Introduction to Terms

We know from Chemistry 20 that acids are substances that dissolve in water to give a solution that
 Tastes sour
 Reacts with many metals to produce hydrogen gas
 Turns litmus red
 Conducts an electric current
 Neutralizes bases
More specifically:
An acid is a substance that dissociates in water to release hydrogen ions, H+(aq) - a strong acid
ionizes 100 % at all concentrations while a weak acid tends to dissociate partially at most
concentrations. This is an Arrhenius definition of an acid.

We know from Chemistry 20 that bases are substances that dissolve in water to produce a solution that
 Tastes bitter, feels slippery
 Turns litmus blue
 Conducts electric current
 Neutralizes acids
More specifically:
A base is a substance that dissociates in water to release hydroxide ions, OH-(aq). A strong base
dissociates 100 % at all concentrations (even if it has low solubility). This is an Arrhenius
definition of a base (Weak bases, which do not produce hydroxide ions by dissociation, are not
considered by this theory).

Salts are substances that dissolve (dissociate) in water to produce

solutions that
 Taste more or less salty
 Do not react with litmus
 Conduct electric current

Factors Affecting Acid/Base Strength

Strong acids are so named because they react completely with water, leaving no non-ionized molecules
in solution. Visually it looks like this:

HX(aq)  H+(aq) + X-(aq)

Because of this, the strong acid completely

ionizes and other sources of H+ (such as the
auto-ionization of water) become negligible
when calculating [H+] by (Le Châtelier’s
Principle). Consequently, [H+] normally
equals the original concentration of the acid.
For example, in a 0.10 mol/L aqueous solution
of the strong acid, nitric acid, HNO3, [H+] =
0.10 mol/L and [NO3-] 0.10 mol/L; the
concentration of HNO3 is virtually zero.

Other Acid Examples:

1
 HClO4 + H2O  H3O+ + ClO4- 100% ionizes (Strong Acid)
HNO3 + H2O  H3O + NO3+ -
100% ionizes (Strong Acid)
Most substances that are acidic in water are actually weak acids. Because weak acids ionize only
partially in aqueous solution, an equilibrium system is formed between the acid and its ions. The
ionization equilibrium is given by:

HX(aq) H+(aq) + X-(aq)

where X- is the conjugate base. For

calculation purposes, the following
is assumed:

However, keep in mind that the

"Before ionization" state never
actually exists in solution - the
solution is always at equilibrium.
The left hand state is theoretical.

Other Acid Example:

H2S + H2O H3O+ + HS- Less 100% ionization (Weak Acid)

Note that weak acid ionization equations are written with an equilibrium arrow ( ) rather than a
reaction arrow () to signify that they are not 100% dissociated.

Acid ionization, and How It Is Related to the Equilibrium Constant (Kc)

 The ionization level is related to the Kc, for each ionization.
 Remember, we don’t include water in the equation, because it is an aqueous system.

o Strong acids have a very large Kc

HCl(aq) + H2O(l)  H3O+(aq) + Cl-(aq) KC = 1.3 x 106
[ H O  ][Cl  ]
Kc  3
[ HCl ]
o Weak acids have a very small Kc
HF(aq) + H2O(l)  H3O+(aq) + F-(aq) KC = 6.6 x 10-5
[ H 3O  ][ F  ]
Kc 
[ HF ]
Organic acids tend to be weak acids.

The smaller the Kc value, the weaker the acid. Weaker acids ionize less ([H+] is smaller compared to
[HX]) and therefore have a less drastic effect on pH.

POINT TO REMEMBER:
Do not confuse a weak acid with a dilute acid. A weak acid has a small Kc, and a dilute acid has a low
concentration. It is possible to have a dilute, strong acid or a concentrated, weak acid.
Don’t confuse strong and weak acids with concentrated and dilute acids.
A weak acid is still dangerous if it is concentrated (glacial acetic acid).
A strong acid is not harmful if it is very dilute (1 drop of HCl in 2 litres or H2O).

2
Strong Bases:
Strong Bases are strong electrolytes that dissociate (break up to OH- ions) in solution 100 % of time.

Examples:
Group-1 hydroxide: LiOH, KOH, NaOH, RbOH
Heavy Group-2 hydroxides: Ca(OH)2 , Sr (OH)2 , Ba (OH)2 , Ionic metal oxides: Li2O, Na2O, K2O, CaO
These are bases which dissociate 100% in water (or in the case of oxides, react with water) to produce
hydroxides.
Reaction Examples :

KOH  OH- + K+ 100% Dissociation

Ca(OH)2  2OH- + Ca2+ 100% Dissociation
Li2O + H2O  2OH- + Li+ 100% Dissociation
CaO + H2O  Ca(OH)2 strong base produced which then dissociates

Some substances result in basic solutions, even though they do not release OH- ions directly in water.
These substances, such as ammonia, remove an H+ ion from water, and result in an indirect release of
OH- ions.
NH3 + H2O OH- + NH4+ Less 100% Dissociation

Note that weak base dissociation equations are written with an equilibrium arrow ( ) rather than a
reaction arrow () to signify that they are not 100% dissociated.

DataBooklet Acid Base Table, and How It Communicates Acid Base Strength
The Acid Base Table contains the names, formulae, conjugate bases and Ka values of several common
acids ranked in order from strongest to weakest. (Acids get stronger as you go up on the right side while
the bases get stronger going down the left side).

3
 The Bases Weaker than H2O(l) Ka values
Strong HX(aq) -----------> H3O+(aq) + Ka > 1
X-(aq)
Acids 100% Rxn
+
H3O (aq) H2O(l)

The
Weak The Basicity of
Bases most weak
bases is not
The explained by
Weak HA(aq) H3O+(aq) A-(aq) Arrhenius
+ 0 < Ka< 1 Dissociation
Acids
Theory
The < 100% Rxn
Weak
Bases

The
- Strong
H2O(l)H2O(l) OH (aq)
Base
Writing Dissociation equations (H+(aq), or H3O+(aq))

When acids dissociate in water, they release H+(aq) ions. This reaction is often written as:

HCl(aq)  H+(aq) + Cl-(aq)

However, it can also be written as:

HCl(aq) + H2O(l)  H3O+(aq) + Cl-(aq)

Because in reality

H+ + H2O  H3O+

H+ protons & H3O+ Hydronium ion

H+ (aq) H3O+ (aq)

These ions are considered the same.

These ions are used interchangeably in chemistry, and you are responsible to
understand and apply each one.

Calculating pH
Up to this point our Science 10 and Chemistry 20 experimental evidence has pointed to pure water being a non-
electrolyte. With better instruments it is found that a small number of water molecules actually dissociate:

H2O(ℓ) H+(aq) + OH-(aq)

4
or using Brønsted conventions (more on this soon):

2 H2O(ℓ) H3O+(aq) + OH-(aq)

This equilibrium lies very far to the left at 25oC. Following the pattern we have used to write Kc expressions for
other reactions, the liquid water reactant would be excluded, giving:

Kc = [H+][OH-] = 1.0 x 10-14 = Kw

An equivalent expression using the hydronium ion could be written. Sometimes called the "water constant", this
number tells us that, among other things, the product of the concentrations of hydrogen (hydronium) ions and
hydroxide ions in pure water are equal (at 1.0 x 10-7 mol/L each). This is what is meant by "neutral" water. The
following conditions summarize the possibilities:

in pure water [H+] = [OH-]

in acidic solution [H+] > [OH-]
in basic solution [H+] < [OH-]

In aqueous systems this equilibrium dominates acid/base behavior. To understand why, we can use LeChâtelier's
Principle.

The concentrations of ions in acidic and basic solutions can be quite small so it is convenient to have a simple
way of referring to them. The pH scale is such a way. Chemists use the "p" function quite a bit because so many
values they work with are small. A "p" placed in front of a symbol is understood to mean -log. So the definition of
pH might be written as:

pH = -log[H+]

Because of the way logs work the pH of a solution in which [H+] = 1.0 x 10-7 mol/L is equal to 7.00. In other
words, the pH of neutral water is 7.00.
Base 10 logs are also a little unusual with regard to significant digits. The digits to the left of the decimal do not
count as significant digits since they describe the place value of the decimal only (e.g. pH of 7.45 has two
significant digits).

The inverse pH function looks like this:

[H+] = 10-pH

With this formula, pH values can be estimated by looking at the exponent on the concentration. And you will be
correct, as long as the acid is STRONG.

