UNIVERSITY INDONESIA OF

AqueousEquilibria:
AcidandBase
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AcidBaseConcepts:
Bronsted Lowry theory
Arrhenius theory of acids and bases.
BronstedLowrytheory
e us t eo y o ac ds a d bases.
Acids substances that dissociate in water to produce
hydrogen ions.
HA (aq) H
+
(aq) + A

(aq)
Bases substances that dissociate in water to produce
hydroxide ions. hydroxide ions.
MOH (aq) M
+
(aq) + OH

(aq)
Limitations to theory.
restricted to aqueous solutions
doesn't account for the basicity of substances that don't
contain OH groups
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AcidBaseConcepts:
Bronsted Lowry theory
BrnstedLowry theory of acids and bases
BronstedLowrytheory
Brnsted Lowry theory of acids and bases
Acid any substance that can transfer a proton to
another substance (proton donor) another substance (proton donor).
Base any substance that can accept a proton
(proton acceptor). (proton acceptor).
Acidbase reaction protontransfer reactions
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AcidBaseConcepts:
Bronsted Lowry theory
Conjugate acidbase pair chemical species
BronstedLowrytheory
Conjugate acid base pair chemical species
whose formulas differ only by one proton.
Conjugate base has one less proton than its acid Conjugate base has one less proton than its acid.
A

is the conjugate base of HA

Conjugate acid has one more proton than its base Conjugate acid has one more proton than its base.
BH
+
is the conjugate acid of B
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AcidBaseConcepts:
Bronsted Lowry theory
Aciddissociation equilibrium
BronstedLowrytheory
Acid dissociation equilibrium.
acid transfers a proton to the solvent, which acts
as a base as a base.
HA (aq) + H
2
O (l) H
3
O
+
(aq) + A

(aq)
Base dissociation equilibrium Basedissociation equilibrium.
Base accepts a proton from the solvent, which
acts as an acid acts as an acid.
NH
3
(aq) + H
2
O (l) OH

(aq) + NH
4
+
(aq)
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AcidBaseConcepts:
Bronsted Lowry theory
All BrnstedLowry bases have one or more
BronstedLowrytheory
All Brnsted Lowry bases have one or more
lone pairs of electrons.
Unshared pair of electrons are used for bonding to Unshared pair of electrons are used for bonding to
the proton.
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BronstedLowry
theory theory
UNIVERSITY INDONESIA OF
BronstedLowry
acid
UNIVERSITY INDONESIA OF
BronstedLowry
base
UNIVERSITY INDONESIA OF
AcidBaseConcepts:
Bronsted Lowry theory
EXAMPLE:
BronstedLowrytheory
EXAMPLE:
Write the proton transfer equilibria for the
following acids or bases in aqueous solution following acids or bases in aqueous solution
and identify the conjugate acidbase pairs in
each one:
C
6
H
5
NH
3
+
(anilinium ion),
H
2
PO
4

(acid reaction),
NH
2
NH
2
(hydrazine, a base), and
PO
4
3
.
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AcidBaseConcepts:
Bronsted Lowry theory
C
6
H
5
NH
3
+
(aq) + H
2
O C
6
H
5
NH
2
+ H
3
O
+
(aq)
BronstedLowrytheory
C
6
H
5
NH
3
(aq) + H
2
O C
6
H
5
NH
2
+ H
3
O (aq)
Conjugate acidbase pairs:
C H NH
+
(acid)/C H NH (base); H O (base)/H O
+
C
6
H
5
NH
3
+
(acid)/C
6
H
5
NH
2
(base); H
2
O (base)/H
3
O
+
(acid)
H PO

(aq) + H O HPO
2
(aq) + H O
+
(aq) H
2
PO
4
(aq) + H
2
O HPO
4
2
(aq) + H
3
O
+
(aq)
Conjugate acidbase pairs:
H PO ( id)/ HPO
2
(b ) H O (b )/H O
+
H
2
PO
4

(acid)/ HPO
4
2
(base); H
2
O (base)/H
3
O
+
(acid)
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AcidBaseConcepts:
Bronsted Lowry theory
NH
2
NH
2
+ H
2
O NH
2
NH
3
+
(aq) + OH

