General Chemistry II

Module 3
Acid-Base Chemistry

Strong Acids and Bases

Strong acids and bases are completely
dissociated in water
HCl + H2O H3O+ + Cl2 H2O H3O+ + OH[H+]Total = [H+]acid + [H+]water
If [H+]acid > 10-6 M then [H+]water can be
neglected since [H+]water 10-7 M

Strong Acid or Base pH

Calculate the pH of a 0.057 M solution of HCl
HCl + H2O H3O+ + ClCHCl = 0.057 M and is >> CH+ water at 10-7 M
pH = -log[H3O+] = -log[5.7 x 10-2] = 1.24
For a strong base make the same
assumptions but in terms of [OH-]
Calculate pOH
Then use pH + pOH = 14 to find pH

Weak Acid-Base Equilibria

The auto-ionization of H2O in equilibria involving
strong acids and bases is negligible and can be
ignored, making calculations much simpler.
However, if [H3O+] < 10-6 M, ignoring the autoionization of H2O will lead to appreciable errors.
In these cases, it must be explicitly considered.
HA(aq) + H2O() H3O+(aq) + A-(aq)
Ka = [H3O+][A-] / [HA]
2 H2O() H3O+(aq) + OH-(aq)
Kw = [H3O+][OH-] = 1.0 x 10-14 at 25C

Weak Acids or Bases

Weak acids and bases are only
partially dissociated in solution and
Cacid/base CH+/OHCalculate pH of a 0.1 M solution of
acrylic acid for which Ka = 5.56 x 10-5
HAcr + H2O H3O+ + AcrKa = [H3O+][Acr-] / [HAcr]
[H3O+] = Ka[HAcr] / [Acr-]
=?

Weak Acid pH Using Approximations

HAcr + H2O H3O+ + Acr(1) From stoichiometry [H3O+] = [Acr-]
(2) For a weak acid CHAcr = [HAcr]original
Ka = [H3O+][Acr-] / [HAcr]
Ka = [H3O+]2 / [HAcr]original
[H3O+] = (5.56 x 10-5 x 0.1)
pH = 2.63
Test CHAcr = [HAcr]original [H3O+] = 0.10 0.0023
CHAcr = 0.0976 (corresponding relative error 2.3%)
Relative error 5% considered acceptable

Weak Acid pH without Approximations

Calculate pH of a 0.1 M solution of acrylic
acid for which Ka = 5.56 x 10-5
HAcr + H2O H3O+ + Acrt = 0 [HAcr] = 0.1 M
t=
[HAcr] = 0.1 x
[H3O+] = [Acr-] = x
Ka = [H3O+][Acr-] / [HAcr] = x2 (0.1 x)
x2 + 5.56 x 10-5x - 5.56 x 10-6 = 0
x = 2.39 x 10-3 = [H3O+]
pH = 2.62

Weak Base Given pKa

Acid Base
HA H+ + A- A- + H2O HA + OHKa = [H+][A- ] / [HA] Kb = [HA][OH-] / [A-]
Ka x Kb = ([H+][A- ] / [HA]) x ([HA][OH- ] / [A-])
Ka x Kb = [H+][OH-] = KW
pKa + pKb = pKW = 14
Given a value for pKa you can always find the value for
pKb using the relationship

pKa + pKb = 14

Fractional Dissociation
The fraction of a weak acid present in the
form AHA + H2O H3O+ + A = [A-] / ([A-] + [HA])
= [A-] / CHA

Calculate the % ionization of hydrocyanic acid with Ka = 4 x 10-10 in a 0.15 M

solution.
HCN(aq) + H2O() H3O+(aq) + CN-(aq)
at equilibrium

0.15 M

7.8 x 10-6 M 7.8 x 10-6 M

% ionization = (7.8 x 10-6) 100%/ (0.15)= 0.0052%

Example:
In 0.12 M solution, a weak acid HY, is 5.0% ionized. Calculate the ionization
constant for the weak acid.
HY(aq) + H2O() H3O+(aq) + Y-(aq)
Ka = [H3O+][Y-] / [HY]
HY

H3O+

Yt=0 0.12

change 0.12(0.95)

0.12(0.05)

at equilibrium0.11 0.0060

0.12(0.05)

0.0060

Ka = (0.0060)(0.0060) / (0.114) = 3.2 x 10-4

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Example:
The pH of a 0.10 M solution of a weak acid, HA, is found to be 2.97. What is the
value of its ionization constant?
HA(aq) + H2O() H3O+(aq) + A-(aq)
Ka = [H3O+][A-] / [HA]
[H3O+] = 10-2.97 = 1.07 x 10-3M
HA H3O+
t=0
change