There is a companion function to pH which is sometimes very convenient--especially when dealing with bases for
which a direct pH calculation cannot be done. It is called pOH:

pOH = -log[OH-]

It is also very helpful to remember:

pH + pOH = 14

5
 Practice Problems: pH Calculations
Hydronium Ion and Hydroxide Ion Concentration:

1. What is the molar H3O+ ion concentration in solutions with the following HO- ion concentrations?
a) 2.0 X 10-4 mol/L
b) 7.3 X 10-7 mol/L
c) 3.0 X 10-10 mol/L
d) 2.5 X 10-8 mol/L

2. In the problem above (1), indicate whether each solution is acidic, basic, or neutral.

3. What is the molar OH- ion concentration in solutions with the following H3O+ ion concentrations?
a) 2.7 X 10-4 mol/L
b) 7.5 X 10-9 mol/L
c) 1.0 X 10-7 mol/L
d) 5.0 X 10-8 mol/L

4. In the problem above (3), indicate whether each solution is acidic, basic, or neutral.

pH:

5. Calculate the pH of solutions with the following hydronium ion concentrations.

a) 1 X 10-4 mol/L f) 5 X 10-7 mol/L
-9
b) 1 X 10 mol/L g) 3 X 10-3 mol/L
c) 0.00001 mol/L h) 3.0 X 10-3 mol/L
d) 0.000000001 mol/L i) 3.000 X 10-3 mol/L
e) 4 X 10-2 mol/L

6. What is the hydronium ion concentration associated with each of the following pH values?
a) 3.0
b) 5.7
c) 2.43
d) 3.43
e) 7.45

7. Solution A has [OH-] = 4.3 X 10-4 mol/L. Solution B has [H3O+] = 7.3 X 10-10 mol/L.
a) Which solution is more basic?
b) Which solution has a lower pH?

8. A solution has a pH of 4.500. What will be the pH of this solution if the hydronium ion concentration is
a) doubled
b) quadrupled
c) increased by a factor of 10
d) increased by a factor of 1000

Additional Problems:

9. In which of the following pairs of solutions does the first listed solution have a lower pH than the second listed solution?
a) 0.1 mol/L HCl and 0.2 mol/L HCl
b) 0.1 mol/L HCl and 0.1 mol/L H2SO4
c) 0.20 mol/L H2SO4 and 0.25 mol/L HNO3
d) 0.2 mol/L H2SO4 and 0.2 mol/L H2CO3

10. What would be the pH of a solution that contains 0.1 mole of each of the solutes NaCl, HNO 3, HCl, and NaOH in enough
water to give 3.00 L of solution?

11. How many hydronium ions are present in a 10.0 mL sample of hydrochloric acid that has a pH of 5.42?

6
pH Calculations Answers
Hydronium Ion and Hydroxide Ion Concentration:

1. c) 3.500
a) 5.0 X 10-11 mol/L d) 1.500
b) 1.4 X 10-8 mol/L
c) 3.3 X 10-5 mol/L
d) 4.0 X 10-7 mol/L Additional Problems:

2. 9.
a) basic a) no
b) basic b) no
c) acidic c) yes
d) acidic d) yes

3. 10. 1.5
a) 3.7 X 10-11 mol/L
b) 1.3 X 10-6 mol/L 11. 2.3 X 1016 H3O+ ion
c) 1.0 X 10-7 mol/L
d) 2.0 X 10-7 mol/L

4.
a) acidic
b) basic
c) neutral
d) basic

pH:

5.
a) 4.0
b) 9.0
c) 5.0
d) 9.0
e) 1.4
f) 9.1
g) 2.5
h) 2.52
i) 2.5229

6.
a) 1 X 10-3 mol/L
b) 2 X 10-6 mol/L
c) 3.7 X 10-3 mol/L
d) 3.7 X 10-4 mol/L
e) 3.5 X 10-8 mol/L

7.
a) Solution A
b) Solution B

8.
a) 4.199
b) 3.900
7
Arrhenius Acids and Bases Worksheet

1) Fill in the following table:

Compound Name Type Ionic Equation Concentration of each

(acid, base ion (mol/L), assuming
or salt) 0.050 mol/L solute
2+ -
MgCl2(aq) Magnesium Salt MgCl2(aq) Mg (aq)+ 2Cl (aq) Mg2+(aq) = 0.050
Chloride Cl-(aq) = 0.10
HClO4(aq)

Ba(OH)2(aq)

NaOH(aq)

HBr(aq)

H3PO4(aq)

KMnO4(aq)

NH4OH(aq)

Al2(SO4)3(aq)

For the following reactions, assume K is large (100% dissociation)

2) If 0.050 mole HCl(aq) is added to 10.0 mL of water, what is the [H+]?

3) If 0.050 mole of Ba(OH)2(aq) is added to 50.0 mL of water, what is the [OH-]?

4) If 0.40 g of NaOH(s) is added to 100.0 mL of water, what is the [OH-]?

5) 12.2 g of Sr(OH)2(s) is added to 150.0 mL of water. Find the [OH-]

6) 4.9 g of H2SO4(l) is dissolved in water to a final volume 50.0 mL. Find the molar concentration of
H2SO4(aq), H+(aq), and HSO4-(aq).

7) 1.0 g of Na2S(s) is dissolved in water to 40.0 mL volume. Find the molar concentration of each ion
in solution.

8
 pH and pOH Review Worksheet
1. Find the pH and pOH for the following:
[H+] pOH pH Show 2 sample calculations
0.0239 mol/L
0.185 mol/L
0.000634 mol/L
7.14 x 10-9 mol/L
2.34 mol/L
5.61 x 10-15 mol/L
1x10-7 mol/L

2. Calculate the [H+] for the following:

pH [H+] Show 2 sample calculations
2.85
12.12
7.00
4.17
0.24
13.69
1.50

3. Find the pH and pOH of a solution if the [H+] = 0.00010 mol/L

4. Find the pH and pOH of a solution if [OH-] = 0.0075 mol/L

5. The pH of an acid solution is 2.30. What is the [H+]?

6. Establish the pH and pOH of 0.0040 mol/L HCl(aq), a strong acid.

7. Find the pH and pOH of 0.0050 mol/L Ba(OH)2(aq), a strong base.

8. The pH of a solution was tested on a pH meter at 8.30.

a. Is this solution acidic or basic?
b. Establish the [H+] and the [OH-].

9. The pOH of a solution of NaOH(aq), a strong base is 4.90. Find the pH, [H+], [OH-] and the
concentration of NaOH(aq).

10. Find the [H+] if the pH = -0.60.

11. 60.0 mL of 0.080 mol/L HBr(aq) is added to 40.0 mL of 0.050 mol/L KOH(aq).
Find the [H+], [OH-], pH and pOH of the resultant solution.

9
 Bronsted-Lowry Acids and Bases
We have seen some examples of solutions that have an effect on pH but do not follow Arrhenius’
definition of acids or bases. If we look at proton transfer, we can explain most all acids and bases.

An acid is a substance that can donate a proton (H+(aq) ion).

A base is a substance that can accept a proton (H+(aq) ion).

An acid base reaction, also known as a neutralization reaction, is the complete or partial transfer of a
hydrogen ion, H+, between the strongest acid (SA) and the strongest base (SB) in a reaction mixture. (as
opposed to redox reactions which are transfer of electrons).

There are three types of equations that can represent neutralizations you are they just yes she will do two
hours into the hell what you get with your will or you I went to sleep and will and in so you gave us to
get very sure at a 90 day you will and you need is a the need to complain you would go a you will and is
in a court is okay I will find you and Laureen run I will leave and there are you will on a you and you
will is your then you read more as you will you and you will be allowed. A and a and you and you will
will you need I used air will will you will will you are something of a all in a in the long old all

1. Molecular equation:
HCl(aq) + NaOH(aq) H2O(l) + NaCl(aq)

2. Ionic Equation:
H+(aq) + Cl-(aq) + Na+(aq) + OH-(aq) H2O(l) + Na+ (aq) + Cl-(aq)

3. Net Equation (Reaction):

H+(aq) + OH-(aq) H2O(l)

In the above example, Na+ and Cl- are spectator ions, and are not involved in the reaction.

