AcidBase Equilibrium Ch101EEE
AcidBase Equilibrium Ch101EEE
Lecture 1
Arrhenius Acids and Bases
HCl H+ + Cl-
An Arrhenius Acid
• Hydrochloric acid completely dissociates to
generate H+ in solution
HCl H+ + Cl-
• Better representation shows formation of
hydronium ion
An Arrhenius Acid
• Hydrochloric acid completely dissociates to
generate H+ in solution
HCl H+ + Cl-
• Better representation shows formation of
hydronium ion
Strong acid
Strong acid
Strong acid
HF + H2O H3O+ + F-
Acid and Base Strength
• Weak acids dissociate incompletely
Strong acid
HF + H2O H3O+ + F-
Ka = 3.5 x 10-4
Acid and Base Strength
• Strong bases dissociate 100%
• Six common strong bases
LiOH lithium hydroxide
NaOH sodium hydroxide
KOH potassium hydroxide
Ba(OH)2 barium hydroxide
Ca(OH)2 calcium hydroxide
Sr(OH)2 strontium hydroxide
Arrhenius Bases
• Strong bases dissociate 100% in aqueous
solution
HF + H2O H3O+ + F-
Acid Ionization Constants
• Hydrofluoric acid is a weak acid used to
etch glass
HF + H2O H3O+ + F-
HF + H2O H3O+ + F-
HF + H2O H3O+ + F-
HF + H2O H3O+ + F-
HF + H2O H3O+ + F-
HF + H2O H3O+ + F-
HF + H2O H3O+ + F-
HF + H2O H3O+ + F-
HF + H2O H3O+ + F-
HF + H2O H3O+ + F-
HF + H2O H3O+ + F-
[H3O+][OH-]
K=
[H2O] [H2O]
Self-Ionization of Water
• Water is an amphiprotic species
[H3O+][OH-]
K=
[H2O] [H2O]
[H3O+][OH-]
K=
[55.6] [55.6]
[H3O+][OH-]
K=
[55.6] [55.6]
Kw = [H3O+][OH-]
Value of Kw at 25oC
Self-Ionization of Water
• Water is an amphiprotic species
• So [H3O+] = [OH-]
What’s [H3O ] in Pure Water?
+
• So [H3O+] = [OH-]
• Let’s use this information with the Kw
equation
What’s [H3O ] in Pure Water?
+
p( ) = -log ( )
pH = -log [H3O+]
pOH = -log [OH-]
pKa = -log Ka
The pH Scale
pH solution [H3O+] [OH-]
[OH-]
10 weakly basic 1 x 10
-10
M 1 x 10-4 M
[H3O+] = 10-pH
Undoing pH Calculations
• Let’s undo the pH calculations we did to
illustrate...
• Calculator designers recognize the opposite
nature of these two calculations
• Use the LOG key again, but in conjunction
with the INV or SHIFT or 2nd key.
Undoing pH Calculations
• What is the acid concentration in a solution
of pH 8.43?
[H3O+] = 10-pH
Undoing pH Calculations
• What is the acid concentration in a solution
of pH 8.43?
[H3O+] = 10-pH
[H3O+] = 10-8.43
Undoing pH Calculations
• What is the acid concentration in a solution
of pH 8.43?
[H3O+] = 10-pH
[H3O+] = 10-8.43
Undoing pH Calculations
• What is the acid concentration in a solution
of pH 8.43?
[H3O+] = 10-pH
[H3O+] = 10-8.43
[H3O+] = 10-pH
[H3O+] = 10-8.43
[H3O+] = 10-pH
[H3O+] = 10-8.43
[H3O+] = 10-pH
[H3O+] = 10-8.43
[H3O+] = 3.7 x 10-9 M
Undoing pH Calculations
• What is the acid concentration in a solution
of pH 2.14?
[H3O+] = 10-pH
Undoing pH Calculations
• What is the acid concentration in a solution
of pH 2.14?
[H3O+] = 10-pH
[H3O+] = 10-2.14
Undoing pH Calculations
• What is the acid concentration in a solution
of pH 2.14?
[H3O+] = 10-pH
[H3O+] = 10-2.14
Undoing pH Calculations
• What is the acid concentration in a solution
of pH 2.14?
[H3O+] = 10-pH
[H3O+] = 10-2.14
[H3O+] = 7.2 x 10-3 M
Undoing pH Calculations
• What is the acid concentration in a solution
of pH 2.14?