0.100
0.10-x

A0
x

at equilibrium0.0989 1.07 x 10-3

1.07 x 10-3

Ka = (1.07 x 10-3)(1.07 x 10-3) / (0.0989) = 1.2 x 10-5

11

Solution of a Salt of a Weak Acid or Base

A solution of a salt of a weak acid or

.
base is not neutral
Consider the equilibrium for the salt
trimethylammonium chloride which results in a
slightly acidic solution as a result of the following
reactions

(CH3)3NHCl(aq) + H2O() (CH3)3NH+(aq) + Cl-(aq)

(CH3)3NH+(aq) + H2O() H3O+(aq) + (CH3)3N(aq)
12

Solution of a Salt of a Weak Acid or Base

Dissolving NaF in water results in a slightly basic
solution as a result of the following reactions.
NaF(aq) + H2O() Na+(aq) + F-(aq)
F-(aq) + H2O() HF(aq) + OH-(aq)
Dissolving CH3CO2Na in water results in a slightly
basic solution as a result of the following reactions.
CH3CO2Na(aq) + H2O() Na+(aq) + CH3CO2-(aq)
CH3CO2-(aq) + H2O() CH3CO2H(aq) + OH-(aq)

13

Salts of a strong acid or base

Dissolving NaCl in water has no effect on the pH of

the solution
NaCl(aq) + H2O() Na+(aq) + Cl-(aq)
Cl-(aq) + H2O() no appreciable reaction
HCl is a strong acid, so Cl- is ineffective as a base,
and the NaCl solution remains neutral.

14

pH of a salt of a weak acid or base

What is the pH of a solution containing 0.10 M
sodium phenate (Ka = 1.4 x 10-10 for phenol)
NaOPh Na+ + OPhOPh- + H2O HOPh + OHpKa + pKb = 14 and pKa = 9.854 so Kb = 7.13 x 10-5
Kb = [HOPh][OH-] / [OPh-]
[HOPh] = [OH-] from stoichiometry
Assuming [OPh-] [NaOPh] = 0.10 M
7.13 x 10-5 = [OH-]2 / 0.1
(by substitution into K expression)
[OH-] = 2.67 x 10-3 (assumption test[HOPh] = [OH ] << [NaOPh])
pH + pOH = 14
pH = 14 2.57 = 11.43
b

Exact Treatment of Acid-Base Equilibria

There are conditions under which the auto-ionization of
H2O cannot be ignored and problems must be solved
exactly without approximations to avoid large errors.

Under such conditions we must use, Ka, Kw, charge

balance, and mass balance to set up a system of n
equations in n unknowns to solve for system
conditions such as pH or the concentration of species
at equilibrium.
16

The Weak Acid Problem: Exact Solution

HA(aq) + H2O() H3O+(aq) + A-(aq)
2 H2O() H3O+(aq) + OH-(aq)
if [HA]0 = C, then
Ka = [H3O+][A-] / [HA]
Kw = [H3O+][OH-]

(1)
(2)

mass balance C = [HA] + [A-]

charge balance [H3O+] = [OH-] + [A-]

(3)
(4)

4 equations in 4 unknowns, [H3O+] and [A-] appear in 3

equations and [OH-] and [HA] appear in 2 equations.
17

The Weak Acid Problem: Exact Solution

Eliminate [OH-] first
[OH-] = Kw / [H3O+]
3 equations in 3 unknowns [H3O+], [A-] and [HA]
Ka = [H3O+][A-] / [HA]
C = [HA] + [A-]
[H3O+] = Kw / [H3O+] + [A-]

(1')
(2')
(3')

We know that Kw = [H3O+][OH-] so [OH-]=Kw / [H3O+]

And [H3O+] = [OH-] + [A-] therefore [H3O+] = Kw / [H3O+] + [A-]
18

The Weak Acid Problem: Exact Solution

Solve 2' for [HA]
[HA] = C - [A-]
2 equations in 2 unknowns [H3O+] and [A-]
Ka = [H3O+][A-] / {C - [A-]}

(1'')

[H3O+] = Kw / [H3O+] + [A-]

(2'')

Solve 2'' for [A-]

[A-] = [H3O+] - Kw / [H3O+]
1 equation in 1 unknown [H3O+]
Ka = [H3O+]{[H3O+]-Kw/[H3O+]} / {C-[H3O+]-Kw/[H3O+]}
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The Weak Acid Problem: Exact Solution

Rearranging gives a cubic equation
[H3O+]3 + Ka[H3O+]2 (Kw + CKa)[H3O+] KwKa = 0
Solve for [H3O+] (assumptions come in handy here)
Substitute into eq. 2 to get [OH-], then substitute into eq.
2' to get [HA], and finally substitute into eq. 2'' to get
[A-].

