Chapter 10

Acid-Base Equilibria
6.1 Properties of Acids and Bases
Definition of ACID and BASE:
Bronsted-Lowry:
An acid is a proton donor.
A base is a proton acceptor.
Acids and bases appear in reactions as conjugate
-
pairs eg HCl/Cl .
+ -
HCl(aq) + H2O(l)  H3O (aq) + Cl (aq)
+ -
NH3(aq) + H2O(l) NH4 (aq) + OH (aq)
-
HCl(aq) + NH3(aq)  NH4 (aq) + Cl (aq)
+
 Molecules which can act either as acids or bases are
"amphoteric". Eg. HSO4- and water itself.
-
H2SO4 (l) + H2O(l) HSO4 (aq) + H3O+(aq)
- 2-
HSO4 (aq) + H2O(l) SO4 (aq) + H3O+(aq)
-
H2O(l) + H2O(l) H3O (aq) + OH (aq)
+

The autoionization of water can be represented

+ -
2H2O(l) H3O (aq) + OH (aq)
The "ion product constant" is just the equilibrium
constant for this process
+ -
Kw = [H3O ][OH ]
Like all equilibrium constants, Kw varies with
temperature but has a value Kw = 1.01  10-14 at 25oC
+ -
In pure water [H3O ] = [OH ] = 10-7M
Strong acids
eg HCl, H2SO4, HNO3, HI, HBr, HClO4
Proton transfer in water is essentially complete.
Because of this, water is said to have a "leveling
effect" on strong acids.
-
HCl(aq) + H2O(l)  H3O (aq) + Cl (aq)
+

If we dissolve 0.1 mol HCl in one dm-3 of water,

the concentrations of the various species are
[H3O+] = 0.1 mol dm-3
[Cl-] = 0.1 mol dm-3
[HCl] = 0
-
[OH ] = 1  10-13 mol dm-3
Strong bases
If we dissolve 0.1 mol of sodium amide Na+NH2-
in 1 litre of water:
- -
NH2 (aq) + H2O(l)  NH3(aq) + OH (aq)
[NH3] = 0.1 mol dm-3
-
[OH ] = 0.1 mol dm-3
-
[NH2 ] = 0
[Na+] = 0.1 mol dm-3
The composition of solution is the same as if we had
dissolved 0.1 mol of NH3 (gas) and 0.1 mol of sodium
+ -
hydroxide (Na OH - ionic solid) in 1 dm-3 of water.
In these cases the equilibrium again lies far to the
right and it is appropriate to use a single headed
arrow.
pH
In order to discuss acid behaviour in a quantitative way
we define the pH function:
pH = - log10 aH3O+ = -log10[H3O+]
(i) in pure water, [H3O+] = 1  10-7 mol dm-3
pH = +7.00
-1
(ii) for 0.1 M HCl in water [H3 O+] = 1 10 mol dm-3
pH = +1.00
(iii) for 0.1 M NaOH in water
-1
[OH ] = 1 10 mol dm-3
-

[H3O+] = 1 10-13 mol dm-3

pH = +13.00 pOH = + 1.00
See fig 6.2
 Concentrations are handled by converting to
"activities".
All concentrations are divided by the reference
concentration 1.00 mol dm-3. When handled in this way
Keq or pH expressions have no units.

Note the symbol "p" in pH = "take the -log10 of"

This symbolism comes up frequently, for example pK = -log10K
 6.2 Acid and Base Strength 16568/1

Most organic and naturally occurring acids are weak - they do not
fully ionise in water.
For a species acting as an acid we can write an acid ionization or
dissociation constant, Ka .
Acetic acid
CH3COOH(aq) + H2O(l) H3O+ (aq) + CH3COO–(aq)
[H3 O+ ][CH3 COO - ] aH3O+  aAc-
Ka =
[CH3 COOH] 
Ka = a
H2O  aHAc

For acetic acid, Ka = 1.76  10-5

By definition, pKa = -log10Ka

(O&N Ka and pKa values - see Table 6.2)
The corresponding pKa value is -log10(1.76  10-5) = 4.75
 SO

If we dissolve either sodium acetate or acetic acid in

water, proton transfers take place. At equilibrium the
concentrations of CH3COOH, H3O+ and CH3COO- will
be given by the above expression. ie.

