Acid-Base Chemistry
There are a couple of ways to define acids
and bases
Brønsted-Lowry acids and bases
Acid: H+ ion donor
Base: H+ ion acceptor
Lewis acids and bases
Acid: electron pair acceptor
Base: electron pair donor
Brønsted-Lowry Acids & Bases
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Brønsted-Lowry Acids & Bases
Brønsted-Lowry Acids & Bases
In most acid-base systems, water may play a
role as either an acid (H+ donor) or a base (H+
acceptor)
Water as an acid
H2O(l) + B(aq) OH-(aq) + HB+(aq)
Water as a base
H2O(l) + HA(aq) H3O+(aq) + A-(aq)
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Conjugate Acids & Bases
Acids react with bases and vice versa
All acids and bases come with a conjugate
pair—a base or acid, respectively, that is
formed in conjunction with the original
species
Examples
HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq)
acid base conjugate conjugate
acid base
Conjugate Acids & Bases
Examples
NaOH(aq) + H2O(l) OH-(aq) + H2O(l) + Na+(aq)
base acid conjugate conjugate
base acid
CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)
acid base conjugate conjugate
base acid
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Strengths of Acids and Bases
Strong acids donate H+ ions more easily
The stronger the acid, the weaker the conjugate
base associated with that acid
Strong bases accept H+ ions more easily
The stronger the base, the weaker the conjugate
acid associated with that base
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Strengths of Acids and Bases
Stronger acids will always react to form weaker
conjugate bases
Stronger bases will always react to form weaker
conjugate acids
Example
H2SO4(aq) + NaOH(aq) + H2O(l) ???
sulfuric acid can react with either OH- or
H2O—which would it prefer?
H2SO4(aq) + OH-(aq) HSO4-(aq) + H2O(l) preferred
reaction
H2SO4(aq) + H2O(l) HSO4-(aq) + H3O+(aq)
Autoionization of Water
Water always undergoes some degree of
dissociation to form H3O+ ions and OH- ions
2 H2O(l) H3O+(aq) + OH-(aq)
The equilibrium constant for this process at
25 oC is:
Kw = [H3O+][OH-] = 1.0 x 10-14
In pure water
[H3O+] = [OH-] = 1.0 x 10-7 M
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Autoionization of Water
Kw is temperature dependent—it increases
with increasing temperature
Autoionization of Water
Example
Determine [H3O+] in a 0.053 M NaOH solution
Step 1: since NaOH is a strong base,
dissociation is complete
[OH-] = 0.053 M
Step 2: Use Kw to calculate [H3O+]
K w = [H 3O + ][OH - ] = 1.0 x 10 -14
Kw 1.0 x 10 -14
[H 3O + ] = -
= = 1.9 x 10 -13 M
[OH ] 0.053
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The pH Scale
pH is a measure of the hydronium ion content
of a solution
pH is defined as:
pH = -log[H3O+]
log is log base 10, not ln (natural log)
[H3O+] is given in molar units (M)
pH of pure water ([H3O+] = 1.0 x 10-7 M):
pH = -log(1.0x10-7) = 7.0
pH of last example ([H3O+] = 1.9 x 10-13 M):
pH = -log(1.9x10-13) = 12.7
The pH Scale
Neutral is defined as the pH of pure water:
pH = 7
Acidic solutions have pH lower than 7:
pH < 7 acidic
Basic solutions have pH larger than 7:
pH > 7 basic
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Figure 16-2
The pH Scale
We can also use pOH to describe a solution
pOH is defined as:
pOH = -log[OH-]
The sum of pH and pOH must equal 14
pH + pOH = 14
assuming room temperature (25 oC)
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The pH Scale
Example
Find [H3O+] of a solution that has pOH = 9.37
Method 1: Calculate pH, then [H3O+]
Step 1: Determine pH
pH = 14 – pOH = 14.00 – 9.37 = 4.63
Step 2: Determine [H3O+]
[H3O+] = 10-pH = 10-4.63 = 2.34 x 10-5 M
The pH Scale
Example (con’t.)