(aq)
BronstedLowrytheory
NH
2
NH
2
+ H
2
O NH
2
NH
3
(aq) + OH (aq)
Conjugate acidbase pairs:
NH NH (base)/NH NH
+
(acid); H O (acid)/OH

NH
2
NH
2
(base)/NH
2
NH
3
+
(acid); H
2
O (acid)/OH
(base)
PO
3
(aq) + H O HPO
2
(aq) + OH

(aq) PO
4
3
(aq) + H
2
O HPO
4
2
(aq) + OH (aq)
Conjugate acidbase pairs:
PO
3
(b )/HPO
2
( id) H O ( id)/OH (b ) PO
4
3
(base)/HPO
4
2
(acid); H
2
O (acid)/OH

(base)
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AcidStrengthand
Base Strength
In an aciddissociation equilibrium the two
BaseStrength
In an acid dissociation equilibrium, the two
bases, H
2
O and A

, are competing for protons.

Direction of reaction to reach equilibrium is Direction of reaction to reach equilibrium is
proton transfer from the stronger acid to the
stronger base. g
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AcidStrengthand
Base Strength
Strong acid completely dissociated in
BaseStrength
Strong acid completely dissociated in
aqueous solution.
Have weak conjugate base Have weak conjugate base.
H
2
O is a stronger base than A

Weak acid partially dissociates in aqueous Weak acid partially dissociates in aqueous
solution.
Ha e strong conj gate base Have strong conjugate base.
A

is a stronger base than H

2
O
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Acid dissociation Aciddissociation
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Conjugateacid
basepairs
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AcidStrengthand
Base Strength
EXAMPLE:
BaseStrength
EXAMPLE:
Determine the direction of reactions involving:
ti id t t i h d lf i id d HS acetic acid, acetate ion, hydrosulfuric acid, and HS

acetic acid, acetate ion, hydrogen sulfate, and

SO
2
SO
4
2
.
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AcidStrengthand
Base Strength
CH
3
COOH + HS

(aq) CH
3
CO
2

(aq) + H
2
S
BaseStrength
CH
3
COOH + HS (aq) CH
3
CO
2
(aq) + H
2
S
HSO
4

(aq)+CH
3
CO
2

(aq)SO
4
2
(aq)+ CH
3
COOH
UNIVERSITY INDONESIA OF
Introductionto
aqueousacids
Introductiontoaqueousacids
UNIVERSITY INDONESIA OF
Introductionto
aqueousbases
IntroductiontoaqueousBases
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HydratedProtons
d H d i I
Hydronium ion H
3
O
+
ion in which H
+
is bonded
andHydronium Ions
Hydronium ion, H
3
O ion in which H is bonded
to the oxygen atom of a solvent water molecule.
Simplest hydrate of the proton [H(H
2
O)]
+
. Simplest hydrate of the proton [H(H
2
O)] .
produces higher hydrates through hydrogen bonding with
other water molecules
l f l [H(H O) ]
+
general formula [H(H
2
O)
n
]
+
Symbols H
+
(aq) and H O
+
(aq) used to represent a Symbols H (aq) and H
3
O (aq) used to represent a
proton hydrated by an unspecified number of water
molecules.
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Dissociationof
W t
Water can act both as an acid and as a base.
Water
Water can act both as an acid and as a base.
Dissociation of water one water molecule
donates a proton to another water molecule. donates a proton to another water molecule.
H
2
O (l) + H
2
O (l) H
3
O
+
(aq) + OH

(aq).
Ionproduct constant for water, Kw. p ,
Kw = [H
3
O
+
] [OH

]
Forward and reverse reactions are rapid.
Position of the equilibrium lies far to the left.
In an aqueous solution, [H
3
O
+
][OH

] = 1.0 x 10
14
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Dissociationof
W t
Relative values of H
3
O
+
and OH

concentrations can be
Water
3
used to determine if an aqueous solution is neutral,
acidic or basic.
1010
14
[H
3
O
+
] =
1.010
[OH
-
]
1.010
14