[H3O+] = 10-pH
[H3O+] = 10-2.14
[H3O+] = 7.2 x 10-3 M
You may experience some
slight round-off error
Undoing pH Calculations
• What is the acid concentration in a solution
of pH 2.14?
[H3O+] = 10-pH
[H3O+] = 10-2.14
[H3O+] = 7.2 x 10-3 M
Sig figs in pH values are the decimal part,
the non-decimal part is the exponent
Undoing pH Calculations
• What is the acid concentration in a solution
of pH 2.14?
[H3O+] = 10-pH
2 decimal places
[H3O ] = 10
+ -2.14
[H3O+] = 10-pH
2 decimal places
[H3O ] = 10
+ -2.14
2 sig figs
[H3O ] = 7.2 x 10 M
+ -3
[H3O+] = 10-pH
2 decimal places
[H3O ] = 10
+ -2.14
2 sig figs
[H3O ] = 7.2 x 10 M
+ -3
[H3O+] = 10-pH
2 decimal places
[H3O ] = 10
+ -2.14
2 sig figs
[H3O ] = 7.2 x 10 M
+ -3
weak strong
acid base
• What kind of reaction is this?
Acid-base neutralization (partial)
Reactions of Acids
• Acids react with metal hydroxides and oxides
methylamine
Reactions of Acids
• Acids react with ammonia and amines to make
quaternary nitrogen salts
methylammonium
chloride
Reactions of Acids
• Acids react with ammonia and amines to make
quaternary nitrogen salts
methylammonium
chloride
A dissolved ionic salt
Reactions of Acids
• Acids react with ammonia and amines to make
quaternary nitrogen salts
[H3O+] = 10-pH
[H3O+] = 10-8.43
[H3O+] = 3.7 x 10-9 M
pOH and pKa
• Exactly analogous to pH calculations
pOH = 14.00 - pH
pOH
• A handy extra factoid…
pH + pOH = pKw = 14.00
Litmus
(acid form)
Measuring pH
• Acid-base indicators (Figure 8.2)
one (or more) conjugate acid-base pairs
changes color over a specific pH range
selected for pH range of interest
HLit Ind- + H+
Litmus pH
(acid form) 6.0
Measuring pH
• Acid-base indicators (Figure 8.2)
one (or more) conjugate acid-base pairs
changes color over a specific pH range
selected for pH range of interest
HLit Lit- + H+
Litmus pH Litmus
(acid form) 6.0 (base form)
Measuring pH
• Acid-base indicators (Figure 8.2)
one (or more) conjugate acid-base pairs
changes color over a specific pH range
selected for pH range of interest
HInd Ind- + H+
Methyl orange
(acid form)
Measuring pH
• Acid-base indicators (Figure 8.2)
one (or more) conjugate acid-base pairs
changes color over a specific pH range
selected for pH range of interest
HInd Ind- + H+
Methyl orange pH
(acid form) 3.6
Measuring pH
• Acid-base indicators (Figure 8.2)
one (or more) conjugate acid-base pairs
changes color over a specific pH range
selected for pH range of interest
HInd Ind- + H+
H+
Measuring pH
• pH meter
one electrode has a glass membrane that
adsorbs/desorbs H+
pH is determined from voltage
4.33
Measuring pH
• pH meter
Buffers
• Buffers are solutions that resist pH changes
• One of the most important aspects of acid-
base chemistry
• Biochemistry depends on a medium with a
stable pH
• In human blood system, this is around pH
7.4
• Unbuffered solutions will show rapid pH
swings
Buffers
• A buffer is made up of…
a solution containing significant amounts of
both an acid and its conjugate base
• The pH of the buffer solution will be close
to the pKa of the acid!
• Let’s look at how one of our blood system
buffers works
• Based on H2CO3 and HCO3-
Buffers
• A buffer is made up of…
a solution containing significant amounts of
both an acid and its conjugate base
• The pH of the buffer solution will be close
to the pKa of the acid!
• Let’s look at how one of our blood system
buffers works.
• Based on H2CO3 and HCO3-
Buffers
• A buffer is made up of…
a solution containing significant amounts of
both an acid and its conjugate base
• The pH of the buffer solution will be close
to the pKa of the acid!
• Let’s look at how one of our blood system
buffers works.
