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AcidBase Equilibria
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The simplest acidbase equilibria are those in which a weak acid or a weak
base reacts with water.
We can write an acid equilibrium reaction for the generic acid, HA.
HA(aq) + H2O(l)
H3O+(aq) + A(aq)
HC2H3O2(aq) + H2O(l)
H3O+(aq) + C2H3O2(aq)
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The equilibrium constant for the reaction of a weak acid with water is called the
acidionization constant (or aciddissociation constant), Ka.
[H O ][A ]
=
+
Ka
[HA]
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Highest pH
Ka
6.8
HF
HNO2
HC2H3O2
HCN
4.5
10
HCN
HC2H3O2
1.7
4.9
10
10
HNO2
10
HF
10
Lowest pH
A large Ka value indicates a stronger acid (more of the acid dissociates) and
small Ka value indicates a weaker acid (less of the acid dissociates).
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Calculations with Ka
Given the value of Ka and the initial concentration of HA, you can calculate the
equilibrium concentration of all species.
Given the value of Ka and the initial concentration of HA, you can calculate the
degree of ionization and the percent ionization.
Given the pH of the final solution and the initial concentration of HA, you can
find the value of Ka and the percent ionization.
We can be given pH, percent or degree ionization, initial concentration, and
Ka.
From pH, we can find [H3O+].
From percent or degree ionization, we can find Ka.
Using what is given, we can find the other quantities.
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HC6H5O(aq) +
Initial
Change
Equilibrium
H3O+(aq) +
H2O(l)
0.10
x
0.10 x
C6H5O(aq)
0
+x
x
0
+x
x
10
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Finally, we write the expression for Ka and substitute the concentrations we now
know.
H3O+ + C6H5O
HC6H5O + H2O
[H O ] [C H O ]
=
+
Ka
[HC 6H5 O]
(3.7 10 6 )2
Ka =
0.10
Ka = 1.4 1010
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16 | 8
3.7 106
x
Degree of ionization =
=
0.10
0.10
Degree of ionization = 3.7 105
Percent ionization is the degree of ionization 100%:
Percent ionization = 3.7 103% or 0.0037%
Simplifying Assumption for Acid and Base Ionizations
The equilibrium concentration of the acid is most often ([HA]0 x).
If x is much, much less than [HA]0, we can assume that subtracting x
makes no difference to [HA]:
([HA]0 x) = [HA]0
This is a valid assumption when the ratio of [HA]0 to Ka is > 103.
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16 | 9
We will use the generic formula HA for parahydroxybenzoic acid and the following
equilibrium:
HA + H2O
H3O+ + A
Initial
HA(aq) +
0.200
Change
Equilibrium
x
0.200 x
[H O ][A ]
=
[HA ]
+
Ka
H3O+(aq) + A(aq)
0
0
H2O(l)
+x
x
2.6 10
+x
x
x2
=
0.200 x
0.200
> 1000, so 0.200 x 0.200
2.6 105
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16 | 10
Ka =
x2
0.200
5.2 10 6 = x 2
x = 2.3 10 3 = [H3 O + ]
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Polyprotic Acids
A polyprotic acid has more than one acidic protonfor example, H2SO4,
H2SO3, H2CO3, H3PO4.
These acids have successive ionization reactions with Ka1, Ka2, . . .
The next example illustrates how to do calculations for a polyprotic acid.
Tartaric acid, H2C4H4O6, is a diprotic acid used in food products.
What is the pH of a 0.10 M solution?
What is the concentration of the C4H4O62 ion in the same solution?
Ka1 = 9.2 104; Ka2 = 4.3 105.
First, we will use the first acidionization equilibrium to find [H+] and
[HC4H4O6]. In these calculations, we will use the generic formula H2A for the
acid.
Next, we will use the second acidionization equilibrium to find [C4H4O62].
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16 | 12
H2A(aq) +
Initial
+x
+x
0.10 x
[H O ][HA ]
=
+
K a1
HA(aq)
0.10
Change
Equilibrium
H3O+(aq) +
H2O(l)
[H2 A ]
9.2 10
x2
=
0.10 - x
0.10
< 1000
9.2 10 4
We cannot use the simplifyin g assumption .