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Example:
Calculate the concentrations of the various species in 0.15 M hydrocyanic acid,
HCN, solution.
Ka = x2 / 0.15 = 4.0 x 10-10
x2 = Ka x 0.15
x2 = 4.0 x 10-10 x 0.15 = 6 x 10 -11
x = 7.8 x 10 -6 M
HCN(aq) + H2O() H3O+(aq) + CN-(aq)
at equilibrium

0.15 M 7.8 x 10-6 M 7.8 x 10-6 M

Check assumptions (i.e., ignoring autoionization of H2O)

Ka = (7.8 x 10-6)2 / (0.15) = 4.1 x 10-10
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Approximations
In order to simplify problems by making approximations,
we look for small terms added to large terms and neglect
the small terms.
After solving a problem, it is extremely important to check
whether or not the assumption made in the approximation
is reasonable.
If the assumption is found to be invalid, make the
opposite assumption and try again.
Remember to check your assumption again after
resolving the problem.
22

Approximations
Consider the dissociation of acetic acid in a solution
containing 0.01M acetic acid
HA(aq) + H2O() H3O+(aq) + A-(aq)
2 H2O() H3O+(aq) + OH-(aq)
C = 0.010 M
Ka = [A-][H3O+]/[HA] = 1.8 x 10-5
Kw = [H3O+][OH-] =1.0 x 10-14
[H3O+][A-] = Ka[HA] = 1.8 x 10-5 [HA]
mass balance on A: C = 0.010 M = [HA] + [A-]
charge balance [H3O+] = [OH-] + [A-]
(2)
4 equations in 4 unknowns

(1)

Approximations
The solution is acidic so let's assume that
[H3O+] >> [OH-], so that we can neglect [OH-]
Then equation (2) becomes [H3O+] [A-] (2')
We also know that acetic acid is a weak acid
(Ka = 1.8x10-5), so HA should only be slightly dissociated.
Thus, [HA] >> [A-], so that we can neglect [A-]
The equation (1) becomes [HA] 0.010 (1')

Approximations
Rearranging the expression for Ka gives
[H3O+][A-] = Ka[HA] = 1.8 x 10-5[HA]
Substituting in for the concentration of [A-] gives
[H3O+][H3O+] = (1.8 x 10-5)(0.010 ) = 1.8 x 10-7
Taking the square root of this expression gives
[H3O+] = 4.2 x 10-4 M
[A-] = 4.2 x 10-4 M
[OH-] = Kw/[H3O+] = 2.4 x 10-11 M

Approximations
Using the mass balance equation and the concentration
determined for A- gives
[HA] = (0.010 4.2 x 10-4)M = 0.0096 M
Check assumptions
[H3O+] >> [OH-]
[HA] >> [A-]

yes

4.2% error, okay

If the resulting concentrations violate assumptions, then

you must resolve the problem without the assumption(s)
that is (are) not satisfied.

General Approach to Approximation Solutions

1. Make as many approximations as you can on the
mass and charge balances by neglecting any
concentrations (expected to be small) when it is added
to another (large one).
2. Solve the simpler approximate system of equations.
3. Check whether your results are consistent with your
approximations.
5. If an approximation fails to provide an answer with the
desired precision, leave the equation in its exact form
and solve the more complicated set of equations.
6. Check your results. An approximation is acceptable if it
introduces an error of < 5%.
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Weak Base Equilibria

The treatment of weak bases is the same as that for weak
acids.
Aqueous ammonia and its organic derivatives, the
amines, are the only common soluble weak bases.
Calculations for basic solutions are treated the same way
as acidic solutions.

28

Example:
Calculate the concentrations of the various species in 0.15M ammonia, NH3,
solution.
NH3(aq) + H2O() NH4+(aq) + OH-(aq)
Kb = [NH4+][OH-] / [NH3] = 1.8 x 10-5
NH3
t=0 0.15

NH4+

OH-

change 0.15-x

Kb = x2 / 0.15-x x2 / 0.15 = 1.8 x 10-5

x = {1.8 x 10-5(.15)}1/2 = 1.64 x 10-3 M

29

Example:
Calculate the concentrations of the various species in 0.15 M ammonia, NH3,
solution.
NH3