[H3 O+ ][CH3 COO - ]

Ka =
[CH3 COOH]
 We can do exactly the same for a base.
Kb quantitative measure of base strength.
pKb = -log10Kb
For example, take ammonia in water.
+ -
NH3(aq) + H2O(l) NH4 (aq) + OH (aq)

NH4  OH
Kb  NH   1.8 x 105
3
Notes
(i) [NH3] is the concentration of NH3 at equilibrium, not
what was put in.
(ii) there is no such thing as NH4OH ( in spite of
incorrectly labelled bottles.)
 Can we obtain a relationship between Ka and Kb
Look at a base and the acid derived from it
e.g. NH3 and NH4+
For the base, we can write
+ -
NH3(aq) + H2O(l) NH4 (aq) + OH (aq)

[NH4+][OH-]
Kb =
[NH3]
While for the conjugate acid we have
NH4+ (aq) + H2O (l) NH3(aq) + H3O+ (aq)
[NH3][H3O+]
Ka =
[NH4+]
Taking the product of the two equilibrium constants
KaKb= [H3O+][OH-] = Kw !!!
 So for NH3 where Kb= 1.8  10-5 ( pKa= 4.75 )
Ka= 5.6  10-10 and pKa= 9.25

This means that instead of listing Kb values we list Ka

values for the corresponding conjugate acids. In this
case, NH4+ is the conjugate acid of the base NH3.

Note that a large Ka implies a small Kb so that the

conjugate base of a strong acid is weak. Conversely
the conjugate base of a weak acid is strong.
 What happens with mixtures of acids or bases ??
The general rule is that the stronger acid donates
protons to the stronger base. Tables of pKa values are
thus useful for predicting the direction of H+ transfer.
In the equilibrium
HF(aq) + CN–(aq) HCN (aq) + F–(aq)
there are two bases and two acids. The Ka values
are
HF: Ka = 6.6  10-4 and HCN: Ka = 6.1  10-10
Since the stronger acid is HF, and the stronger
base is CN-, we should expect the equilibrium to
lie well to the right.
 We can show this to be true as follows:
[HCN][F–]
K=
[CN–][HF]

[H3O+][F–]
HF
[HF] Ka 6.6  10-4
= = =
[H3O+][CN–] HCN
Ka 6.17  10 -10
[HCN]
= 1.1  10 6

HF(aq) + CN–(aq) HCN (aq) + F–(aq) same as

[HF(aq) + H2O(l) H3O+(aq) + F–(aq) ]

[HCN (aq) + H2O(l)

- H3O+(aq) + CN–(aq)]
 Indicators 10/1

These are typically weak organic acids, whose

conjugate bases differ in colour from the acid form.

eg. phenolphthalien, KIn = 2  10-5 (In– is coloured)

They have intense colours and are used at very low

concentrations so that they don't affect the pH of a
solution.
 How does an indicator work ? eg phenolphthalein
HIn(aq) + H2O(l) In–(aq) + H3O+ (aq)
colourless coloured
[H3O+][In-]
= Ka (In)
[HIn]

[HIn] [H3O+]
=
[In-] Ka (In)

If [H3O+] decreases during a titration the indicator changes

from the acid form to the base form with an accompanying
color change.
Notice that if [H3O+] = Ka (In) (or the pH = pKa (In)), equal
amounts of the acid and base forms of indicator are present -
endpoint.
Generally we will see the colour of only the acid form if
[HIn] > 10  [In-]