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9.2 10 4 (0.10 x ) = x 2
9.2 10 5 9.2 10 4 x = x 2
x 2 + 9.2 104 x 9.2 105 = 0
a =1
b = 9.2 104
x=
c = 9.2 105
b b 2 4ac
2a
(9.2 10 4 ) (1.92 10 2 )
x=
= 4.6 10 4 9.6 10 3
2
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16 | 14
x = 9.1 103
and
x = 1.0 102
HA(aq) +
Initial
Change
Equilibrium
Ka2
0.0091
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H2O(l)
H3O+(aq)
+
0.0091
A2(aq)
0
+x
+x
0.0091 x
0.0091 + x
H3O+ A 2
=
HA
4.3 105 =
(0.0091 + x )x
(0.0091 x )
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4.3 10 5 =
0.0091 x
0.0091
x = 4.3 10 5 M
Our assumption was valid.
pH = 2.04
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BaseIonization Equilibrium
The simplest acidbase equilibria are those in which a weak acid
or a weak base reacts with water.
We can write a base equilibrium reaction for the generic base, B.
B(aq) + H2O(l)
HB+(aq) + OH(aq)
Ammonia is a weak base. It reacts with water as follows:
NH3(aq) + H2O(l)
NH4+(aq) + OH(aq)
Kb =
[HB ][OH ]
[B]
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Writing Kb Reactions
The bases in Table 16.2 are nitrogen bases; that is, the proton they accept
adds to a nitrogen atom. Next well practice writing the Kb reactions.
Ammonium becomes ammonium ion:
NH3+ H2O NH4+ + OH
Ethylamine becomes ethyl ammonium ion:
C2H5NH2 + H2O C2H5NH3+ + OH
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10
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C6H5NH2(aq)
+
Initial
Change
Equilibrium
C6H5NH3+(aq) + OH(aq)
H2O(l)
0.035
x
0.035 x
0
+x
x
0
+x
x
C6H5NH2 + H2O
[C H NH ][OH ]
+
Kb =
[C 6H5N]
4.2 1010 =
x2
(0.200 x )
0 .2 0 0
> 1 0 0 0 , s o w e c a n a s s u m e th a t 0 .2 0 0 x = x
4 .2 1 0 1 0
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11
4.2 1010 =
x2
0.200
x 2 = 8.4 1011
x = 9.2 106 M
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Salt Solutions
We will look at the cation and the anion separately, and then
combine the result to determine whether the solution is acidic,
basic, or neutral.
The conjugate acid of a strong base is very weak and does not
react with water. It is therefore considered to be neutral.
Na+ + H2O No Reaction (NR)
The conjugate base of a strong acid is very weak and does not
react with water. It is therefore considered to be neutral.
Cl + H2O NR
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12
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NaC2H3O2
Na+ is the conjugate acid of NaOH, a strong base. It does not
react with water, so it is neutral.
C2H3O2 is the conjugate base of HC2H3O2, a weak acid. It reacts
with water to give a basic solution.
The cation is neutral; the anion is basic.
NaC2H3O2 is basic.
NH4Cl
NH4+ is the conjugate acid of NH3, a weak base. It reacts with water to give
an acidic solution.
Cl is the conjugate base of HCl, a strong acid. It does not react with water,
so it is neutral.
The cation is acidic; the anion is neutral.
NH4Cl is acidic.
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16 | 26
13
NH4F
NH4+ is the conjugate acid of NH3, a weak base. It reacts with
water to give an acidic solution.
F is the conjugate base of HF, a weak acid. It does not react with
water, so it is basic.
The cation is acidic; the anion is basic. We need more information
in this case. We compare Ka for HF to Kb for NH3.
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K w 1.0 10 14
For NH4 : K a =
=
= 5.6 10 10
5
K b 1.8 10
+
K w 1.0 10 14
For F : K b =
=
= 1.5 10 11
4
K a 6.8 10
NH4F is acidic.
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14
Would this substance be used for acidosis (blood pH < 7.40) or alkalosis (blood
pH > 7.40)?
NH4+ is the conjugate acid of a NH3, a weak base. NH4+ is acidic.
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Kw
Kb
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15
What is Kb for the F ion, the ion added to the public water supply
to protect teeth?
For HF, Ka = 6.8 104.