Find [H3O+] of a solution that has pOH = 9.37
Method 2: Calculate [OH-], then [H3O+] using Kw
Step 1: Determine [OH-]
[OH-] = 10-pOH = 10-9.37 = 4.27 x 10-10 M
Step 2: Determine [H3O+] using Kw
[H3O+] = Kw/[OH-] = (1.0x10-14)/(4.27x10-10)
= 2.34 x 10-5 M
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Ionization Constants
The extent of dissociation of an acid or base
in H2O can be quantified using its ionization
constant
Acids:
HA(aq) + H2O(l) H3O+(aq) + A-(aq)
acid base c. acid c. base
[H 3O + ][A- ] [H 3O + ][conjugate base]
Ka = =
[HA] [acid]
[HA] = undissociated acid in solution
Ionization Constants
Ka is a specific equilibrium constant
Acids:
HA(aq) + H2O(l) H3O+(aq) + A-(aq)
acid base c. acid c. base
[H 3O + ][A- ] [H 3O + ][conjugate base]
Ka = =
[HA] [acid]
[HA] = undissociated acid in solution
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Ionization Constants
Example:
Acetic acid has a Ka = 1.8 x 10-5
Determine the pH of a 0.2 M acetic acid solution
CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)
We can approach this like any equilibrium
problem from Chap. 15
CH3COOH CH3COO- H3O+
initial 0.2 0 0
-x x x
equil .2 – x x x
Ionization Constants
Example (con’t.):
[CH 3COO - ][H 3O + ]
K a = 1.8 x 10 -5 =
[CH 3COOH]
x2
1.8 x 10 -5 = x = 0.0019 M
.2 x
pH = -log[H3O+] = -log(.0019) = 2.7
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Ionization Constants
Kb is a specific equilibrium constant for bases
Bases:
B(aq) + H2O(l) HB+(aq) + OH-(aq)
base acid c. acid c. base
[HB+ ][OH - ] [OH - ][conjugate acid]
Kb = =
[B] [base]
[B] = undissociated base in solution
Ionization Constants
Example:
Determine [B] in a 1.82 x 10-3 M solution of NH3
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)
NH3 NH4+ OH-
initial 1.82x10-3 0 0
-x x x
equil 1.82x10-3 – x x x
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Ionization Constants
Example:
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)
[NH +4 ][OH - ] x2
K b = 1.8x10 -5 = =
[NH 3 ] 1.82x103 - x
x = 1.72 x 10-4 M = [NH4+] = [OH-]
[NH3] = 1.82 x 10-3 M – 1.72 x 10-4 M
= 1.65 x 10-3 M
Polyprotic Acids
Some acids contain more than one hydrogen
atom that may be donated to form H+ ion
These are called polyprotic acids
Examples include:
H2SO4 sulfuric acid (2 H+ ions)
H3PO4 phosphoric acid (3 H+ ions)
H2CO3 carbonic acid (2 H+ ions)
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Polyprotic Acids
Each H atom has a unique Ka associated with
its release to form H+ ion
Consider phosphoric acid:
H3PO4(aq) + H2O(l) H2PO4-(aq) + H3O+(aq) 1st
Ka1 = 7.5 x 10-3
H2PO4-(aq) + H2O(l) HPO42-(aq) + H3O+(aq) 2nd
Ka2 = 6.2 x 10-8
HPO42-(aq) + H2O(l) PO43-(aq) + H3O+(aq) 3rd
Ka3 = 3.6 x 10-13
The first H atom is easiest to pull off, so it has the
higher Ka value
Strengths of Acids
Acid strength is determined by a combination
of factors:
Bond polarity—the H-A bond must be polar in
order for the H atom to be transferred to water
as H+
The H atom in CH4 is non-acidic because the
C-H bond is not polar
The H-Cl bond in HCl is polar, and HCl is a
strong acid
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Strengths of Acids
Acid strength is determined by a combination
of factors:
Bond strength—the stronger the bond, the
weaker the acid—it is harder to pull away the
H atom to form H+
Acid Bond Energy Ka
HF 617 kJ/mol 7.2 x 10-4
HCl 427 kJ/mol ~106
HBr 362 kJ/mol ~108
HI 295 kJ/mol ~109
Strengths of Acids
Oxoacids are those with a H-O-Z linkage
Electronegativity of Z—the higher the
electronegativity of Z, the stronger the acid
Acid Z Ka
HOCl 3.0 3.5 x 10-8
HOBr 2.8 2.5 x 10-9
HOI 2.5 2.3 x 10-11
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Strengths of Acids
Oxoacids are those with a H-O-Z linkage
The more O atoms attached to Z, the stronger
the acid
Acid O atoms Ka
HOCl 1 3.5 x 10-8
HOClO 2 1.1 x 10-2
HOClO2 3 ~103
HOClO3 4 ~108
Relationship Between Ka and Kb
The Ka of an acid and the Kb of its conjugate
base are related:
HA(aq) + H2O(l) A-(aq) + H3O+(aq)
acid c. base
[A- ][H 3O + ]
Ka =
[HA]
A-(aq) + H2O(l) HA(aq) + OH-(aq)