We can restate this condition as

[HIn]
> 10
[In-]
We can get this in terms of [H3O+] as follows:
[H3O+][In-]
= Ka (In)
[HIn]

Therefore [H3O+] > 10 Ka (In)

If we take the -log of both sides, we obtain
pH < pKa (In) - 1
By a simlar argument the colour of the base form is seen when
pH > pKa (In) + 1
 Clearly colour changes occur around 1 pH unit
either side of the pKa (In).

eg. bromothymol blue

Ka (In)= 1.6  10-7 which gives pKa (in) = 6.8

: indicator changes colour at 5.8 < pH < 7.8

It is very important to choose the correct indicator

to suit the endpoint of the acid-base reaction being
studied.
see fig 6.5.
 6.3 Weak Acids and Bases
Weak Acids
Any acid with a Ka < 1 (pKa > 0) may be regarded
as "weak".
e.g. acetic acid, CH3COOH (=HAc)
Hac(aq)+H2O (l) H3O+ (aq)+Ac–(aq) Ka = 1.73×10-5
Here the equilibrium lies towards the left.

Water itself acts as a very weak acid pKa = 14

2H2O(l) OH– (aq) + H3O+ (aq)
Ka = Kw = 10-14 at 298 K
Sample calculation for a weak acid
Hac(aq) +H2O (l) H3O+ (aq)+Ac–(aq) Ka = 1.7 10-5
How much H3O+ is produced when 0.1 mol dm-3 HAc is added to
water and what is the pH of the resulting solution?
First write down the equilibrium expression

aH3O+  aAc - [H3O+][Ac-]

Ka =
Ka = a
H2O  aHAc
[HAc]

Ignore the [H3O+] due to autoionisation of water - very small.

[HAc] [H3O+] [Ac-]
Initial concentration 0.1 0 0
Change at equilibrium - + +
Equilibrium concentration 0.1 -   
 -5 2
Ka = 1.73  10 =
(0.1- )
Solve by quadratic formula, or assume  << 0.1
2

1 73  10 - 5 = .
0.1   = 1.3 10-3 mol dm-3
Our approximation is OK. We could try one more iteration

0.1- = 0.0987
Solving the equation again: 2
-5
1.73  10 =
0.0987
  = 1.3  10-3 mol dm-3

Clearly [H3O+] = 1.3 x 10-3 mol dm-3

 HAc dissolves to form a solution of
pH = -log10(1.3  10-3) = 2.88
Weak Bases
Examples:
NH3
sodium acetate, NaAc

React with water and produce OH-

Ac–(aq) + H2O(l) HAc (aq) + OH–(aq)

The resulting solutions are alkaline (pH > 7), but

not nearly as alkaline as a solution of strong base
of same concentration.
Sample calculation for a weak base:
Work out the pH of a solution of 0.1 mol dm-3 of sodium
benzoate, NaBz.
given the data Ka(HBz) = 6.5  10-5.

NaBz (s) Bz–(aq) + Na+ (aq)

Bz–(aq) + H2O(l) HBz (aq) + OH–(aq)
Kb = Kw/Ka = 1  10-14/ 6.5  10 -5 = 1.5  10 -10
Let[HBz] = 
We can proceed exactly as for the last example.
[OH–] = 3.9  10-6 mol dm-3
10 - 14
[H3O ]+
=
3.9  10 - 6
= 2.6  10 -9
mol dm-3

The pH comes out to = 8.6

 Hydrolysis reactions with water cause the salts of
weak acids and bases to have pH values above and
below 7.