[H
3
O
+
] = [OH

], neutral solution and [H

3
O
+
] = 1.0 x 10
7
M.
[ O
+
] [O ] id l i d [ O
+
] 0 0
7
[OH
-
] =
.
[H
3
O
+
]
[H
3
O
+
] > [OH

], acid solution and [H

3
O
+
] > 1.0 x 10
7
M.
[H
3
O
+
] < [OH

], basic solution and [H

3
O
+
] < 1.0 x 10
7
M.
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Hydronium ion Hydronium ion
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Dissociationof
water
UNIVERSITY INDONESIA OF
Dissociationof
W t
EXAMPLE:
Water
EXAMPLE:
Calculate the molarity of OH

in a solution
with an H O
+
concentration of 0 35 M Is this with an H
3
O
+
concentration of 0.35 M. Is this
solution acidic, basic or neutral?
I l i i h OH i f 8 5 Is a solution with an OH

concentration of 8.5
10
5
M acidic, basic or neutral?
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Dissociationof
W t
If we know either the [H
3
O
+
] or [OH

] we can
Water
If we know either the [H
3
O ] or [OH ], we can
calculate the other from the relationship
Kw = [H O
+
][OH

] Kw = [H
3
O ][OH ].
OH
-
| |
=
110
14
035
= 2.910
14
Since [H
3
O
+
] > 1.0 10
7
this solution is acidic.
| |
0.35
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Dissociationof
W t Water
| |
1010
14
10
H
3
O
+
| |
=
1.010
8.510
5
=1.210
10
I thi [H O
+
] < 1 0 10
7
In this case, [H
3
O
+
] < 1.0 10
7
;
therefore, the solution is basic.
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The pH Scale
pH scale logarithmic scale used to express
ThepHScale
pH scale logarithmic scale used to express
the hydronium ion concentration.
pH = log[H O
+
] pH = log[H
3
O ].
[H
3
O
+
] = antilog(pH) = 10
pH
.
Significant figures in a logarithm are the digits to Significant figures in a logarithm are the digits to
the right of the decimal point.
number to the left of the decimal point is an exact number to the left of the decimal point is an exact
number related to the integral power of 10 in the
exponential expression for [H3O+]
UNIVERSITY INDONESIA OF
The pH Scale
pH decreases as [H
3
O
+
] increases
ThepHScale
pH decreases as [H
3
O ] increases.
Acidic solutions, pH < 7.
Basic solutions pH > 7 Basic solutions, pH > 7.
Neutral solutions, pH = 7.
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pH pH
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Measuring pH
Acidbase indicators (HIn) substances that
MeasuringpH
Acid base indicators (HIn) substances that
change color in a specific pH range.
Weak acids Weak acids.
Have different colors in their acid (HIn) and
conjugate base (In) forms conjugate base (In ) forms.
Change color over a range of ~ 2 pH units.
Can determine the pH of a solution to within ~ 1 Can determine the pH of a solution to within ~ 1
pH unit.
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Measuring pH
pH meter
MeasuringpH
pH meter.
An electronic instrument that measures a pH
dependent electrical potential of the test solution dependent electrical potential of the test solution.
Determines pH values more accurately than acid
base indicators. base indicators.
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Acidbase
indicators
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Natural indicators Naturalindicators
Naturalindicators
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Measuring pH
EXAMPLE:
MeasuringpH
EXAMPLE:
Calculate the pH of a 1.25 x 10
3
M HNO
3
solution.
SOLUTION: SOLUTION:
HNO
3
is a strong acid which completely dissociates
in water.
Therefore, [H
3
O
+
] = initial concentration of the
undissociated acid.
[H
3
O
+
] = 1.25 x 10
3
M
pH = log [H
3
O
+
] = log (1.25 x 10
3
) = 2.903
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ThepHofstrongacids
d b
Strong acids 100 % dissociated in aqueous
andstrongbases
Strong acids 100 % dissociated in aqueous
solution (HClO
4
, HCl, HNO
3
).
[H O
+
] = [A