F + H2O <==> HF + OH
Is the sum of
H3O+ + F <==> HF + H2O; K1 = 1/Ka
2H2O <==> H3O+ + OH; K2 = Kw
Overall reaction:
F + H2O <==> HF + OH
K w 1.0 10 14
K b = K1 K 2 =
=
K a 6.8 10 -10
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ClO(aq) +
Initial
Change
Equilibrium
HClO(aq) +
OH(aq)
0.70
+x
+x
0.70 x
H2O(l)
We are told that Ka = 3.5 108. That means that Kb= 2.9 107.
This allows us to substitute into the Kb expression to solve for x.
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16 | 32
16
ClO + H2O
HClO + OH
Kb =
0.70
2.9 107
[HClO] OH
ClO
x2
7
2.9 10 =
(0.70 x )
> 1000, so we can assume that 070 x = 0.70.
x2
7
2.9 10 =
0.70
x 2 = 2.0 10 -7
x = 4.5 10 -4 M
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16 | 33
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17
CommonIon Effect
The commonion effect is the shift in an ionic equilibrium caused by the
addition of a solute that takes part in the equilibrium.
Buffers
A buffer solution is characterized by the ability to resist changes in pH when
limited amounts of acid or base are added to it.
A buffer is made by combining a weak acid with its conjugate base or a
weak base with its conjugate acid.
What is the pH of a buffer made by mixing 1.00 L of 0.020 M benzoic acid,
HC7H5O2, with 3.00 L of 0.060 M sodium benzoate, NaC7H5O2? Ka for benzoic
acid is 6.3 105.
This problem involves dilution first. Once we know the concentrations of
benzoic acid and benzoate ion, we can use the acid equilibrium to solve for x.
We will use HBz to represent benzoic acid and Bz to represent benzoate ion.
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16 | 35
[HBz] =
(0.020 M)(1.0 L)
= 0.0050 M
(1.0 + 3.0) L
[Bz ] =
(0.060 M)(3.0 L)
= 0.045 M
(1.0 + 3.0) L
Initial
Change
Equilibrium
HBz(aq) + H2O(l)
0.0050
H3O+(aq) + Bz(aq)
0
0.045
+x
+x
0.0050 x
0.045 + x
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18
H3O+ Bz
Ka =
[HBz]
x (0.045 + x )
6.3 105 =
(0.0050 x )
We can assume that
0.045 + x 0.045 and 0.0050 x 0.0050
0.045 x
6.3 10 5 =
0.0050
x = 7.0 10 6 M
Our assumption was valid.
[H3O + ] = x = 7.0 10 6 M
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Calculate the pH of a 0.10 M HF solution to which sufficient sodium fluoride has been
added to make the concentration 0.20 M NaF. Ka for HF is 6.8 104.
[HF] = 0.10 M
H2O(l)
HF(aq) +
Initial
Change
Equilibrium
Ka =
[H3O+ ] [F ]
[HF]
[F] = 0.20 M.
H3O+(aq) +
F(aq)
0.10
0.20
+x
+x
0.10 x
0.20 + x
6.8 10 4 =
x (0.20 + x )
(0.10 - x )
0.10 x 0.10
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19
6.8 10 4 =
0.20x
0.10
x = 3.4 10 4 M
Our assumption was valid.
[H3O + ] = x = 3.4 10 4 M
pH = log [H3O + ] = log (3.4 10 4 )
pH = 3.47
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HendersonHasselbalch Equation
Buffers at a specific pH can be prepared using the
HendersonHasselbalch Equation.
Buffers are prepared from a conjugate acidbase pair in which the
ionization is approximately equal to the desired H3O+
concentration.
Consider a buffer made up of a weak acid HA
and its conjugate base A:
HA(aq) + H2O(l) H3O+(aq) + A(aq)
The acidionization constant is
Rearranging to solve for [H3O+]
Ka =
[H3O + ][A ]
[HA]
[HA]
[H3O+ ] = Ka
[A ]
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20
[HA]
log[H3O + ] = log K a x
[A ]
[HA]
log[H3O+ ] = log Ka log
[A ]
This is equivalent to
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[HA]
pH = pKa log
[A ]
[A ]
pH = pK a + log
[HA]
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pH = pK a + log
[base]
[acid]
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21
H3O+(aq) + A(aq)
pH = pK a + log
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[base]
[acid]
pKa = 6.237
[base] = 0.600 M
[acid] = 0.250 M
Substituting:
pH = 6.237 + log
[0.600]
[0.250]
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22
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23
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