Sodium acetate solutions are "basic" (pH > 7)

CH3COO– (aq) + H2O(l) CH3COOH (aq) + OH– (aq)

Ammonium chloride solutions are "acidic" (pH < 7)

NH4+ (aq) + H2O (l) NH3 (aq) + H3O+ (aq)

The steps in calculation of acid base equilibria for
a weak acid or base:
(i) Look up the value of Ka
(ii) For base find a numerical value for Kb in terms of
Ka and Kw
(iii) set up the equilibrium expression in terms of a
variable 
(iv) invoke approximation to find 
(v) For base caclculate [H3O+] from [OH-]
(vi) use the definition of pH
Exercise:
Calculate the pH of a 0.100 M sodium acetate
solution.
 6.4 Buffer Solutions

Solutions that maintain an approx constant pH despite

small additions of acid and base. Usually a weak acid and
its conjugate base.
eg 0.001 mol dm-3 Hac and 0.001 mol dm-3 NaAc
This is a "buffer solution".
What is the pH?
HAc + H2O H3O+ + Ac– Ka = 1.73  10-5

[H3O+][Ac-]
Ka =
[HAc]
 Suppose mol of HAc dissociates per dm3
[Hac] [H3O+] [Ac-]
Initial concentrations 0.001 0 0.001
 at equilibrium -  
Equilibrium conc 0.001 -   

-5  (0.001 + )
1.7 x 10 =
(0.001 - )
 1.7  10-5
pH = 4.8
Question:
What happens if we add some strong acid solution
to this?
Say we add 1 cm3 of 0.1 mol dm-3 HCl solution (this
solution has pH = 1) to 1 dm3 of buffer.
Answer:
pH changes only by a very small amount !!
Why?
HAc + H2O H3O+ + Ac–
get more of add more of
this this
Hac is a weak acid so assume all of the extra H3O+ reacts with Ac-
and is converted into HAc
 extra 1 10-4 mol dm-3 HAc formed:
[Hac] [H3O+] [Ac-]
Initial concentrations 0.0011 0 0.0009
 at equilibrium -  
Equilibrium conc 0.0011-   

 (0.0009 + )
1.7 x 10 - 5 =
(0.0011 - )

  = 1.996  10-5
 pH = 4.7

ie very little change.

 If we add base?
 same thing - only a minor change.
How much acid or base can we add?
What is the capacity of the buffer?
No more moles of acid than the moles of buffer base
present.
What happens if we add water to a buffer?
Nothing! eg dilute our buffer by a factor of 2
0.005M Hac and 0.005M NaAc

 (0.0005 + )
1.7 x 10 - 5 =
(0.0005 - )
x 10-5 pH = 4.7 as before.
Examples of Buffers Buffer region
H2CO3/HCO3–pH = 5.5 - 6.5
HCO3–/CO32– pH = 9.3 - 11.3
H2PO4–/HPO42–pH = 6.8 - 8.2
HPO42–/PO43– pH = 12.6 - 14.6
 How do we design a buffer solution ?
Choose an acid HA whose pKa is as close as possible
to the desired pH value.
Mix the appropriate acid with its salt (conjugate
base) A–, choosing the concentrations using
 
HA 
pH  pKa - log10  0 
[ A- ] 
Application  0
Say we need a buffer solution having pH = 4.00
Formic acid has a Ka = 1.77  10-4 and a pKa of 3.75
 
HA 
4.00  3.75 - log10  0 
[ A- ] 
 0
The buffer will use HCOOH, and Na+COO–, in the ratio
10-0.25 = 0.56
 6.5 Acid-Base Titration Curves
The shape of a titration curve in an acid-base titration
depends on the Ka value and the concentrations of the
participating acid and base.

Strong acid and strong base

The reaction we need to consider is neutralization:
H3O+(aq) + OH–(aq) 2H2O(l)

Consider a titration of 100.0 cm-3 of 0.100M HCl with

0.1M NaOH.
1. Initially [H3O+] = 0.100M ie. pH = 1
n(H3O+) = 0.1 M  0.1dm-3 = 0.01 mol
2. Add 10 cm-3 NaOH
n(OH–) = 0.1 M  0.01dm-3 = 0.001 mol.
0.001 mol H3O+ neutralised
n(H3O+) = 0.01 -0.001 = 0.009 mol

[H3O+] = 0.009mol/0.1+0.01 dm-3 = 0.082M

pH = 1.1 Only small change in pH.

