 x 0.30
because
[0.30]>1000x1.786x104
[OH-] = x = 7.319 x 10-3 M

86
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26/02/2012
Acids,BasesandSalts

Step 7: From the [OH-], calculate the pOH.
pOH = -log (7.319 x 10-3) = 2.1355
Step 8: Convert pOH to pH.
pH = 14 pOH = 14 2.1355
2 1355 = 11
11.86
86
Step 9: Check that your answer makes sense.
We expect CO32- ions will undergo base
hydrolysis. pH > 7.
87
Acids,BasesandSalts
Dissolve 45.0 g of NH4Cl in 1.50 L of water. What is the pH

of this solution? Molar mass of NH4Cl is 53.5 g/mole.
88
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26/02/2012
Acids,BasesandSalts

Step 1: Determine the concentration of the solution.
45.0 g
0.841 mole
53.5 g/mole
0.841 mole
0.561 M NH 4 Cl
1.50 L
89
Acids,BasesandSalts

Step 2: Identify the ions involved.
NH4Cl (s) NH4+ (aq) + Cl- (aq)
Foundontheleft
side of the acid
sideoftheacid
table;undergoacid
hydrolysis
Spectatorion
90
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26/02/2012
Acids,BasesandSalts

Step 3: Write the net ionic equation for the hydrolysis.
Set up ICE table.
NH4+ (aq) + H2O () NH3 (aq) + H3O+ (aq)
[I]
0.561
[C]
x
[E] 0.561 x
0
+x
x
0
+x
x
Stoichio
metric
ratio
91
Acids,BasesandSalts

Step 4: Determine the Kb for the base hydrolysis.
NH4+ (aq) + H2O () NH3 (aq) + H3O+ (aq)
Look up in the acid table the Ka for NH4+
Ka
92
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26/02/2012
Acids,BasesandSalts

Step 5: Write the Ka expression for the acid hydrolysis.
NH4+ (aq) + H2O () NH3 (aq) + H3O+ (aq)
[[NH 3 ] [H 3O ]
Ka
[ NH 4 ]
93
Acids,BasesandSalts

Step 6: Substitute in the equilibrium concentrations
from the ICE table.
[I]
[[C]]
[E]
0.561
x
0.561 x
0
+x
+x
x
0
+x
+x
x
[NH 3 ] [H 3O ]
x2
Ka
5.6x10 -10
0.561 - x
[ NH 4 ]
94
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26/02/2012
Acids,BasesandSalts

Step 7: Solve for x, where x = [H3O+].
[NH 3 ] [H 3O ]
x2
Ka
5.6x10 -10
0.561 - x
[ NH 4 ]
Make assumption: 0.561 x 0.561
x2
Checkassumption:
Ka
5.6 x10 -10
[Initial]>1000xKa
0.561
[H3O+] = x = 1.8 x 10-5 M
Assumption is valid because

0.561 > 1000 x 5.6 x 10-10
95
Acids,BasesandSalts

Step 8: Convert to pH.
[H3O+] = x = 1.8 x 10-5 M

pH = - log (1.8 x 10-5 ) = 4.74
96
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Acids,BasesandSalts
Titrations
Equivalencepoint:
Equivalence point:
Thepointinthereactionatwhichbothacidandbasehavebeen
consumed.
Neitheracidnorbaseispresentinexcess.
Endpoint:
Thepointatwhichtheindicatorchangescolor.
Titrant:
Thesolutionaddedtothesolutionintheflask.
TitrationCurve:
AplotofpHofthesolutionbeinganalyzedasafunctionofthe
amountoftitrantadded.
97
Acids,BasesandSalts
Acid-Base Indicators
ColorofsomesubstancesdependsonthepH.
p
p
HIn(aq)+H2O() In(aq)+H3O+(aq)
>90%acidformthecolorappearstobetheacidcolor
>90%baseformthecolorappearstobethebasecolor
Intermediatecolorisseeninbetweenthesetwostates.
Completecolorchangeoccursover2pHunits
Markstheendpointofatitrationbychanging
M k h
d i
f i i b h i
color.
Theequivalencepointisnot necessarilythesame
astheendpoint.
98
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26/02/2012
Acids,BasesandSalts
Theacidandbaseformsofthe
indicatorphenolphthalein.Inthe
acidform(Hln),themoleculeis
colorless.Whenaproton(plus
H2O)isremovedtogivethebase
form(ln),thecolorchangesto
pink.
i k
99
Acids,BasesandSalts
100
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26/02/2012
Acids,BasesandSalts
Titration of a Strong Acid with a Strong Base
ThepHhasalowvalueatthebeginning.
The pH has a low value at the beginning
ThepHchangesslowly
untiljustbeforetheequivalencepoint.
ThepHrisessharply
perhaps6unitsper0.1mL additionoftitrant.
ThepHrisesslowlyagain.
The pH rises slowly again.
AnyAcidBaseIndicatorwilldo.
AslongascolorchangeoccursbetweenpH4and10.
101
Acids,BasesandSalts
The pH curve for the