] = initial concentration of the acid [H

3
O ] = [A ] = initial concentration of the acid.
[undissociated HA] = 0.
Monoprotic acid pH log[H O
+
] Monoprotic acid, pH = log[H
3
O
+
]
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ThepHofstrongacids
d b
Strong bases
andstrongbases
Strong bases.
Alkali metal hydroxides, MOH.
watersoluble ionic solids watersoluble ionic solids
exist in aqueous solution as alkalimetal cations and
hydroxide anions
calculate pH from [OH]
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ThepHofstrongacids
d b
Strong bases
andstrongbases
Strong bases.
Alkalineearth metal hydroxides, M(OH)2 (M = Mg,
Ca Sr Ba) Ca, Sr, Ba).
less soluble than alkali hydroxides, therefore lower [OH]
most important strong base lime, CaO p g
produces Ca(OH)2 when mixed with water
used in steel making, water purification, and chemical
manufacture manufacture
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Equilibria inSolutions
f W k A id
Weak acids partially dissociated; can write an acid
ofWeakAcids
p y ;
dissociation equilibrium equation.
HA (aq) + H
2
O (l) H
3
O
+
(aq) + A

(aq)
P i i f id di i i ilib i h i d Position of aciddissociation equilibrium characterized
by the aciddissociation constant, Ka.
[H O
+
][A
-
]
The larger the value of Ka, the stronger the acid.
K
a
=
[H
3
O
+
][A
-
]
[HA]
g , g
Ka values can be determined from pH measurements.
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Aciddissociation
constant
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Weak acids Weakacids
UNIVERSITY INDONESIA OF
Weak acids Weakacids
UNIVERSITY INDONESIA OF
Equilibria inSolutions
f W k A id
EXAMPLE:
ofWeakAcids
EXAMPLE:
The pH of a 0.200 M solution of nicotinic acid
(HC H NO ) is 2 78 (HC
6
H
4
NO
2
) is 2.78.
Determine the value of Ka for this acid.
UNIVERSITY INDONESIA OF
Equilibria inSolutions
f W k A id
SOLUTION:
ofWeakAcids
SOLUTION:
To determine Ka first write the balanced
equation for the dissociation equilibrium and equation for the dissociation equilibrium and
the equilibrium equation that defines Ka.
HC H NO ( ) H O(l)H O
+
( ) C H NO ( ) HC
6
H
4
NO
2
(aq)+H
2
O(l)H
3
O
+
(aq)+C
6
H
4
NO
2
(aq)
[H O
+
][C H NO
-
]
K
a
=
[H
3
O ][C
6
H
4
NO
2
]
[HC
6
H
4
NO
2
]
UNIVERSITY INDONESIA OF
Equilibria inSolutions
f W k A id
To determine Ka we need to know the
ofWeakAcids
To determine Ka we need to know the
concentrations of the species in the
equilibrium mixture We can determine the equilibrium mixture. We can determine the
concentration of H
3
O
+
from the pH.
[H O
+
] = antilog ( pH) = antilog ( 2 780) = 1 66 [H
3
O
+
] = antilog (pH) = antilog (2.780) = 1.66
x 10
3
M.
UNIVERSITY INDONESIA OF
Equilibria inSolutions
f W k A id
Dissociation of one HC
6
H
4
NO
2
molecule
ofWeakAcids
Dissociation of one HC
6
H
4
NO
2
molecule
produces one H
3
O
+
and C
6
H
4
NO
2

ion; the H
3
O
+
and C
6
H
4
NO
2

concentrations are equal and C

6
H
4
NO
2
concentrations are equal.
[H
3
O
+
] = [C
6
H
4
NO
2

] = 1.66 x 10
3
M
Th [HC H NO ] i ilib i The [HC
6
H
4
NO
2
] concentration at equilibrium
is equal to the initial concentration minus the
f HC H NO h di i amount of HC
6
H
4
NO
2
that dissociates.
UNIVERSITY INDONESIA OF
Equilibria inSolutions
f W k A id
The [HC
6
H
4
NO
2
] concentration at equilibrium
ofWeakAcids
The [HC
6
H
4
NO
2
] concentration at equilibrium
is equal to the initial concentration minus the
amount of HC
6
H
4
NO
2
that dissociates amount of HC
6
H
4
NO
2
that dissociates.
[HC
6
H
4
NO
2
] = 0.200 (1.66 x 10
3
) = 0.198 M
K =
[H
3
O
+
][C
6
H
4
NO
2
-
]
=
1.6610
3
( )
1.6610
3
( )
=13910
5
K
a
=
[HC
6
H
4
NO]
=
0.198
( )
=1.3910
UNIVERSITY INDONESIA OF
CalculatingEquilibrium
ConcentrationsinWeak
Equilibrium concentrations and the pH of a
AcidSolutions
Equilibrium concentrations and the pH of a
solution of a weakacid can be calculated from
the value of Ka the value of Ka.
To solve acidbase equilibrium problems, think
about the chemistry about the chemistry.
UNIVERSITY INDONESIA OF
CalculatingEquilibrium
ConcentrationsinWeak
EXAMPLE:
AcidSolutions
EXAMPLE:
Calculate the concentration of all species
present (H O
+
C H O