3. Add another 10 cm-3 NaOH etc. etc.

4. When total 100 cm-3 NaOH added all the original acid
has been neutralised.
H3O+(aq) + OH–(aq) 2H2O(l)
0.01 mol 0.01mol
This is the equivalence point.
At the equivalence point for a strong acid /strong base
pH =7

5.When a total of 100.1 cm-3 NaOH added.

100.1 -100 cm-3 NaOH unreacted

n(OH-) = 0.0001 dm-3 /0.1M = 1  10-5 mol

[OH-] = 1.0  10-5 / 0.2001 = 4.998  10 -5 M

pOH =4.3

pH =9.7 A large change in pH.

Weak acid - strong base
eg 0.1M Hac and 0.1M NaOH
take 100.00 cm-3 of 0.100M CH3COOH and titrate with 0.100M
NaOH.

At the start, the pH is 2.88, calculated using the Ka value.

As OH– is added it will react with the acid according to

CH3COOH(aq) + OH–(aq) CH3COO–(aq) + H2O(l)
In effect, this just produces a buffer solution.
 For this particular buffer we know that

[CH COOH ] 
3
pH = pK a - log 10  – 
[CH 3 COO ] 
When 50.0 cm-3 of NaOH has been added, half of the HAc has
reacted and formed Ac- ie. [Hac] = [Ac-] then
pH = pKa - log101, pH = pKa .
This is called the half equivalence point which corresponds to an
equimolar buffer. The pH rises relatively slowly about this point.

When 100 cm-3 of NaOH has been added the equivalence point is
reached. 10-2 mol of CH3COO– will have formed , but now in a
total volume of 200 cm-3 so [CH3COO–] = 0.05 M

pH value comes out to 8.73.

 The last part of the titration is dominated by the further
addition of base so the pH in this region closely follows that
for a strong acid vs strong base titration.

Strong acid - weak base

Inverse of the above - equivalence point <7

Weak acid - weak base

Equivalence point depends on the relative sizes of
Ka and Kb
 6.6 Polyprotic Acids
Can donate two or more hydrogen ions to acceptor
molecules. An example of a diprotic acid would be
carbonic acid H2CO3
CO2(aq) + H2O(l) H2CO3(aq)
H2CO3(aq) + H2O (l) H3O+ (aq) + HCO3–(aq)
Ka1 = 4.2 10-7
HCO3- (aq) + H2O (l) H3O+ (aq) + CO32–(aq)
Ka2 = 4.8 10-11
(So H2CO3 is a stronger acid than HCO3-)

In calculations involving such simultaneous

equilibria the [H3O+] enters in two equilibrium
expressions. Its value is the same in both!!
 Usually the Ka1 is significantly larger than
Ka2 because the second proton is more
tightly held (-ve charge on conjugate base of
original acid).

When this is true, the equilibria can be

handled sequentially.

Titration curve will show 2 equivalence

points.
 ACID RAIN

QuickTime™ and a
Photo - JPEG decompressor

CO2 NO2 SO2 are needed to see this picture

Check out the WEB. USA EPA at

http://www.epa.gov/docs/acidrain/ardhome.html
Ph of rainwater in USA
 ACID RAIN
Fossil fuel burning gives : CO2 NO2 SO2
2H2O (l) + CO2 (g) H3O+(aq) + HCO3- (aq)
2NO2 (g) + H2O (l)` HNO2(aq) + HNO3 (aq)
2SO2 (g) + O2 (g) 2SO3 (g)
SO3 (g) + H2O (l) H2SO4 (aq)
Marble/limestone (CaCO3) destroyed.
CaCO3 + H2SO4 (aq)
Ca2+ (aq) + SO42-(aq) + H2O (l) + CO2 (g)
Calcium carbonate more soluble at low Ph!
 Solubility Equilibria
A saturated solution is one in which an
equilibrium exists between a solid substance
and its dissolved form.