titration of 100
100.0
0 mL of
0.10 M HCl with 0.10 M
NaOH.
Note:
At the equivalence
point pH = 7
Either indicator will
give a fairly accurate
result
102
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26/02/2012
Acids,BasesandSalts
For the titration

of a strong
base with a
strong acid the
titration curve is
just flipped
over.
The pH curve
for the titration
of 100.0 mL of
0.50 M NaOH
with 1.0 M HCl.
103
Acids,BasesandSalts
Weak Acid - Strong Base Titration
Step1
Step
1
A stoichiometry problem
Astoichiometry
problem reactionis
reaction is
assumedtoruntocompletion thendetermine
remainingspecies.
Step2 An equilibriumproblem determine

position of eak acid eq ilibri m and calc late
positionofweakacidequilibriumandcalculate
pH.
104
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26/02/2012
Acids,BasesandSalts
Weak Acid - Strong Base Titration

The pH curve for the titration of
50.0 mL of 0.100 M HC2H3O2 with
0.100 M NaOH.
Note:
At the equivalence point pH > 7
Choice of indicator is important
pKa = pH at the point halfway to
the equivalence point
The
Th pH
H iis ffairly
i l constant
t t around
d
halfway to the equivalence point
i,.e it is a buffer solution
105
Acids,BasesandSalts
Comparison of strong
and weak
acid titration curves.
106
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26/02/2012
Acids,BasesandSalts
The pH curves for the

titrations of 50.0-mL
samples of 0.10 M
acids with various Ka
values with 0.10 M
NaOH.
107
Acids,BasesandSalts
For the titration of

a weak base with a
strong acid the
titration curve is
just flipped over.
The pH curve for
the titration of
100.0 mL of 0.050
M NH3 with 0.10 M
HCl.
Note at
equivalence point
pH < 7
108
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26/02/2012
Acids,BasesandSalts
Titration of a Weak Polyprotic Acid

NaOH
H3PO4
NaOH
H2PO4-
NaOH
HPO42- PO43-
109
Acids,BasesandSalts
Buffer Solutions
TwocomponentsystemsthatchangepHonly
slightlyonadditionofacidorbase.
li htl
dditi
f id b
Thetwocomponentsmustnotneutralizeeachother
butmustneutralizestrongacidsandbases.
Aweakacidanditsconjugatebase.
Aweakbaseanditsconjugateacid
A
kb
d it
j t
id
Afteradditionofstrongacidorbase,dealwith
stoichiometry first,thenequilibrium.
110
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26/02/2012
Acids,BasesandSalts
How A Buffer Works
111
Acids,BasesandSalts
The Henderson-Hasselbalch Equation

A variation of the ionization constant expression.
Consider a hypothetical weak acid, HA, and its salt NaA:
HA(aq) H+(aq) + A-(aq)
Ka
H A
HA
pK a pH log
pH pK a log
log K a log H log
HA
or pH pK a log
HA
HA
conjugate base
conjugate acid
112
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26/02/2012
Acids,BasesandSalts
The Henderson-Hasselbalch Equation

Onlyusefulwhenyoucanuseinitial
y
y
concentrationsofacid
andsalt.
Thislimitsthevalidityoftheequation.
Limitscanbemetby:
0.1
A 10
HA
and both A 10K a and HA 10K a