A couple of examples can help our understanding of identifying which substances donate and accept
protons:
NH3(g) + H2O(l) NH4+(g) + OH-(aq)

H2O donated a proton to become OH- so it is an acid

NH3 accepted a proton and became NH4+ so it is a base

This reaction can be reversed

NH4+(g) + OH-(aq) NH3(g) + H2O(l)

OH- accepted a proton and became H2O so it is a base

NH4+ donated a proton and became NH3 so it is an acid

Both the forward and reverse reactions have acids and bases.

The pair of substances that donate protons in the forward reaction, and then accept protons when the
reaction is reversed are called conjugate acid base pairs, and vice versa..

In the above example

10
 NH3/NH4+ and H2O/OH- are conjugate acid base pairs.

Overall:
 Strong acids (A) tend to have weak conjugate bases (CB), and vice versa for strong bases.
 Weak acids (B) tend to have strong conjugate bases (CB), and vice versa for weak bases.
e.g.
A B CA CB
HCl(aq) + H2O(l) H3O (aq) + Cl-(aq)
+

A B CA CB
H2O(l) + H2O(l) H3O+(aq) + OH-(aq)

Amphoteric Substances

Water can act as both a base and an acid. Substances like these are called amphoteric (amphiprotic).

If two substances are mixed and both of them can be an acid, the stronger acid (larger Ka) is the
substance that will act as the acid.
A B CA CB
HClO4(aq) + HSO4-(aq) H2SO4(aq) + ClO4-(aq)

Hydrogen sulphate is usually an acid, unless mixed with a stronger acid, then it acts as a base (the
hydrogen sulphate is an amphoteric substance).

Another way to explain this is to compare the acids (or bases) on both sides. If the stronger acid is on the
left (reactant side) it will give up a proton and the products will be favored.
If the stronger acid is on the right, the reverse reaction will be favored.

11
Bronsted Lowry Acid Base Conjugate Pairs Worksheet

1. Label all the entities as either acid (A), base (B), conjugate Acid (CA) or Conjugate Base (CB), write
in either or  , and write the conjugate pairs in the parentheses provided.

a. SO32-(aq) + H3O+(aq) HSO3-(aq) + H2O(l) ( , ); ( , )

b. H3O+(aq) + OH-(aq) H2O(l) + H2O(l) ( , ); ( , )

c. H2O(l) + H2O(l) H3O+(aq) + OH-(aq) ( , ); ( , )

d. HCO3-(aq) + H3O+(aq) H2CO3(aq) + H2O(l) ( , ); ( , )

e. HCO3-(aq) + OH-(aq) CO32-(aq) + H2O(l) ( , ); ( , )

f. HCO3-(aq) + HOCl(aq) H2CO3(aq) + OCl-(aq) ( , ); ( , )

g. NH4+(aq) + OH-(aq) NH3(aq) + H2O(l) ( , ); ( , )

h. CF3COOH(aq)+ OH-(aq) CF3COO-(aq) + H2O(l) ( , ); ( , )

i. H2O(l) + HCN(aq) H3O+(aq) + CN-(aq) ( , ); ( , )

j. H3O+(aq) + PO43-(aq) H2O(l) + HPO42-(aq) ( , ); ( , )

k. H3O+(aq) + HPO42-(aq) H2O(l) + H2PO4-(aq) ( , ); ( , )

l. H2PO4-(aq) + HBO32-(aq) HPO42-(aq) + H2BO3-(aq) ( , ); ( , )

m. NH3(aq) + H3O+(aq) NH4+(aq) + H2O(l) ( , ); ( , )

n. CH3COOH(aq) + OH-(aq) CH3COO-(aq) + H2O(l) ( , ); ( , )

o. H2O(l) + HNO2(aq) H3O+(aq) + NO2-(aq) ( , ); ( , )

p. H2O(l) + S2-(aq) OH-(aq) + SH-(aq) ( , ); ( , )

12
 Acid Base Strength As It Relates to the Equilibrium Constant (Ka)

The equilibrium constant is used to measure strengths of acids.

The larger the Ka, the greater the dissociation and the more H+(aq) ions are present.

HCl(aq) Ka = 1.3 x 106

HF(aq) Ka = 6.6 x 10-4
H2CO3(aq) Ka = 4.4 x 10-7

The acid base table shows strength of acids.

The acidity of a chemical substance in water is dependent on which entity - water or the conjugate base
of the acid - has a greater hold on the proton that’s responsible for the solution pH! It’s very a much a
tug-of-war over one proton between two possible conjugate bases (remember water is the conjugate base
of H3O+(aq)) as is outlined in the following simple illustrations:

a. CH3COOH(aq) + H2O(l) H3O+(aq) + CH3COO-(aq)

O O O
CH3 C H CH3 C H CH3 C H
O - + H O+
O H + O H O O
H H H
The “Tug-of-War”

 The acetate ion is a stronger conjugate base than water since the reaction shown proceeds
towards products only a few percent at normal concentrations

b. HCl(aq) + H2O(l) ------> H3O+(aq) + Cl-(aq)

H H H
Cl - + H O+
Cl H + O Cl H O
H H H
The “Tug-of-War”

 In this second case hydrochloric acid is a strong acid because chloride ion is a weak conjugate
base when compared to water.

 In general, weak acids have conjugate bases that are stronger Brønsted-Lowry bases than water.
In fact, the stronger the conjugate base the weaker the acid.

 All the strong acids have conjugate bases that lie above water in most common acid base tables.
Except for sulphuric acid the conjugate bases of strong acids generally form neutral solutions.

13
  The diagrams below illustrate how, on an acid base table, weak acid/weak base strength and their
respective conjugates’ strengths are related.

HHO
3
+ +
3O (aq)
(aq) HHO
22O(l)
( l) H
H3O
O++(aq)
3 (aq) HO
H22 O((l)l )

Acid Conjugate Conjugate

Getting Base Base
Getting Acid Getting
Weaker Stronger getting Weaker
Stronger

HHO
22O(l)
( l) OH- -(aq)
OH (aq) HO
H22O((l)l ) OH- (aq)
OH-(aq)

Dissociation Reactions in water.

All reactions are relative to water, so the Ka of water is 1.00

Acid dissolving in water is exothermic, therefore adding heat will drive the reaction to the left,
decreasing the dissociation and then decreasing the Ka value.

The Reactions of Polyprotic Acids and Bases

Polyprotic acids donate 1 H+ ion at time, and therefore have different Ka values for each dissociation
e.g.
H2CO3(aq) + H2O(l)  H3O+(aq) + HCO3-(aq) Ka = 4.4 x 10-7

HCO3-(aq) + H2O(l)  H3O+(aq) + CO32-(aq) Ka = 4.7 x 10-11

Each proceeding Ka is smaller than the previous, and this makes sense because the removal of the next
H+ is from a negatively charged species.

 When you calculate the pH of a polyprotic acid – the first Ka is much greater than the second Ka,
so the pH is essentially found using the first Ka.
 The second dissociation only occurs when mixed with a base, to force the removal of the second
(or third) H+ ion.
 The conjugate base of polyprotic acids are amphoteric and are found as both acids and bases in
the acid base table.

14
The Reactions of Polyprotic Acids and Bases – A Worksheet

1. Provide Brønsted-Lowry predictions of all the reactions that are likely to occur in the following
scenarios:

a. Sulphuric acid is titrated with sodium hydroxide in the presence of methyl orange
indicator.

b. Hydrochloric acid is continuously added (i.e. it is always present) to an aqueous solution

of sodium borate in the presence of phenolphthalien.

c. An aqueous solution of sodium carbonate is titrated with nitric acid (which means it is
added continuously). Which of phenol red, bromothymol blue or methyl orange would
be the best choice for indicating: (i) the 2nd quantitative reaction? (ii) the 1st
quantitative reaction?

d. Oxalic acid is titrated with sodium hydroxide in the presence of methyl orange indicator.

e. A solution of sodium hydroxide is continuously added to hydrosulphuric acid containing

some indigo carmine.

f. A sample of aqueous sodium sulphite containing orange (IV) is titrated with perchloric
acid. How many quantitative reactions occur before the endpoint?