HC H O and OH

) and present (H
3
O
+
, C
4
H
7
O
2
, HC
4
H
7
O
2
, and OH ) and
the pH in 0.250 M butyric acid (HC
4
H
7
O
2
).
UNIVERSITY INDONESIA OF
CalculatingEquilibrium
ConcentrationsinWeak
The species present initially are HC
4
H
7
O
2
(acid)
AcidSolutions
e spec es p ese t t a y a e C
4 7
O
2
(ac d)
and H
2
O (acid or base)
The possible protontransfer reactions are p p
HC
4
H
7
O
2
(aq) + H
2
O (l) H
3
O
+
(aq) + C
4
H
7
O
2

(aq)
Ka = 1.5 x 10
5
H
2
O (l) + H
2
O (l) H
3
O
+
(aq) + OH

(aq)
Kw = 1.0 x 10
14
Since Ka >> Kw, the principal reaction is
dissociation of HC
4
H
7
O
2
.
UNIVERSITY INDONESIA OF
CalculatingEquilibrium
ConcentrationsinWeak
[HC
4
H
7
O
2
]=0.250x
AcidSolutions
[
4 7 2
]
[H
3
O
+
]=x
[C
4
H
7
O
2

]=x
K
a
=1.510
5
=
[H
3
O
+
][C
4
H
7
O
2
-
]
[HC H O ]
=
x ( ) x ( )
0250 x
( )
Assume that x is negligible compared with the
initial concentration of the acid; therefore 0 250
[HC
4
H
7
O
2
] 0.250 x
( )
initial concentration of the acid; therefore 0.250
x ~ 0.250.
Using this value in the denominator, solve for x. g ,
x ~1.910
3
UNIVERSITY INDONESIA OF
CalculatingEquilibrium
ConcentrationsinWeak
AcidSolutions
K
a
=1.510
5
=
[H
3
O
+
][C
4
H
7
O
2
-
]
[HC
4
H
7
O
2
]
=
x ( ) x ( )
0.250 x
( )
[
4 7 2
]
( )
x ~1.910
3
Thebigequilibriumconcentrationsare[HC
4
H
7
O2]=0.2500.0019=
0.248M;[H
3
O
+
]=[C
4
H
7
O
2

]=1.9x10
3
M
K 1.010
14
12
[OH
-
] =
K
w
[H
3
O
+
]
=
1.0 10
1.910
3
= 5.310
12
pH = log (1 9 x 10
3
) = 2 72 pH=log(1.9x10
3
)=2.72
UNIVERSITY INDONESIA OF
PercentDissociationin
W k A id S l ti WeakAcidSolutions
Percent dissociation
[HA] dissociated
100 Percent dissociation =
[HA] undissociated
100
Value depends on the acid.
Increases with increasing value of Ka.
UNIVERSITY INDONESIA OF
Percent
dissociation
UNIVERSITY INDONESIA OF
aciddissociation
constant
UNIVERSITY INDONESIA OF
Polyprotic acids
Polyprotic acid acids that contain more than
Polyprotic acids
Polyprotic acid acids that contain more than
one dissociable proton.
Dissociate in a stepwise manner Dissociate in a stepwise manner.
Each dissociation step has its own Ka.
Stepwise dissociation constants decrease in
the order Ka1 > Ka2 > Ka3.
More difficult to remove a positively charged
proton from a negative ion.
UNIVERSITY INDONESIA OF
Polyprotic acids
Diprotic acid solution contains a mixture of
Polyprotic acids
Diprotic acid solution contains a mixture of
acids, H
2
A, HA