NH4+

at equilibrium0.15 M

OH1.64 x 10-3 M 1.64 x 10-3 M

[H3O+] = Kw/[OH-] = (1.0 x 10-14)/(1.64 x 10-3) = 6.25 x 10-12 M

Check assumptions (i.e., ignoring autoionization of H2O and that ionization of
NH3 is very minor)
Kb = (1.64 x 10-3)2 / (0.15)= 1.8 x 10-5
The ionization constant for aqueous ammonia is the equal to the constant for
acetic acid. This tells us that NH3 and CH3CO2H ionize to the same extent in
aqueous solutions of the same concentration.
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Example:
The pH of an aqueous ammonia solution is 11.37. Calculate the molarity of the
aqueous ammonia solution.
pOH = 14.00 pH = 2.63 = -log10[OH-]
[OH-] = 10-2.63 = 2.34 x 10-3 M
NH3(aq) + H2O() NH4+(aq) + OH-(aq)
Kb = [NH4+][OH-] / [NH3] = 1.8 x 10-5
NH3

NH4+

x-y

at equilibrium

OHy

x-2.34 x 10-3 M

2.34 x 10-3 M

2.34 x 10-3 M

Kb = (2.34 x 10-3)2 / (x - 2.34 x 10-3) = 1.8 x 10-5

x = {(2.34 x 10-3)2 / 1.8 x 10-5} + 2.34 x 10-3 = 0.31M

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Buffers
A buffer solution is any solution that maintains an
approximately constant pH despite small additions of
acid or base and maintains a constant pH when
diluted.
The most common kinds of buffer solutions are.
1. A solution composed of a weak acid and a soluble
salt of that acid.
2. A solution composed of a weak base and a soluble
salt of that base.
3. A solution of a salt of a polyprotic acid
32

Buffers
Buffer solutions play important roles in controlling the
solubility of ions in solution and in maintaining the pH
in biochemical and physiological processes.
Human blood has a pH of approximately 7.4. This pH is
maintained by carbonate, phosphate and protein buffer
systems.
Careful control of the pH of our blood is very important, if
the pH drops below 7.0 or rises above 7.8 the result is
rapid death.
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Buffers
HA(aq) + H2O() H3O+(aq) + A-(aq)
Ka = [H3O+][A-] / [HA]
or

[H3O+] = Ka[HA] / [A-]

pH = pKa + log [A-]) / [HA])

The key to effective buffer action is to keep the [HA] and

[A-] nearly equal and fairly large.
How does a buffer resist change in pH?
The strong acid or base added to a buffer solution is
consumed by [A- ] or [HA]. As long as [A-] or [HA] is not
fully consumed the log term [A-] / [HA] does not change
very much and therefore pH does not change very much

34

Henderson-Hasselbach Equation
The Henderson-Hasselbach equation for solutions of a
weak acid and a salt of that weak acid (or solutions of
a base and a salt of that weak base)
pH pKa + log10[A-]/[HA]
pH pKa + log10[B]/[BH+]
pKa in the 2nd equation refers to the pKa of BH+

35

Henderson-Hasselbach Equation

pH pKa + log10[A-]/[HA]
The pH at which a buffer operates depends on the ratio of
conjugate acid and base in the buffer solution and on the
ionization constant of the weak acid or base involved
For 1% [A-] or [HA] in a buffer (ratio 1:100) this
corresponds to a range of pH pKa 2
Effective buffering capacity is usually restricted to pKa 1
corresponding to a ratio of 10:1 or 1:10 for [A-] and [HA]

Henderson-Hasselbach Equation
The correct Henderson-Hasselbach equation includes
activity coefficients.
Because K depends on T and activity rather than
concentration, ignoring these effects will sometimes
lead to significant errors.

37

Composition of a Buffer
What ratio of sodium acetate and
acetic acid (Ka
= 1.8 x 10-5 must be taken to give a
buffer
solution of pH =5
NaOAc Na+ + OAcHOAc + H2O [H3O+] + [OAc-]
Ka = [H3O+] [OAc-] / [HOAc]
[OAc-] / [HOAc] = Ka / [H3O+] = 1.8 x
10-5 / 1 x 10-5

Example:
Calculate the concentration of H3O+ and the pH of a solution that is 0.15 M in
acetic acid and 0.15 M in sodium acetate.
pH pKa + log10([A-]0/[HA]0)
= -log10(1.8 x 10-5) +log10(0.15/0.15) = 4.7
[H3O+] = 1.8 x 10-5 M
Compare this to the solution with only 0.15 M acetic acid, where we found that
[H3O+] = 1.6 x 10-3 M, almost 100 times as large as in the buffer solution. ???