15
 Relative strengths of Bases
Bases accept protons

All bases react with water to produce the conjugate acid and the hydroxide ion.
e.g.
CN-(aq) + H2O(l) HCN(aq) + OH-(aq)

[ HCN ][OH  ]
Kb 
[CN  ]

To find the Kb:

Remember that weak bases (measured by Kb) have fairly strong conjugate acids (measured by Ka). And
strong bases (measured by Kb) have fairly weak conjugate acids (measured by Ka). This suggests there
is a relationship between the Ka of the acid and the Kb of the base

It turns out that

Kw = Ka x Kb

Proof for above formula:

NH3(g) + H2O(l) NH4+(g) + OH-(aq)

[ H 3 O  ][ NH 3 ]
Ka  
[ NH 4 ]

NH4+(g) + OH-(aq) NH3(g) + H2O(l)


[ NH 4 ][OH  ]
Kb 
[ NH 3 ]
To show Ka x Kb = Kw


[ NH 4 ][OH  ] [ H 3 O  ][ NH 3 ]
x 
 [ H 3 O  ]x[OH  ]  K w
[ NH 3 ] [ NH 4 ]

K w 1.0 x10 14

Kb  
For the base NH3: K a 5.8 x10 10
Kb = 1.7 x 10-5

The Kb is stronger than the Ka, so NH3 is a stronger base than NH4+ is an acid.

Recall from equilibrium that both reactions would still favour the reactants (K<1).

16
 Predicting Which Substances React as Acids and Bases,
and Which Side is Favoured:
You may be given a couple of compounds, and will need to identify which acids and bases will react. –

Five Steps to Doing This:

1. List the substances present.

a. Remember that ionic compounds may be ions if they are soluble.
b. Acids/bases will dissociate if they are strong
c. Molecular compounds are listed as molecules.
2. Don’t forget to list water!!
3. Use the table on page 11 to identify the strongest acid (highest on the list)
4. Use the table on page 11 to identify the strongest base (lowest on the list)
5. Move one (1) H+ ion from the acid to the base to get the conjugate base and acid.

Predict the equilibrium quickly using the following:

 Products will be favoured if the acid is above the base
 Reactants will be favoured if the base is above the acid.
 Sometimes you don’t get a reaction!!

Example:
NaOH(aq) is mixed with vinegar (ethanoic acid).

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

Products are favoured because ethanoic acid is found above hydroxide ion.

Example:
Ammonium nitrate is produced from reacting ammonia with nitric acid.

HNO3(aq) + NH3(aq) NO3-(aq) + NH4+(aq)

Products are favoured because nitric acid is found above ammonia.

17
Bronsted-Lowry Acids and Bases Worksheet

1. For the acid base pair H2S/HS- in aqueous solution:

a. Name the acid. Establish the reaction of the acid in water, the equilibrium expression and the Ka value.

b. Name the base. Establish the reaction of the base in water, the equilibrium expression and the K b value.

2. Given the two solutions: 0.10 mol/L HOCl(aq), and acid solution, and 0.10 mol/L NaOCl(aq), a salt solution:
a. Name the acid and its conjugate base.

b. Which is the stronger – the acidic properties of 0.10 mol/L HOCl(aq) or the basic properties of 0.10
mol/L OCl-(aq)?

3. For the three acids below, write the acid formula with their Ka values and their conjugate base.
a. Phosphoric acid
b. dihydrogen phosphate ion
c. hydrogen phosphate ion

4. For the bases SO42-(aq) and SO32-(aq), write the reaction of each base in water, the equilibrium expression and
the Kb value.

5. Given the four acids, H2SO4(aq), HCOOH(aq), H2SO3(aq) and HI(aq):

a. Write the reaction of the acids in water, with their Ka values.

b. Name the acids and rank them in decreasing order of their strengths. Label the acids as strong or weak.

6. Given the four bases, HSO4-(aq), SO32-(aq), CH3COO-(aq) and CO32-(aq), name the base and use the table to
rank them in increasing order of their relative strength.

7. Classify as acidic or basic the four solutions whose pH only is given. Establish the [H3O+] for the acid
solutions and the [OH-] for the basic solutions.

a. Solution A pH = 9.0 c. Solution C pH = 4.0

b. Solution B pH = 11.4 d. Solution D pH = 1.5

8. Rank the following acids in decreasing order of their strengths and label them as strong or weak acids.

I. Hydrochloric acid VI. Ethanoic acid

II. Hypochlorous acid VII. Methanoic acid
III. Perchloric acid VIII. Oxalic acid
IV. Nitrous acid IX. Hydrogen oxalate ion
V. Nitric acid
18
9. For the acids listed in the previous problem, write the conjugate bases and rank them in increasing order of
their strengths.

10. Does 0.10 mol/L NaHCO3(aq) have stronger acidic properties than 0.10 mol/L Na2CO3 has basic properties?
(remember that Na+ is a spectator ion)

11. For the reaction:

12. HIO3(aq) + HCO3-(aq)  H2CO3(aq) + IO3-(aq)

a. Using the Bronsted-Lowry definitions, establish:

b. The acid
c. The base
d. The conjugate acid
e. The conjugate base
f. The Kb for the conjugate base, if the Ka for the acid is 1.9 x 10-1.

19
 Balancing Brønsted-Lowry Neutralization Reactions

1. List and label all species in the reaction mixture as acid (A), base (B), both or neither.
a. Strong acids are written as H3O+(aq) and the appropriate conjugate base. Weak acids are
written in molecular form. Metal hydroxides and other salts, if they are soluble, are written
in dissociated form.
2. Find the strongest acid, SA (highest acid on the LHS of an acid base table).
3. Find the strongest base, SB (lowest base on the RHS of an acid base table)..
+
4. Exchange an H from the SA to the SB to give the product conjugate base and acid.
5. Guidelines for estimating” the extent of reaction (WA = , weak acid: WB = weak base).
+ -
a. H3O (aq) + Base (below NO3 (aq)) 100% reaction, quantitative.
-
b. OH (aq) + Acid (above HCN(aq)) 100% reaction, quantitative.
c. WA + WB(WA above WB) >50% reaction, equilibrium favours the products.
d. WA + WB(WA below WB) <50% reaction, equilibrium favours the reactants.
6. For polyprotic acids/bases repeat steps 1 through 5 for the species list of the products of each
reaction. The net acid base reaction is the sum of all the quantitative reactions.

Practice

1. Use the Brønsted-Lowry theory balancing rules to predict an equation for a-f.
(a) Sodium cyanide forms basic solutions in water.

(b) Aqueous solutions of sodium bicarbonate and ammonium chloride are mixed.

(c) Potassium hydrogen sulphate and sodium acetate are mixed in aqueous solution.

(d) Hypochlorous acid and aqueous sodium bicarbonate are mixed. Is the acid completely
neutralized? Explain

20
(e) Hydrochloric acid and aqueous sodium hydroxide are mixed during a titration analysis.

(f) The calcium carbonate dissolved in an Albertan lake neutralizes acid pollution (assume
the polluting acid is sulphuric acid).

(g) If acid precipitation (see f) reacts with the limestone (calcium carbonate) in public statues
and building stone predict a likely percent reaction. Explain!

(h) Household ammonia and sodium bicarbonate are mixed in aqueous solution.

(i) Vinegar and Liquid Drano® (mostly NaOH(aq)) are mixed.

(j) In the classic Volcano demonstration baking soda(NaHCO3(s)) dissolves in vinegar and
reacts to produce a gas. Is baking soda capable of completely neutralizing vinegar?

21
 Predicting Bronsted Lowry Acid Base Reactions
1. Write the possible acid-base reaction that occurs between the two substances given in each
section, (a) to (d). Use the general rule only to predict whether reactants or products are
favoured at equilibrium.
a. Methanoic acid is added to an aqueous solution of sodium hydrogen phosphate.
b. Calcium sulfate is added to a solution of acetic acid in water.
c. Oxalic acid is added to an aqueous solution of magnesium sulfide.
d. Ammonia is added to an aqueous solution of sodium carbonate.

2. Carbonic acid is added to a solution of potassium fluoride.

H2CO3(aq) + F-(aq) HF(aq) + HCO3-(aq)

a. A possible acid base reaction is given above. Are products or reactants favoured? Justify
your choice.

3. The soluble salt, NaNO3, is added to an aqueous solution of phosphoric acid. Write the equation
for a possible reaction and establish whether a reaction occurs (justify your answer).

4. Acetic acid is added to a solution of ammonia in water. Write an equation for the reaction and
establish the Keq to show whether products or reactants are favoured at equilibrium.

5. Potassium nitrite is added to an aqueous solution of sulfurous acid. Write an equation for the
reaction and establish if the products or reactants are favoured.