, and H
2
O.
Strongest acid H A Strongest acid H
2
A.
principal reaction dissociation of H
2
A
all of H O
+
comes from first dissociation step all of H
3
O
+
comes from first dissociation step
UNIVERSITY INDONESIA OF
Polyprotic acids Polyprotic acids
UNIVERSITY INDONESIA OF
Polyprotic acids Polyprotic acids
UNIVERSITY INDONESIA OF
Equilibria inSolutions
f W k B
Weak bases partially dissociated; can write a
ofWeakBases
Weak bases partially dissociated; can write a
basedissociation equilibrium equation
B (aq) + H O (l) BH
+
(aq) + OH

(aq) B (aq) + H
2
O (l) BH (aq) + OH (aq)
Position of basedissociation equilibrium
characterized by the base dissociation characterized by the basedissociation
constant, Kb.
[BH
+
][OH
-
]
K
b
=
[BH ][OH ]
[B]
UNIVERSITY INDONESIA OF
Equilibria inSolutions
f W k B
C. Amines organic compounds that are weak
ofWeakBases
C. es o ga c co pou ds t at a e ea
bases.
Derivatives of ammonia.
One or more hydrogen atoms are replaced by another
group.
Lone pair of electrons on nitrogen atom Lone pair of electrons on nitrogen atom.
can be used for bonding to a proton
To solve for equilibrium concentrations and To solve for equilibrium concentrations and
solution pH, use the same procedure for solving
weak acid problems.
UNIVERSITY INDONESIA OF
Weak bases Weakbases
UNIVERSITY INDONESIA OF
Weak bases Weakbases
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Weak bases Weakbases
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RelationBetweenKa
d Kb
For a conjugate acidbase pair, can calculate
andKb
j g p ,
either Ka or Kb from the other.
Sum of an aciddissociation reaction and a base
dissociation reaction is the dissociation of water dissociation reaction is the dissociation of water.
Equilibrium constant for the net reaction (dissociation
of water) = the product of the equilibrium constants
for the individual reactions.
Ka Kb = Kw.
For Ka Kb to remain constant the strength of a For Ka Kb to remain constant, the strength of a
conjugate base must decrease as the strength of the
acid increases.
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RelationBetweenKa
d Kb
EXAMPLE:
andKb
CalculateK
b
forlacticacid(HC
3
H
5
O
3
)givenK
a
=1.4
10
4
.
Write the equilibrium reaction for K WritetheequilibriumreactionforK
b
.
K
w
=K
a
K
b
;
K
110
14
C H O ( ) H O HC H O OH
K
b
=
K
w
K
a
K
b
=
110
1.410
4
= 7.1410
11
C
3
H
5
O
3

(aq)+H
2
OHC
3
H
5
O
3
+OH

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AcidBasePropertiesof
S l
pH of a salt solution is determined by the acid
Salts
pH of a salt solution is determined by the acid
base properties of the constituent cations and
anions.
In an acidbase reaction, the influence of the
stronger partner is dominant.
strong acid + strong base neutral solution
strong acid + weak base acidic solution
weak acid + strong base basic solution weak acid + strong base basic solution
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AcidBasePropertiesof
S l
Salts that yield neutral solutions
Salts
Salts that yield neutral solutions.
Derived from a strong base and a strong acid.
Neither the cation nor the anion reacts with water Neither the cation nor the anion reacts with water
to produce H
3
O
+
or OH

ions.
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AcidBasePropertiesof
S l
Salts that yield acidic solutions
Salts
Saltsthatyieldacidicsolutions.
Derivedfromaweakbaseandastrongacid.
Anion is inert Anionisinert.
Cation isaweakacid.
reacts with water (hydrolysis reaction) to produce H O
+
reactswithwater(hydrolysisreaction)toproduceH
3
O
+
small,highlychargedcations arealsoacidic
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AcidBasePropertiesof
S l
Salts that yield basic solutions
Salts
Salts that yield basic solutions.
Derived from a strong base and a weak acid.
Cation is inert Cation is inert.
Anion is a weak base.
reacts with water to produce OH