base c. acid
[HA][OH ]
Kb =
[A- ]
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Relationship Between Ka and Kb
The Ka of an acid and the Kb of its conjugate
base are related:
The product Ka x Kb = Kw
[A- ][H 3O + ] [HA][OH ]
Ka Kb =
[HA] [A ]
= [H 3O + ][OH - ] = K w
This is true of any conjugate pair of acid and
base
Salts of Acids and Bases
When an acid and a base undergo an
exchange reaction, the result is a salt and
water:
HX(aq) + MOH(aq) MX(aq) + H2O
acid base salt
If a strong base is neutralized with a strong
acid, the resulting solution contains only the
salt
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)
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Salts of Acids and Bases
Determine the pH of 0.284 M solution of sodium
acetate, NaCH3COO
NaCH3COO(aq) + H2O
Na+(aq) + CH3COOH(aq) + OH-(aq)
Complete ionic equation:
Na+(aq) + CH3COO-(aq) + H2O
Na+(aq) + CH3COOH(aq) + OH-(aq)
[CH 3COOH][OH - ] K
K = -
= w = 5.56 x 10 -10
[CH 3COO ] Ka
Salts of Acids and Bases
Determine the pH of 0.284 M solution of sodium
acetate, NaCH3COO
[CH3COO-] [CH3COOH] [OH-]
initial 0.284 0 0
-x x x
equil 0.284 – x x x
x2 assume x is
5.56 x 10 -10 = negligible
0.284 - x
x 2 = 1.58 x 10 -10 x = 1.26 x 10 -5 M = [OH - ]
pOH = -log(1.26x10-5) = 4.90 pH = 9.1
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Salts of Acids and Bases
Weak acid and salt of a strong base:
If stoichiometric amounts are combined, the
solution will be slightly basic
Determine pH of a solution with 0.020 M NaOH and 0.020
M acetic acid
CH3COOH(aq) + NaOH(aq) NaCH3COO(aq) + H2O
Complete ionic equation:
CH3COOH(aq) + Na+(aq) + OH-(aq)
Na+(aq) + CH3COO-(aq) + H2O
Sodium is a spectator ion and does not actively
participate in the reaction
Salts of Acids and Bases
CH3COOH(aq) + OH-(aq) CH3COO-(aq) + H2O
CH3COOH OH- CH3COO-
initial 0 0 0.020
x x -x
equil x x 0.020 – x
[CH 3COO - ] 0.020 - x assume x is
K = 1.8 x 10 9 = -
=
[CH 3COOH][OH ] x2 negligible
0.020
x2 = = 1.11 x 10 -11 x = 3.33 x 10 -6
1.8 x 10 9
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Salts of Acids and Bases
CH3COOH(aq) + OH-(aq) CH3COO-(aq) + H2O
[OH-] = [CH3COOH] = 3.3 x 10-6 M
pOH = -log(3.3 x 10-6) = 5.5
pH = 14.0 – 5.5 = 8.5
Salts of Acids and Bases
Salts of weak bases:
A principle ingredient of chlorine bleach is sodium
hypochlorite, NaOCl
Determine the pH of a solution containing 1.00% by weight
NaOCl
MW = 74.44 g/mol
Kb(ClO-) = 2.9 x 10-7
(1.00 g NaOCl)/(74.44 g/mol) = .0134 mol NaOCl
(99.00 g H2O)/(.9971 g/mL) = 99.29 mL H2O
[ClO-] = (.0134 mol)/(.09929 L) = .135 M
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Salts of Acids and Bases
Determine the pH of a solution containing 1.00% by
weight NaOCl
ClO-(aq) + H2O HOCl(aq) + OH-(aq)
[HOCl][OH - ]
Kb = = 2.9 x 10 -7
[ClO - ]
[ClO-] [HOCl] [OH-]
initial .135 0 0
-x x x
equil .135 – x x x
Salts of Acids and Bases
Determine the pH of a solution containing 1.00% by
weight NaOCl
ClO-(aq) + H2O HOCl(aq) + OH-(aq)
x2 assume x is
2.9 x 10 -7 = x = 1.98 x 10 -4
.135 - x negligible
[OH-] = 1.98 x 10-4 M
pOH = -log(1.98 x 10-4) = 3.70
pH = 10.30
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Lewis Acids and Bases
Remember:
Lewis Acid = electron pair acceptor
Lewis Base = electron pair donor
A Lewis acid reacts with a Lewis base to form
a coordinate covalent bond
H +
.. coordinate
N + H+ N covalent bond
H H H H
H H
NH3 + H+ NH4+
Lewis Acids and Bases
Metal cations are potential Lewis acids
Any empty valence orbitals can accept an
electron pair from a Lewis base to form a
coordinate covalent compound
If the coordinate covalent compound is an
ion, it is called a complex ion
Ag+(aq) + 2 NH3(aq) Ag(NH3)2+(aq)
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Lewis Acids and Bases
One electron pair on the oxygen atom in
water can act a Lewis base to hydrated metal
ions
Fe3+ + 6 H2O Fe(H2O)63+(aq)
OH- is a good Lewis base
Al(OH)3(s) + OH-(aq) Al(OH)4-(aq)
electron pair from OH- inserts into the empty
2p orbital on aluminum to form covalent bond
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