6. Ammonium chloride (NH4Cl(s))is added to an aqueous solution of hypochlorous acid,

HOCl(aq). Will a reaction occur?

7. Will a reaction occur between sulfurous acid (H2SO3(aq)) and hydrogen phosphate ion (HPO42-
(aq))?

8. A solution of 0.10 mol/L HBr(aq) is added to a solution of 0.10 mol/L H2SO4(aq). Will a
reaction occur?

9. Hydrogen sulfide gas is bubbled into a solution of sodium hydrogen carbonate. Write the
possible reaction and use the KC for the reaction to predict whether a reaction will occur.

10. Acetic acid is added to a solution of lithium cyanide. Write the net equation for a possible
reaction and predict whether products or reactants are favoured at equilibrium.

22
 A. Calculating pH and [H3O+] for Weak Acids in Aqueous
Solutions
Strong Acids – easy – they dissociate completely, so the [acid] = [H3O+] and then you can easily
calculate pH.

Weak acids – a bit tougher, but they are just equilibrium questions.

The Ka is used, along with the initial acid concentration to help us find the [H3O+].

Example Question Of Calculating the pH of a Weak Acid:

Find the [H3O+] for 0.050 mol/L acetic acid at 25 °C.

CH3COOH has a Ka = 1.8 x 10-5 (from page 11 DataBooklet)

Make an ICE chart

CH3COOH(aq) + H2O(l)  H3O+(aq) + CH3COO-(aq)
I[ ] 0.050 0 0
C[ ] -x +x +x
E[ ] 0.050 – x x x

[ H 3 O  ][CH 3 COO  ]
Ka 
[CH 3 COOH ]
( x)( x)
1.8 x10 5 
(0.050  x)
Here we can make an assumption that since the Ka is so small, then x should be a lot smaller than 0.050
mol/L (less than 5%). Therefore we can drop “x” from the denominator ([CH3COOH]).
Therefore we have the formula
( x)( x)
1.8 x10 5 
(0.050) NO QUADRATIC!!!!
x2 = (0.050)(1.8 x 10-5)

x = 9.5 x 10-4

So at equilibrium, [H3O+] = 9.5 x 10-4 mol/L

We can also calculate Ka using [H3O+]

23
Example Question of Finding the Ka, given pH and Initial Concentration of Weak Acid
Establish the Ka for 0.10 mol/L HF(aq) at 25 °C. The pH meter recorded a pH of 2.10 for the acid
solution.
pH = 2.10 so therefore [H3O+] = 7.9 x 10-3 mol/L

Make an ICE chart

HF(aq) + H2O(l)  H3O+(aq) + F-(aq)
I[ ] 0.10 0 0
C[ ] -7.9 x 10-3 +7.9 x 10-3 +7.9 x 10-3
E[ ] 0.10 – 7.9 x 10-3 7.9 x 10-3 7.9 x 10-3

[ H 3 O  ][ F  ]
Ka 
[ HF ]
[7.9 x103 ][7.9 x103 ]
Ka 
[0.10  7.9 x103 ]
Ka = 6.8 x 10-4
Watch out for the addition of any ion to an acid base system that is found in the Ka expression!!!!

Example of a Common Ion Effect Question

Find the [H3O+] of a 1.0 L aqueous solution containing 0.050 mol of acetic acid, CH3COOH, and 0.20
mol of potassium acetate, KCH3COO, at 25 °C.

Potassium acetate is a soluble salt and ionizes completely.

KCH3COO(aq)  K+(aq) + CH3COO-(aq)
0.20 mol/L 0.20 mol/L 0.20 mol/L

Acetic acid is a weak acid, and has a Ka of 1.8 x 10-5

Make and ICE table to solve this.

CH3COOH(aq) + H2O(l)  H3O+(aq) + CH3COO-(aq)
Initial [ ] 0.050 0 0.20
Change [ ] -x +x +x
Equilibrium [ ] 0.050-x x 0.20 + x

[ H 3 O  ][CH 3 COO  ]
Ka 
[CH 3 COOH ]

[ x][0.20  x]
1.8 x105 
[0.050  x]
Ionization of weak acids is so small, it has no significant impact by including it with 0.20 or 0.050 mol/L

[ x][0.20]
1.8 x105 
[0.050]
6
x  4.5 x10 mol / L
When you compare this result with the one above for weak acids, you see that the concentration of H3O+
decreases, adding an ion (called a common ion) will push the equilibrium to the left. This common ion
effect is behind the principles of buffers.
24
A Few Questions on Strong Acids (easy) and Weak Acids (easy if you use ICE Charts)

1. Calculate the [H3O+] for 0.010 mol/L HOCl(aq) at 25 °C.

2. Given 0.0050 mol/L HCN at 25 °C, establish:
a. [H3O+]
b. pH
c. pOH
3. Calculate the [H3O+] and the pH of a 1.0 L aqueous solution of 0.0050 mol/L HF(aq), in which 0.020
mol of barium fluoride (BaF2(aq)) has been dissolved.
4.
a. Establish the pH of 1.0 x 10-4 mol/L H2CO3(aq) at 25 °C.
b. H2CO3(aq) is a diprotic acid. Show mathematically that further ionization of HCO3-(aq) is
insignificant in calculating the pH value.

Acid Base Titrations:

Titration is a method for measuring the concentration of a solution. We perform titrations reactions in
our Electrochemistry Unit as well. Neutralization reactions are the basis for acid-base titrations that
involve the progressive addition of a solution of known concentration to a solution of unknown
concentration.

The solution that is added, is added by using a burette. The original unknown solution can be measured
out using a pipette or another burette. The diagram below illustrates the titration apparatus you will use
in this course.

Titration Apparatus and Terms Used in Titration Analysis

25
 Burette

Titrant
(goes in burette)

The Titrant is what you titrate with.

The Sample is what is being titrated.

In an acid base titration the

indicator is added to the sample in the
Erlenmeyer flask .

Generally speaking:

An indicator takes itsacid form in anacid sample , and

An indicator takes itsbase form in abase sample .

Stopcock

One drop
1
( mL)
20

Erlenmeyer
Flask
Sample and Indicator

EQUIVALENCE POINT:
When a base is added to an acid, the acid is neutralized. The [H+] decreases while the [OH−] increases.
Eventually the [H+] = [OH−]. The concentrations are equal. The equivalence point is reached. Finding
the equivalence point in acids and bases is fairly easy because we use acid base indicators that change
colour around the equivalence point. More on indicators later.

Indicators like litmus are used to indicate when we have reached this point. If we continue to add a base,
the solution becomes basic. Originally, little change occurs when the base is first added
Near the equivalence point, there is a drastic change in [H+] and [OH−]. One drop of base added to an
acid near the equivalence point could change the [H+] from 10−2 to 10−7

Sample problem:
10.0 mL of an unknown concentration of NaOH is placed in a flask. A drop of indicator is added. A 2.00
mol/L solution of HCl is added until a colour change occurs. If it takes 25.0 mL of HCl to reach the
equivalence point, what is the concentration of the NaOH?

1. Find #moles of 1 species.

2. Solve for moles of unknown species by using mol ratio in balanced equation.
(The ratio is not always 1:1)
3. Find C or V of unknown species from moles calculated in step 2.

H+(aq) + OH-(aq) H2O(l)

26
 2.00molHCl( aq ) 1molNaOH ( aq ) 1
0.025mLHCl( aq )   
1LHCl( aq ) 1molHCl( aq ) 0.0100 LNaOH ( aq )

= 5.00 mol/L NaOH(aq)

Charts and Graphs of Neutralization Reactions: pH Curves

The variation in pH that occurs during an acid-base titration provides valuable analytical evidence about
the nature of the reactants and the products of an acid base neutralization reaction. Calculations of pH
changes during the titration of a strong acid by a strong base, or vice versa, are accomplished using
stoichiometric calculations.

The diagram below shows the features to be expected when a strong acid sample is titrated with a strong
base. Several key points are worth emphasising here.
Strong Acid/Strong
Strong Acid/Strong Base Titrations Base Titrations

 The sharp drop in pH occurs when

a quantitative exchange of the
acid’s proton has been completed.
These equivalence points appear
only when the acid proton has been
donated/removed completely
(100%).
 Proton exchange reactions that are
at equilibrium do not result in
large changes in pH.
 The # of equivalence points = the #
of protons exchanged
quantitatively .

Why is a Titration Curve Shaped Like It Is?