113
Acids,BasesandSalts
Characteristics of the Henderson-Hasselbalch Equation

pHdependsonlyontheratio[A]/[HA]
ThismeansthatthepHofabuffersolutiondoesnot
changeondilution.
When[A]=[HA]thenpH=pKa.Thisisalsothepoint
wheretheratiochangesleastupontheadditionofeither
acidorbase.Thereforeasystemisbestatbufferingata
pH=pKa.
pHchangesastheLogoftheratio[A
pH changes as the Log of the ratio [A]/[HA].Therefore
]/[HA] Therefore
pHisnotverysensitivetothevalueof[A]/[HA]
Thelargerthevalueof[A]and[HA]themoreacidor
basethatcanbeaddedwithoutsignificantlychangingthe
pH(i.e.thegreaterthebufferingcapacityofthesolution).
114
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26/02/2012
Acids,BasesandSalts
Buffer Solutions
Considerthecaseofaceticacid
CH3COOH(aq)+H2O() H3O+ (aq)+CH3COO(aq)
pKa =4.75
[CH3COO]/[CH3COOH]
0.1
05
0.5
1
2
10
pH
3.75
4 45
4.45
4.75
5.05
5.75
115
Acids,BasesandSalts
Preparing a Buffer Solution of a Desired pH

What
WhatmassofNaC
mass of NaC2H3O2 mustbedissolvedin0.300Lof0.25M
must be dissolved in 0.300 L of 0.25 M
HC2H3O2 (Ka =1.8x105)toproduceasolutionwithpH=5.09?
(Assumethatthesolutionvolumeisconstantat0.300L)
116
58

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26/02/2012

We will cover the following topics:

Arrhenius Definition of Acids and Bases

When an acid and base reacts, an ionic compound is produced as

Arrhenius Theory of Acid and Bases

LiOH(aq) + HBr(aq) LiBr(aq) + H2O()

If we write the net ionic equation for both of these reactions we

Monoprotic and Polyprotic acids

Monoprotic and Polyprotic acids

HPO4 2- (aq) + H2O () H3O+ (aq) + PO43- (aq)

Monoprotic and Polyprotic bases

Monoprotic and Polyprotic bases

Brnsted-Lowry Acids and Bases

Brnsted-Lowry Acids and Bases

We need a broader definition!

Brnsted-Lowry Acids and Bases

Brnsted-Lowry Acids and Bases

This species accepts

Brnsted-Lowry Acids and Bases

CONJUGATE ACID-BASE PAIRS

Brnsted-Lowry Acids and Bases

Brnsted-Lowry Conjugate Acids-Bases Pairs

We will cover the following topics:

HCO3- (aq) + H3O+ (aq) H2CO3 (aq) + H2O ()

HSO4- (aq) + H3O+ (aq) H2SO4 (aq) + H2O ()

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

Recall the pH scale

For an increase in 1 pH unit, the solutions [H+] decreases 10x.

These are strong acids

CH3COOH (aq) + H2O ()

H3O+ (aq) + CH3COO- (aq)

The [H+] (or [H3O+]) concentration of a 0.10 M CH3COOH

H3O+ (aq) + A- (aq)

These are weak acids except

These last two are too weak to act as acids in water.

Illustration of Strong and

Illustration of Strong and Weak Acids

(a) A strong acid HA is completely ionized in water.

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

pH and pOH scales

[OH-] > [H+]

These are strong bases.

NH3 (aq) + H2O ()

NH4+ (aq) + OH- (aq)

The [OH-] concentration of a 0.10 M NH3 solution is

BH+ (aq) + OH- (aq)

Conjugate bases of strong acids are VERY weak bases.

These are weak bases

HCO3- is a weaker acid than phenol and a stronger acid

HCO3- is a weaker base than citrate ion and a stronger base

Brnsted-Lowry Acids and Bases

We will work with the reference table

to determine the Acid-Base Equilibria and Relative Strengths of

1. When H2CO3 and SO32- are mixed, an equilibrium is set up.

1. When H2CO3 and SO32- are mixed, an equilibrium is set up.

HCO3- (aq) + HSO3- (aq)

Compare the Ka of the two acids

H2CO3 is a slightly stronger acid than HSO3-.

1. When H2CO3 and SO32- are mixed, an equilibrium is set up.

What is the value of K for this equilibrium?

Since K >1, equilibrium favors products

2. When H2PO4- and CO32- are mixed, an equilibrium is set up.

2. When H2PO4- and CO32- are mixed, an equilibrium is set up.