39

If 0.020 mole of gaseous HCl is added to1.00 L of solution that is 0.200 M in

aqueous ammonia and 0.100 M in ammonium chloride, how much does the pH
change? Assume no volume change due to the addition of gaseous HCl.
pH of original buffer solution
pH pKa + log10([NH3]0/[NH4+]0)

Kb of NH3=1.7610-5

= -log10(5.68 x 10-10) + log10(0.200/0.100) = 9.546

After HCl is added
HCl(aq) + NH3 (aq) NH4+ (aq) + Cl- (aq)
[NH3] = (0.200 - 0.020) M = 0.180 M
[NH4+] = (0.100 + 0.020) M = 0.120 M
pH after the HCl is added
pH pKa + log10[NH3]0/[NH4+]0
= -log10(5.68 x 10-10) + log10(0.180/0.120) = 9.421
pH = 9.421-9.546= -0.125 (correct significant figures would be two digits)
40

Preparation of Buffer Solutions

When designing a buffer solution, chose an acid so that
the desired pH pKa and then adjust the initial [HA]0
and [A-]0 to achieve the desired pH.
pKa values for commonly used buffers are given in Table
9-2.
The absolute concentrations of [HA]0 and [A-]0 are not
important in pH determination, just their ratio.

41

Preparation of Buffer Solutions

However, absolute concentrations affect the ability of the
buffer solution to resist pH changes when acid or base
is added.
The greater the initial concentrations of [HA]0 and [A-]0,
the smaller the change in pH induced by addition of
acid or base.

42

Buffer Capacity
The buffer capacity, , is a measure of how well a solution
resists changes in pH when strong acid or base is
added.
= dCb/dpH = -dCa/dpH
where Ca and Cb are the # of moles of strong acid and
strong base per liter needed to produce a unit change
in pH.
*The larger is the greater the buffer capacity and the
better the buffer.
43

Buffer Capacity
The buffer capacity said to be exhausted if enough strong
acid (base) is added to use up the original amount of
the weak base (acid).
Buffer solutions are often prepared by mixing other
solutions.
When solutions are mixed, the concentrations of the
dissolved species change because the volume
changes.
44

Example:
Calculate the concentration of H3O+ and the pH of the solution prepared by
mixing 200 mL of 0.150 M acetic acid and 100 mL of 0.100 M sodium hydroxide
solutions.
NaOH(aq) in H2O () Na+(aq) + OH- (aq)
OH-(aq) + CH3CO2H (aq) CH3CO2- (aq) + H2O()
# moles = Molarity x Volume
t=0 (mol)

0.0100

0.0300

mixing(M)

0.0333

0.100

change

0.0333-x

0.100-x

0.0667

0.0333

after reaction

pH pKa + log10[CH3CO2-]0/[CH3CO2H]0
= -log10(1.8 x 10-5) + log10(0.0333/0.0667) = 4.44
45

Preparation of a Buffer from Solutions

Calculate the pH of a buffer solution prepared by mixing 200 mL of 0.150 M acetic acid and
100 mL of 0.100 M sodium hydroxide solutions. (K a HOAc = 1.8 x 10-5)
On mixing NaOH and HOAc react to form NaOAc
NaOH + HOAc NaOAc + H2O
There are fewer moles of NaOH than HOAC and the solution will contain only HOAc
and
NaOAc after mixing
Moles NaOAc = Moles NaOH (= Molarity x Volume)
= 0.1 x 0.1 = 0.010
Moles HOAc = HOAcinitial NaOAc (moles NaOAc = moles of HOAc reacted)
HOAc = (0.2 x 0.15) 0.010 = 0.020
When the solutions are mixed the total volume = 200 + 100 = 300 mL
[NaOAc] = 0.010 / 3 = 0.00333 and [HOAc] = 0.00667
For a buffer solution
pH = pKa + log[OAc] / [HOAc]
pH = -log (1.8 x 10-5) + log (0.00333 / 0.00667) = 4.443
pH = 4.44 (correct number of significant figures)

Example:
Calculate the number of moles of solid ammonium chloride, NH4Cl, that must be
used to prepare 1.00 L of a buffer solution that is 0.10 M in aqueous ammonia,
and that has a pH of 9.15.
NH3(aq) + H2O() NH4+ (aq) + OH- (aq)
Ka(NH4+) = 5.68 x 10-10 or pKa = 9.245
pH pKa + log10([NH3]/[NH4+])
9.15 = 9.245 + log10(0.10/[NH4+])
log10(0.10/[NH4+]0) = -0.095
[NH4+] = 0.10 M / (10-0.095) = 0.12 M
So moles of ammonium chloride = [NH3] + [NH4+] = 0.22 M

47