The pH increases slowly at first because the pH scale is logarithmic, which means that a pH of 1 will
have 10 times the hydronium ion concentration than a pH of 2. Thus, as the hydronium ion is initally
removed, it takes a lot of base to change its concentration by a factor of 10, but as more and more
hydronium ion is removed, less base is required to change its concentration by a factor of 10. Near the
equivalence point, a change of a factor of 10 occurs very quickly, which is why the graph is extremely
steep at this point. As the hydronium ion concentration becomes very low, it will again take a lot of base
to increase the hydroxide ion concentration by 10 fold to change the pH significantly.
Strong Base/Weak
Acid Titration

27
Strong Base/Weak Acid Titration

Line 2 is the weak acid. Note that it starts

with a higher pH than the strong acid (Line 1),
and has a smaller range of equivalence. This
smaller range is a result of the “buffering”
effect of the conjugate base of the weak acid.
For a strong base, weak acid titration, the
equivalence point ends up being greater than 22
7.0. The reason for this is that when the acid
and base neutralize each other, the conjugate
acid is water (very weak, and no effect on pH)
and the conjugate base of the weak acid is still 1
weak, but has some effect on pH. For
example CH3COOH, acetic acid neutralizes to
acetate ion (CH3COO-) and this weak base is
strong enough to raise the pH slightly, so the
equivalence point is above 7.0.
Buffering regions appear where weak acids or
bases are being titrated (this occurs before the
equivalence point) – More on this later. Strong Acid/Weak
Base Titration
Strong Acid/Weak Base Titration

Fourth line is the weak base. Note that it starts

with a lower pH than the strong base (Third 3
Line), and has a smaller range of equivalence.
This smaller range is a result of the “buffering”
effect of the conjugate acid of the weak base. 4
For a strong acid, weak base titration, the
equivalence point ends up being less than 7.0.
The reason for this is that when the acid and
base neutralize each other, the conjugate base is
water (very weak, and no effect on pH) and the
conjugate acid of the weak base is still weak,
but has some effect on pH. For example
ammonia (NH3) neutralizes to ammonium ion
(NH4+) and this weak acid is strong enough to
lower the pH slightly, so the equivalence point
is below 7.0.

Polyprotic Acid Titrations

When more than one proton is neutralized the second proton is a weaker acid, (has a smaller Ka). This
weakness is shown as a gentler less pronounced rise in the second equivalence point, a third equivalence
point is even less pronounced. Remember, the number of equivalence points is equal to the number of
protons exchanged quantitatively.
Strong Base Polyprotic
Acid Titration

28
An example of a polyprotic acid is H2CO3 which
neutralizes in two steps:

H2CO3 (aq) + OH- (aq) H2O (l) + HCO3- (aq)

HCO3- (aq) + OH- (aq) H2O (l) + CO32- (aq)

The titration curve for these reactions will look like

the one above, with two equivalence points.

Thermometric Titration

It is possible to monitor acid base titrations

by other means such as following the
change in temperature or conductivity of
the reaction mixture. Prominent changes
in the graph of the plotted data signify
complete neutralization (See Diagram
Below).

Thermometric titration works best when a

strong acid is neutralized by a strong base.
Remember that these reactions are
exothermic and temperature changes are
significant enough to be easily measured.
The maximum point on the graph
corresponds to the completion of the
reaction.

29
 Neutralization Reactions Worksheet

1. For the neutralization reactions between the following acids and bases, write three balanced
equations:
(i) The molecular equation
(ii) The ionic equation
(iii)The net reaction

b. HNO2(aq) and KOH(aq)

c. HCl(aq) and NaOH(aq)
d. CH3COOH(aq) and KOH(aq)
e. HClO4(aq) and Mg(OH)2(aq)

2. A solution of copper(I) hydroxide, CuOH(aq) was neutralized with sulfurous acid, H2SO3(aq). Write
a balanced equation for the net reaction. (Hint: a precipitate is formed)

3. Find the concentration of an HF(aq) solution if 15.0 mL of 0.200 mol/L KOH(aq) just neutralizes
20.0 mL of HF(aq)

4. 20.8 mL of 0.100 mol/L HBr(aq) were required to neutralize 26.0 mL of Mg(OH)2(aq) of unknown
concentration. Find the concentration of the base.

5. 26.6 mL of 0.040 mol/L H2SO4(aq) are required to neutralize 21.2 mL of NH4OH(aq) of unknown
concentration. Find the concentration of the NH4OH solution.

6. In a 0.10 mol/L solution of HBr(aq) what is the [H+], and the [OH-]?

7. Given 0.15 mol/L Ba(OH)2(aq), establish the [H+] and the [OH-].

8. Given 0.0020 mol/L HClO4(aq), establish the [H+] and the [OH-].

9. 10.0 mL of 1.0 mol/L HCl(aq) is added to 10.0 mL of 0.50 mol/L NaOH(aq). What is the [H+] and
the [OH-] of the resultant solution?

10. 42.8 mL of 0.23 mol/L NaOH(aq) were titrated to equivalence point against 37.9 mL of H2SO4(aq).
Find the concentration of the H2SO4(aq) solution.

11. What volume of 0.25 mol/L KOH(aq) is required to neutralize 41.5 mL of 0.10 mol/L H2SO4(aq)?

30
Predicting a pH Curve

Predicting the pH titration curve of a strong base added to a strong acid is simply a matter of
performing a series of excess-limiting acid base calculations corresponding to each stage of the titration.
The same calculations can be done for almost any combination of weak acid/bases but this goes beyond
the scope of Chemistry 30.

Consider the titration of a strong acid by a strong base (both 0.10 mol/L):

0.0 mL of KOH(aq) : HNO3(aq) + KOH(aq) ------> HOH(l) + KNO3(aq)

(It is acceptable 50 mL 0.0 mL
+
to use Arrhenius’ 5.0 mmol 0.0 mmol (5.0 mmol of H (aq) left in 50 mL)
theory here) pH0 = log(5.0 mmol/50 mL) = 1.00

5.0 mL of KOH(aq) : HNO3(aq) + KOH(aq) ------> HOH(l) + KNO3(aq)

50 mL 5.0 mL
+
5.0 mmol 0.50 mmol (4.5 mmol of H (aq) left in 55 mL)
pH5 = log(4.5 mmol/55 mL) = 1.09

10.0 mL of KOH(aq) : HNO3(aq) + KOH(aq) ------> HOH(l) + KNO3(aq)

50 mL 10.0 mL
+
5.0 mmol 1.00 mmol (4.0 mmol of H (aq) left in 60 mL)
pH10 = log(4.0 mmol/60 mL) = 1.18

+
When 0.0 mmol of H (aq) are left in 100 mL of aqueous solution the pH will be 7.00. Thereafter every
drop of KOH(aq) that is added will send the pH above 7.00. At this point it is necessary to calculate the
pOH and convert it to a pH. See below

55.0 mL of KOH(aq) : HNO3(aq) + KOH(aq) ------> HOH(l) + KNO3(aq)

50 mL 55.0 mL
5.0 mmol 5.50 mmol (0.5 mmol of OH-(aq) excess in 105 mL)
(# sig. digs. ignored here) pOH55 = log10(0.5 mmol/105 mL) = 2.32#
pH55 = 14.00 - 2.32 = 11.68

Continuing in this manner will give you a data set of pH values versus volume of KOH(aq) added. The
table on the next page will make it possible to predict and record your data as you add a total of 100 mL
of 0.10 mol/L KOH(aq) to 50.0 mL of 0.10 mol/L HNO3(aq) in 5.0 mL aliquots. A plot of pH (y- axis)
versus volume of base added (x-axis) is a pH curve.

31
 Practice Plotting a pH Curve

Your assignment is to complete the following table and draw a graph of pH versus volume of base added
on the graph paper provided.

Volume n H+ Volume nOH- nH+/nOH- Vtotal pH

HNO3(aq) KOH(aq) excess
50 0

50 5

50 10

50 15

50 20

50 25

50 30

50 35

50 40

50 45

50 49

50 49.9

50 50 7.00

50 50.1

50 51

50 55

50 60

50 65

50 70

50 75

50 80

50 85

50 90

50 95

50 100

32
Calculating Equivalence Point pH
The equivalence point pH in an acid base titration is determined by the acidity/basicity of the conjugate
produced upon neutralization:

 If strong acid is neutralized by strong base the resultant solution pH is 7. (except for H2SO4(aq))
 If a weak monoprotic base is neutralized by strong acid the resultant solution has a pH <7.
 If a weak monoprotic acid is neutralized by strong base the resultant solution has a pH >7.
-
 ( Amphiprotic conjugates may be acidic -above HCO3 (aq)in the acid base data table or basic-
-
below HCO3 (aq)in the acid base data table)

In the second scenario a calculation using the total solution volume and Ka gives the solution pH. For
the third scenario a calculation using the total solution volume and the Kb of the conjugate gives the
solution pH. An example may help in understanding this procedure.