• Based on H2CO3 and HCO3-
Buffers Partially Neutralize
• A buffer works by partially neutralizing
additions of strong acid or strong base
• Additions of strong base are converted to a
weak base by the acid form of the buffer
compound
Buffers Partially Neutralize
• A buffer works by partially neutralizing
additions of strong acid or strong base
• Additions of strong base are converted to a
weak base by the acid form of the buffer
compound
H3O+ + HCO3- H2 O +
H2CO3
strong
acid
Buffers Partially Neutralize
• A buffer works by partially neutralizing
additions of strong acid or strong base
• Additions of strong acid are converted to a
weak acid by the base form of the buffer
compound
[base form]
pH = pKa + log
[acid form]
Henderson-Hasselbalch Equation
• The pH of a prepared buffer can be
calculated from the Henderson-Hasselbalch
equation
[base form]
pH = pKa + log
[acid form]
[base form]
pH = pKa + log
[acid form]
[base form]
pH = pKa + log
[acid form]
[base form]
pH = pKa + log
[acid form]
Henderson-Hasselbalch Equation
• What is the pH of a buffer made from
0.015 M HPO42- and 0.010 M H2PO4-?
base form
[base form]
pH = pKa + log
[acid form]
Henderson-Hasselbalch Equation
• What is the pH of a buffer made from
0.015 M HPO42- and 0.010 M H2PO4-?
base form acid form
[base form]
pH = pKa + log
[acid form]
Henderson-Hasselbalch Equation
• What is the pH of a buffer made from
0.015 M HPO42- and 0.010 M H2PO4-?
base form acid form
[0.015 M]
pH = pKa + log
[0.010 M]
Henderson-Hasselbalch Equation
• What is the pH of a buffer made from
0.015 M HPO42- and 0.010 M H2PO4-?
base form acid form
[0.015 M]
pH = pKa + log
[0.010 M]
[0.015 M]
pH = pKa + log
[0.010 M]
[0.015 M]
pH = 7.21 +
log [0.010 M]
[0.015 M]
pH = 7.21 +
log [0.010 M]
pH = 7.21 + log 1.5
Henderson-Hasselbalch Equation
• What is the pH of a buffer made from
0.015 M HPO42- and 0.010 M H2PO4-?
base form acid form
[0.015 M]
pH = 7.21 +
log [0.010 M]
pH = 7.21 + log 1.5
pH = 7.21 + 0.18
Henderson-Hasselbalch Equation
• What is the pH of a buffer made from
0.015 M HPO42- and 0.010 M H2PO4-?
base form acid form
[0.015 M]
pH = 7.21 +
log [0.010 M]
pH = 7.21 + log 1.5
pH = 7.21 + 0.18 = 7.39
Henderson-Hasselbalch Equation
• What is the pH of a buffer made from
0.015 M HPO42- and 0.010 M H2PO4-?
base form acid form
[0.015 M]
pH = 7.21 +
log [0.010 M]
pH = 7.21 + log 1.5
pH = 7.21 + 0.18 = 7.39
Close to physiological
ratio
2 H3O + 2 K a2
[H 3O ] + K a1[H 3O ] + K a1K a2 [H 3O ] + K a1K a2 K a3
+ 3 + 2 +
+ 2 +
1 - K w + K yC -
[H 3O ] + 2 K a2 [H3O ] + 3 K a2 K a3 -1
K w H O+ 2 a1 a
[H O + ]3 + K [H O + ]2 + K K [H O + ] + K K K 2
H3O + yCb - H O + 3
+
3 a1 3 a1 a2 3 a1 a2 a3
3
2
3 H 3O + 2 H 3O K a1 + K a1K a2
+ +
= -yCb 2.303[H 3O + ]Va
K + 2 +
K a1[H 3O ] + 2 K a1K a2 [H3O ] + 3 K a1K a2 K a3
w
+ yC
H O +
H 3O + a + 3 + 2 +
[H3O ] + K a1[H 3O ] + K a1K a2 [H 3O ] + K a1K a2 K a3
3
1 + K
- w
2
H3O +
2
Kw
H 3O + yCb -
+
H 3O
+
Blood Buffering
[base form]
pH = pKa + log
[acid form]
H2CO3/HCO3- Blood Buffering
[base form]
pH = pKa + log
[acid form]
H2CO3/HCO3- Blood Buffering