reacts with water to produce OH

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AcidBasePropertiesof
S l
Salts that contain acidic cations and basic
Salts
Salts that contain acidic cations and basic
anions.
Derived from a weak acid and a weak base.
Both the cation and the anion can undergo
protontransfer reactions.
pH depends on the relative acid strength of the
cation and the base strength of the anion.
Ka (for the cation) > Kb (for the anion); acidic solution Ka (for the cation) > Kb (for the anion); acidic solution
Kb (for the anion) > Ka (for the cation); basic solution
Ka (for the cation) = Kb (for the anion); neutral solution ( ) ( )
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AcidBasePropertiesof
S l
EXAMPLE:
Salts
EXAMPLE:
Determine whether aqueous solutions of the
following salts are acidic neutral or basic following salts are acidic, neutral or basic.
Write the hydrolysis reaction for those
solutions which are either acidic or basic solutions which are either acidic or basic.
NH
4
Br, K
3
PO
4
, CsI, [(CH
3
)
3
NH]F.
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AcidBasePropertiesof
S l
SOLUTION: To determine the acidity of an
Salts
SOLUTION: To determine the acidity of an
aqueous solution of a salt, we must determine
if the salt is derived from if the salt is derived from
1) a strong acid/strong base reaction,
2) weak acid/strong base reaction 2) weak acid/strong base reaction,
3) strong acid/weak base reaction, or
4) eak acid/ eak base reaction 4) weak acid/weak base reaction.
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AcidBasePropertiesof
S l
Salts derived from a strong base and a strong
Salts
Salts derived from a strong base and a strong
acid:
Examples are NaCl and Ca(NO ) which are Examples are NaCl and Ca(NO
3
)
2
, which are
derived from NaOH and HCl and from Ca(OH)
2
and
HNO
3
, respectively.
3
, p y
Neither cation nor anion hydrolyzes.
The solution has a pH of 7. The solution has a pH of 7.
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AcidBasePropertiesof
S l
Salts derived from a strong base and a weak
Salts
Salts derived from a strong base and a weak
acid:
In this case the anion is a relatively strong In this case the anion is a relatively strong
conjugate base.
Examples are NaClO and Ba(C
2
H
3
O
2
)
2
Examples are NaClO and Ba(C
2
H
3
O
2
)
2
.
The anion hydrolyzes to produce OH

(aq) ions.
The cation does not hydrolyze The cation does not hydrolyze.
The solution has a pH above 7.
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AcidBasePropertiesof
S l
Salts derived from a weak base and strong
Salts
Salts derived from a weak base and strong
acid:
In this case the cation is a relatively strong In this case the cation is a relatively strong
conjugate acid.
Examples are NH
4
Cl and Al(NO
3
)
3
Examples are NH
4
Cl and Al(NO
3
)
3
.
The cation hydrolyzes to produce H
+
(aq) ions.
The anion does not hydrolyze The anion does not hydrolyze.
The solution has a pH below 7.
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AcidBasePropertiesof
S l
Salts derived from a weak base and a weak acid:
Salts
Salts derived from a weak base and a weak acid:
Examples are NH
4
C
2
H
3
O
2
, NH
4
CN, and FeCO
3
.
Both cation and anion hydrolyze. Both cation and anion hydrolyze.
The pH of the solution depends on the extent to
which each ion hydrolyzes.
The pH of a solution of NH
4
CN is greater than 7
because CN

(K
b
= 2.0 10
5
) is more basic than
+
( 6 0
10
) i idi NH
4
+
(K
a
= 5.6 10
10
) is acidic.
Consequently, CN

hydrolyzes to a greater extent than

NH
+
does NH
4
does.
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AcidBasePropertiesof
S l Salts
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AcidBasePropertiesof
S l
NH
4
Br: derived from the weak base NH
3
(aq)
Salts
NH
4
Br: derived from the weak base NH
3
(aq)
and the strong acid HBr (aq). Acidic (NH
4
+
is
the weak conjugate acid of NH
3
).
3
NH
4
+
(aq) + H
2
O NH
3
(aq) + H
3
O
+
(aq)
K
3
PO
4
: derived from the strong base KOH (aq) K
3
PO
4
: derived from the strong base KOH (aq)
and the weak acid HPO
4
2
(aq).
Basic(PO
4
3
is the weak conjugate base of Basic(PO
4
is the weak conjugate base of
HPO
4
2
.)
PO
4
3
(aq) + H
2
O HPO
4
2
(aq) + OH