Example 1. What is the equivalence point pH when 50 mL of a 0.40 mol/L acetic acid solution is
neutralized completely (just) by 35 mL of aqueous sodium hydroxide?
Answer:
20 mmol of acetic acid (nHA= 50 mL x 0.40 mol/L) has been neutralized.

Since nA- = nHA , 20 mmol of acetate ion have been produced.

• The total solution volume at equivalence is 85 m L.

• [CH3COO-(aq) ] = 20 mmol = 20 mol/L = 0.24 mol/L

85 mL 85

Kw 1.0 x 10-14
• Since K b of A- = = = 5.6 x 10-10
K a of HA 1.8 x 10-5

Clearly CH3COO-(aq) + H2O(l) OH-(aq) + CH3COOH(aq)

Initially 0.24 mol/L 0 mol/L 0 mol/L

At Equilibrium 0.24 - x x x when amount x has reacted

to reach equilibrium.
[OH-(aq) ] [CH3COOH(aq) ]
=> Kb = Law of Mass Action
[CH3COO-(aq) ]

=> Kb = x2
(0.24 - x ) pH

9.06
Solving forx gives [OH-(aq) ] = 1.1 x 10-5 mol/L so
that pOH = 4.94. Subtracting this latter value from
14.00 gives a solution pH of 9.06 -see opposite.

Volume of base added

33
 Calculating Equivalence Point pH Worksheet
1. What is the first equivalence point pH when 50 mL of 0.10 mol/L phosphoric acid is neutralized
by 50 mL of aqueous sodium hydroxide ? (This is a Ka calculation) (4.25)

2. What is the second equivalence point pH when 50 mL of 0.10 mol/L phosphoric acid is
neutralized by 100 mL of aqueous sodium hydroxide ? (9.86)

3. What is the second equivalence point pH when 20 mL of 0.10 mol/L oxalic acid is neutralized by
40 mL of aqueous sodium hydroxide ? (8.40)

4. Predict the first equivalence point pH when 20 mL of 0.10 mol/L phosphoric acid is neutralized
by 20 mL of aqueous sodium hydroxide ? (A Ka calculation) (4.25)

5. Calculate an equivalence point pH when 30 mL of 0.20 mol/L methanoic acid is neutralized by

50 mL of aqueous potassium hydroxide ? (8.31)

6. Calculate an equivalence point pH when 14.5 mL of 0.10 mol/L hydrofluoric acid is neutralized
by 18.2 mL of aqueous potassium hydroxide ? (7.91)

34
pH Indicators

 Acid-base indicators are substances that can have one color in acidic solutions and another color
in basic solutions.
 The color change for each indicator is related to specific pH values and is used in titrations to
signal the equivalence point for the neutralization reaction.
 They are usually organic compounds, weak acids or weak bases that establish equilibrium
between their ionic and molecular forms in solution.
 The molecular form has one color while the ion has another color.

e.g. Phenolphthalein is a weak acid whose formula is abbreviated to HPh

HPh(aq) H+(aq) + Ph−(aq)

colorless pink

 When an acid is added, the Le Chatelier’s principle dictates that equilibrium shifts to the left
producing the colorless molecule.
 When a base is added, the equilibrium shifts to the right producing pink Ph−.
 Most indicators have a range of pH values where both forms exist and an intermediate color is
shown.
o This pH range where we see an intermediate colour is called the indicator endpoint, or
end point of the titration. At this point, both colors are present in equal amounts.
 We choose an indicator that has an endpoint that encompasses the expected equivalence point of
the acid and base with which we are titrating.

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 Questions on Indicators (But They Are Easy and FUN!!)

1. Hydrochloric acid, HCl(aq) was slowly added to a solution of sodium carbonate, Na2CO3(aq), that contained
the indicators bromocresol green and phenolphthalein. The reaction mechanism has two steps represented by
the net equations below. Each step has its own equivalence point.
a. H+(aq) + CO32-(aq) HCO3-(aq)
+ -
b. H (aq) + HCO3 (aq) H2CO3(aq)

c. Establish the colour for bromocresol green at pH = 9.5, pH = 7, pH = 4.2, pH = 2. What would be the
endpoint for bromocresol green?
d. Establish the colour for phenolphthalein at = 9.5, pH = 7, pH = 4.2, pH = 2. What would be the endpoint
for phenolphthalein?
2. Four tests were made on an unknown acid with four different colour indicators. Use the results in the table
below to establish the pH and [H3O+] of the acid.

Test Number Indicator Result

1 Orange IV Yellow
2 3. Methyl Orange Yellow
3 Litmus Red
4 Methyl Red Red

4. A solution of HCl(aq) which has a pH value of 4.2 has been divided into 4 test tubes. One of the colour
indicators listed below is added to each test tube. Establish the colour for each indicator.
a. Test tube 1 Orange IV c. Test tube 3 Bromocresol Green
b. Test tube 2 Methyl Red d. Test tube 4 Indigo Carmine
5. Four test tubes contain different concentrations of H3O+. Bromocresol green is added to each. What is the
colour for each test tube?
a. Test tube 1 [H3O+] = 1.0 x 10-1 mol/L
b. Test tube 2 [H3O+] = 1.0 x 10-3 mol/L
c. Test tube 3 [H3O+] = 1.0 x 10-5 mol/L
d. Test tube 4 [H3O+] = 1.0 x 10-7 mol/L

36
6. A solution of 1.65 x 10-4 mol/L HNO3(aq) is divided into three test tubes. One of the colour
indicators listed below is added to each sample. What colour would each test tube be?
a. Test tube 1 Methyl Red
b. Test tube 2 Phenolphthalein
c. Test tube 3 Methyl Orange
7. A solution of HI(aq) was divided into two beakers. A drop of methyl red was added to one
sample and the colour was yellow. A drop of bromothymol blue was added to the other
sample and again the colour was yellow. What is the concentration of the HI(aq) sample?
8. Colour indicators can be used to establish the [H3O+] for an acid. For slight variations in acid
concentrations, the colour change is gradual but distinct. Orange IV changes from red to
yellow in the pH range 1.4 to 2.8. In the laboratory, this colour indicator was added to a
solution of 0.10 mol/L HCOOH(aq), methanoic acid, at 25 °C, and the colour was compared
to several solutions of HCl(aq) with concentrations that increased consecutively from 1.0 x
10-3 mol/L. The same colour indicator, Orange IV, had been added to each of the HCl(aq)
samples. The reddish yellow in the 0.10 mol/L HCOOH(aq) solution matched a
corresponding colour in the HCl(aq) whose concentration was 4.0 x 10-3 mol/L. Use this
experiment to establish the Ka value for 0.10 mol/L HCOOH(aq) at 25 °C.
9. Estimate the pH of the following samples:
a. Separate samples of a solution will cause methyl violet to be blue, cresol red to be
yellow, orange IV to be orange and bromocresol green to be yellow.
b. Separate samples of a solution cause thymol blue to be blue, alizarin yellow to be yellow
and bromothymol blue to be blue.
c. Separate samples of a solution cause indigo carmine to be blue, phenol red to be orange,
bromothymol blue to be green and phenolphthalein to be colourless.
10. For the colour indicator methyl orange, the pH range is 3.2 to 4.4. Use this to roughly
establish the Ka value for methyl orange at 25 °C.

37
 Acid Base Indicator Worksheet:
For each of the following:
 Write a Bronsted-Lowry acid-base equation.
 Predict what color should be observed based upon the extent of reaction or what is
favored reactants or products.

1. A methyl orange indicator solution (Mo-(aq)) is put into a hydrochloric acid solution.

2. A bromothymol blue indicator solution (Bb-(aq)) is mixed with a sodium hydrogen

carbonate solution.

3. A phenolphthalein indicator solution (HPh(aq)) is added to a sodium hydroxide

solution.