The solubility of a salt is the largest amount

which will dissolve in a specified volume of
solvent at a particular temperature before
solid becomes visible.

Solubility is highly temperature dependent.

 Ionic Equilibria
For substances having a low solubility we can use
equilibria in order to determine the concentrations of
aquated ions.
For example, if we take the salt MXn the dissolution
process can be written
MXn(s) + H2O(l) M+(aq) + nX–(aq)
a M +  (a X - ) n
K= a
MXn

This is a heterogeneous process for which aMXn = 1

K = [M+] [X-]n
This expression is valid providing some MXn(s) is
present.
 K is called the "solubility product constant",
denoted Ksp.

For example, for the silver halides, we have

Species Ksp
AgCl 1.6 10-10
AgBr 7.7 10-13
AgI 1.5 10-16

Using this data we can work out the solubility

of these compounds in water.
The Effect of pH on Solubility
Salts containing anions which are weak or strong
bases have enhanced solubility in acid solutions.
For metal hydroxides this is easy to explain:
M(OH)2 M2+(aq) + 2OH-(aq)
The solubility product for this metal hydroxide is then
Ksp = [M2–] [OH–]2
If we have a saturated solution of M(OH)2 and add some
acid, the [OH–] falls.
By LeChatelier's principle, Q < Ksp, so more M(OH)2
dissolves to re-establish equilibrium.
Example 4 - Acid Rain
Example 4 - Acid Rain
Calculate the solubility of CaCO3 in natural water
pH=7 in rain (pH=6.5) and acid rain (pH= 5.6).
CaCO3(s) Ca2+ + CO32-
Ksp = 8.7  10-9
It would be tempting to write [Ca2+] = [CO32-] = S but
this isn’t correct because CO32- reacts in water to
form HCO3- and H2CO3
The proportions of each present depends on pH - see Fig 6-12:
pH f(H2CO3) f(HCO3–) f(CO32–)
5.6 8.80  10-1 1.2 10- 1 2.00  10-9
6.5 4.99  10-1 4.99  10-1 5.00  10- 6
7.0 1.92  10-1 8.07  10-1 3.87  10- 4
 Let: [Ca2+] = x
then [CO32-] = f(CO32-) . x
 Ksp = [Ca2+][CO32-] = 8.7 x 10-9
= x . f(CO32-) . x = x2 f(CO32-)

(i) pH = 7:
x = (8.710-9 / 3.8710-4)0.5 = 0.0047 M

(ii) pH = 6.5:
x = (8.710-9 / 5.010-6)0.5 = 0.0417 M

(iii) pH = 5.6:
x = (8.710-9 / 2 10-9)0.5 = 2.085 M
 QuickTime™ and a
Photo - JPEG decompressor
are needed to see this picture

Effect on marble monuments.

 QuickTime™ and a
Photo - JPEG decompressor
are needed to see this picture

Effect on trees
 Back to the Sunken Treasu
money.
What happens to silver co

1622 - 1985 .
1. Zero oxygen so growth
that synthesize H2S from s

2Ag(s) + H2S(aq) Ag2S(s) + H2 (g)

This thin black layer protects the coins/artifacts.

2. Decomposing wood generates CO2:

CO2(aq) +2H2O (l) HCO3- (aq) ) + H3O+(aq)

HCO3-(aq)+2H2O(l) +Ca+(aq) CaCO3(s) + H3O+(aq)

Result: Corroded coins encased in limestone.

1985:
3. Remove limestone
Soak in buffered acidic bath

CaCO3(s) + 2H3O+(aq) CO2(g)+3H2O(l) +Ca2+(aq)

We now have silver coins with a grotty black AgS
layer.

If we can remove this without destroying the look

of the original coins then the coins will be worth
much much more than the Ag content

How do we do this?

Electrochemistry!