PO
4
(aq) H
2
O HPO
4
(aq) OH
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AcidBasePropertiesof
S l
CsI: derived from the strong base CsOH (aq)
Salts
CsI: derived from the strong base CsOH (aq)
and the strong acid HI (aq). Neutral.
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Acidbase
propertiesofsalts
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Acidbase
propertiesofsalts
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FactorsthatAffectAcid
S h
The extent of dissociation of an acid HA is
Strength
The extent of dissociation of an acid HA is
often determined by the strength and polarity
of the HA bond of the H A bond.
The weaker the HA bond, the stronger the acid.
The more polar the H A bond the stronger the The more polar the HA bond, the stronger the
acid.
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Factorsthataffect
acidstrength
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FactorsthatAffectAcid
S h
For binary acids
Strength
Forbinaryacids.
HAbondstrengthdecreasesdownagroupinthe
periodic table periodictable.
increaseinthesizeofAdownagroupproducespoorer
orbitaloverlapandaweakerbond
HAbondstrengthisthemostimportantfactorfor
determiningacidstrengthforbinaryacidsof
elementsinthesamecolumn.
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FactorsthatAffectAcid
S h
For binary acids
Strength
Forbinaryacids.
HA bond polarity is the most important factor for
determining acid strength for binary acids of determining acid strength for binary acids of
elements in the same row.
increaseinHAbondpolarityastheelectronegativity of
Aincreases
ingeneral,electronegativities increasefromlefttoright
across the periodic table acrosstheperiodictable
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Factorsthataffect
acidstrength
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Factorsthataffect
acidstrength
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FactorsthatAffectAcid
S h
Oxoacids HnYOm (Y = a nonmetallic atom n
Strength
Oxoacids, HnYOm (Y = a nonmetallic atom, n
and m are integers).
Y is always bonded to one or more hydroxyl (OH) Y is always bonded to one or more hydroxyl (OH)
groups.
can also be bonded to one or more oxygen atoms can also be bonded to one or more oxygen atoms
Dissociation of oxoacid involves breaking an OH
bond.
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FactorsthatAffectAcid
S h
Oxoacids, HnYOm (Y = a nonmetallic atom, n
Strength
Oxoacids, HnYOm (Y a nonmetallic atom, n
and m are integers).
Strength of the acid increases as the OH bond is g
weakened or becomes more polar.
For oxoacids that contain the same number of OH
groups and the same number of O atoms acid strength groups and the same number of O atoms, acid strength
increases with increasing electronegativity of Y.
For oxoacids that contain the same atom Y but different
b f id h i i h numbers of oxygen atoms, acid strength increases with
increasing oxidation number of Y, which increases, in
turn, with an increasing number of oxygen atoms.
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Factorsthataffect
acidstrength
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Factorsthataffect
acidstrength
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Factorsthataffect
acidstrength
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LewisAcidsandBases
Lewis base electronpair donor
ewis Acids and ases
Lewis base electron pair donor.
All Lewis bases are BrnstedLowry bases.
All Brnsted Lowry bases are Lewis bases All BrnstedLowry bases are Lewis bases.
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LewisAcidsandBases
Lewis acid electronpair acceptor
ewis Acids and ases
Lewis acid electron pair acceptor.
More general definition than BrnstedLowry.
Include cations and neutral molecules having Include cations and neutral molecules having
vacant valence orbitals that can accept a share in
pair of electrons from a Lewis base. pair of electrons from a Lewis base.
Cationic Lewis acids metal ions.
Neutral Lewis acids halides of group 3A elements Neutral Lewis acids halides of group 3A elements
and oxides of nonmetals.
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Lewisacidbase
theory
Lewisacidbasetheory
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Lewisacidbase
theory
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Lewisacidbase
theory
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Keyconcept
summary summary