[HCO3-]
pH = pKa + log
[acid form]
H2CO3/HCO3- Blood Buffering
[HCO3-]
pH = pKa + log
[acid form]
H2CO3/HCO3- Blood Buffering
[HCO3-]
pH = pKa + log
[acid form]
H2CO3/HCO3- Blood Buffering
[HCO3-]
pH = pKa + log
[H2CO3]
H2CO3/HCO3- Blood Buffering
[HCO3-]
pH = pKa + log
[H2CO3]
H2CO3/HCO3- Blood Buffering
[HCO3-]
pH = pKa + log
[H2CO3]
H2CO3/HCO3- Blood Buffering
[HCO3-]
7.4 = pKa + log
[H2CO3]
H2CO3/HCO3- Blood Buffering
[HCO3-]
7.4 = pKa + log
[H2CO3]
H2CO3/HCO3- Blood Buffering
[HCO3-]
7.4 = pKa + log
[H2CO3]
[HCO3-]
7.4 = 6.37 +
log [H2CO3]
H2CO3/HCO3- Blood Buffering
[HCO3-]
7.4 = 6.37 +
log [H2CO3]
[HCO3-]
7.4 = 6.37 +
log [H2CO3]
[HCO3-]
7.4 - 6.37 = log
[H2CO3]
[HCO3-]
1.03 = log
[H2CO3]
[HCO3-]
1.03 = log
[H2CO3]
H2CO3/HCO3- Blood Buffering
[HCO3-]
1.03 = log
[H2CO3]
[HCO3-]
101.03 =
log [H2CO3]
[HCO3-]
10.72 =
log [H2CO3]
[HCO3-]
10.72 =
log [H2CO3]
[HCO3-]
10.72 =
log [H2CO3]
•••••
••
O—H •••• +
++ • O—H H
H O—H
O—H
HH
H
H H
H
ACID
ACID BASE
BASE
Lewis Acids & Bases
Other good examples involve metal ions.
•• ••
O—H
2+ Co
2+ •• ••
O—H
Co
H
ACID BASE H
Lewis Acids & Bases
Other good examples involve metal ions.
•••••
••
•O—H
O—H 2+
Co 2+ •••••
••
2+
Co 2+
Co
Co •O—H
O—H
H
H
ACID BASE H
H
ACID BASE
Such bonds as the H2O ---> Co bond are often called
COORDINATE COVALENT BONDS because
both electrons are supplied by one of the atoms of the
bond.
Lewis Acids & Bases
The combination of metal ions
(Lewis acids) with Lewis
bases such as H2O and NH3
------> COMPLEX
IONS
All metal ions form complex
ions with water —and are of
the type [M(H2O)x]n+ where
x = 4 and 6. [Cu(NH3)4]2+
Lewis Acids & Bases
Add NH3 to light blue [Cu(H2O)4]2+ ------>
light blue Cu(OH)2 and then deep blue
[Cu(NH3)4]2+
Lewis Acids & Bases
[Ni(H2O)6]2+ + 6 NH3 ---> [Ni(NH3)6]2+
+ DMG
Lewis Acids & Bases
The Fe2+ in heme can interact with O2 or CO in a
Lewis acid-base reaction.
Lewis Acids & Bases
Many complex ions containing water undergo
HYDROLYSIS to give acidic solutions.
Lewis Acids & Bases
Many complex ions containing water undergo
HYDROLYSIS to give acidic solutions.
[Cu(H2O)4]2+ + H2O ---> [Cu(H2O)3(OH)]+ + H3O+
Lewis Acids & Bases
Many complex ions containing water undergo
HYDROLYSIS to give acidic solutions.
This explains why water solutions of Fe3+, Al3+,
Cu2+, Pb2+, etc. are acidic.
Lewis Acids & Bases
This explains AMPHOTERIC nature of
some metal hydroxides.
Al(OH)3(s) + 3 H+ --> Al3+ + 3 H2O
Here Al(OH)3 is a Brønsted base.
Al(OH)3(s) + OH- --> Al(OH)4-
Here Al(OH)3 is a Lewis acid.
Lewis Acids & Bases
This explains AMPHOTERIC nature of
some metal hydroxides.
Al(OH)3(s) + 3 H+ --> Al3+ + 3 H2O
Here Al(OH)3 is a Brønsted base.
Al(OH)3(s) + OH- --> Al(OH)4-
Here Al(OH)3 is a Lewis acid.
••
••
Al3+
3+
Al O—H
O—H
--
••
••
••
••
Amphoterism of Al(OH)3
AgCl(s)
Lewis Acids & Bases
Formation of complex ions explains why you can dissolve
a ppt. by forming a complex ion.
AgCl(s) Ag+ + Cl- Ksp = 1.8 x 10-10
Ag+ + 2 NH3 --> Ag(NH3)2+ Kform = 1.6 x 107
-------------------------------------
AgCl(s) + 2 NH3 Ag(NH3)2+ + Cl-
Knet = Ksp • Kform = 2.9 x 10-3