4. According to the table of acid-base indicators in the data book, what is the color of
each of the following indicators in the solutions of given pH?

a. phenolphthalein in a solution with a pH of 11.70 __________________

b. bromothymol blue in a solution with a pH of 2.80 __________________

c. litmus in a solution with a pH of 8.20 __________________

d. methyl orange in a solution with a pH of 3.90 __________________

5. Complete the analysis for each of the following diagnostic tests. If [the specified
indicator] is added to a solution, and the colour of the solution turns [the given color],
then the solution pH is ________.

a. methyl red red pH is: __________

b. alizarin yellow red pH is: __________

c. bromocresol green blue pH is: __________

d. bromothymol blue green pH is: __________

6. Separate samples of an unknown solution turned both methyl orange and

bromothymol blue to yellow, and turned bromocresol green to blue. Estimate the pH
of the unknown solution

I. methyl orange yellow pH is: __________

II. bromothymol blue yellow pH is: __________

38
 III. bromocresol green blue pH is: __________

The estimated pH of the unknown solution is: ____________

Calculate the approximate hydronium ion concentration of the unknown

solution

39
 Indicator Equilibrium Worksheet

1. Draw annotated line diagrams for the following indicators:

a. thymol blue

b. bromothymol blue

c. thymolphthalein

d. methyl orange

2. What are the colours of the following indicators at the given pH?

a. methyl violet at pH 2.0 b. cresol red at pH 4.0 c. thymol blue at

pH 9.0

d. methyl orange at 8.0 e. phenolphthalein at pH 7.0 f. phenol red at pH

7.0

g. bromocresol green at 8.0 h. alizarin yellow at pH 14.0 i. indigo carmine

at pH 9.0

3. Estimate the pH and [H+(aq)] of the following samples (use a number line in each
case)?
a. Separate samples of a solution cause methyl violet to be blue, cresol red to be
yellow, orange (IV) to be orange and bromocresol green to be yellow! (1.8 -
2.8; 2 mmol/L - 0.02 mol/L)

b. Separate samples of a solution cause thymol blue to be blue, alizarin yellow to be

yellow and bromothymol blue to blue! (9.6 - 10.1; 3x10-10 to
8x10-11 mol/L)

c. Separate samples of a solution cause indigo carmine to be blue, phenol red to be

orange, bromothymol blue to be green and phenolphthalein to be colourless!
(6.6-7.6; 3x10-8 to
3x10-7 mol/L)

40
Buffers

Buffers absorb additions of acids or bases, but have only a slight change in pH.
Many chemical and biological systems operate at a constant (or stable) pH.
In our blood, the pH stays around 7.4 even though there are many reactions going on that
release acids and bases. Buffer systems react as Bronsted-Lowry acids and bases.

In blood, this conjugate acid-base pair undergoes reactions to help control the pH. When
excess hydronium ions, H3O+(aq), enter the blood, the hydrogen carbonate ion undergoes
the following reaction to reduce the [H3O+(aq)]

HCO3 -(aq) + H3O+(aq) H2CO3(aq) + H2O(l)

In this way, excess H3O+(aq) cannot build up and drastically affect the pH.

Whenever excess hydroxide ions, OH-(aq), form in the blood they have a strong affinity
(attraction) for H+(aq). Carbonic acid provides a source of protons (hydrogen) for the OH-
(aq), and the following reaction occurs.
H2CO3(aq) + OH-(aq) HCO3-(aq) + H2O(l)

Just as your body uses a weak acid and conjugate base pair for buffering, chemists use
this same concept to make buffers in the lab.

Weak acids or weak bases (and their conjugates bases or acids) are used as buffers.
They are found in similar concentrations.

A Calculation Example to See the Effect Buffers Have on pH

Find the [H3O+] and the pH for a 1.00 L aqueous solution containing 0.050 mol of acetic
acid and 0.050 mol of sodium acetate. Remember: Ka = 1.8 x 10-5
CH3COOH(aq) + H2O(l) H3O+(aq) + CH3COO-(aq)

Initial [ ] 0.050 0 0.050

Change [ ] -x +x +x
Equilibrium [ ] 0.050-x x 0.050 + x

[ H 3 O  ][CH 3 COO  ]
Ka 
[CH 3 COOH ]
[ x][0.050  x]
1.8 x105 
[0.050  x]
X is insignificant compared to the concentrations of 0.050 mol/L.
[ x][0.050]
1.8 x105 
[0.050]
5
x  1.8 x10 mol / L

41
pH = 4.7 Acetic acid/Acetate ion is a buffer for the pH region of 4.7

Whenever the ratio of your buffer is 1, then the [H3O+] = Ka and the pH is the pKa
That is the negative log of the Ka!!!

Let’s look at how a buffer works:

CH3COOH(aq) + H2O(l) H3O+(aq) + CH3COO-(aq)

 If we add acid, the equilibrium shifts left, and consumes H3O+ and forms acetic
acid.
 If we add base the equilibrium shifts right and forms H3O+ ion and acetate ion.

Add 0.010 mol/L HCl(aq) (this is a very large addition in a buffer system).

So now there is an extra 0.010 mol/L H3O+ in solution. So the system will try to
consume this acid b/c there is a base (CH3COO-) present.
[CH3COOH] goes from 0.050 mol/L to 0.060 mol/L
[CH3COO-] goes from 0.050 mol/L to 0.040 mol/L
Temperature stays the same, so the Ka is the same (1.8 x 10-5)
[CH 3COOH ]
[ H 3O  ]  K a
[CH 3COO  ]
[0.060]
[ H 3O  ]  [1.8 x105 ]
[0.040]
+ -5
[H3O ] = 2.7 x 10 mol/L pH = 4.6

So we added a huge amount of acid, and the pH only changed by 0.1 units.

If we added 0.010 mol/L H3O+(aq) to water, the pH would change by 2!!

 Buffers work best if the strength of the acid and base are equal.
 Buffers also work best when the concentration of the acid and base are equal.
 Once the weak acid or base are consumed (called the buffering capacity), then
there will be a rapid change in pH.

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Working with Buffers Visually Using Titration Curves

The buffering regions can be seen as the boxed areas in the following graphs. It is those
regions where the solution pH does not change significantly despite the addition of strong
acid (or strong base) that the solution is said to be buffered. Buffering regions are noted
before and between the equivalence points of weak acid strong base or weak base strong
acid pH titration curves.

pH pH

- +
Volume of OH ( aq)
Added Volume of H O
3 ( aq)
Added

pH pH

- +
Volume of OH ( aq)
Added Volume of H 3
O ( aq)
Added

The areas after the equivalence point (final equivalence point for polyprotic and
polybasic substances) are not buffering regions.
 After the equivalence point, depending on the titration, strong acid (or strong
base) in excess is being added to a solution in which the pH is dominated by the
presence of the same strong acid (or strong base). For example; if you add a
small amount of strong acid to a solution of a strong acid there’s going to be very
little change in pH! Please note: buffering regions are not seen in the titration of
strong acids and strong bases.

Remember:
 A buffer is comprised of two components - a weak base and a weak acid.

43
 A buffer is usually a weak conjugate acid base pair.
For example:
- - 2- -
CH3COOH(aq)/CH3COO (aq); H2PO4 (aq)/HPO4 (aq); H2CO3(aq)/HCO3 (aq); generically
HA(aq)/A-(aq).
+ -
 A buffer resists changes in pH when small amounts of H3O (aq) or OH (aq) are
added to them.
 Diluting a buffer system, within reason, has no effect on the system pH.

44
Questions that Deal with Buffers (Still Need those ICE Charts)

1. A buffer solution consists of a 1.00 L aqueous solution containing 0.0080 mol of

benzoic acid, and 0.0080 mol of sodium benzoate. Establish the pH region for this
buffer solution at 25 °C.
(Note: Ka = 6.3 x 10-5 for C6H5COOH(aq))

2. Suggest a possible buffer solution that could function for the pH region of 6.36.

3. For the hydrochloric acid solution, 1.0 x 10-6 mol/L HCl(aq), establish
a. [H3O+] and pH
b. [OH-] and pOH

4. For nitric acid, 0.0035 mol/L HNO3(aq) at 25 °C, establish

a. [H3O+] and pH
b. [OH-] and pOH

5. For 0.025 mol/L HNO2(aq), nitrous acid, the pH reading is 2.4. Use the pH to
establish the Ka value for the acid at flask temperature.

45