Chapter 4:

Chemical Reactions in Aqueous Solutions

Solute Concentrations, Molarity
o Solution: homogeneous mixture of two or more substances.

o Solute: the substance being dissolved.

o Solvent: the substance doing the dissolving.

o Concentration of a solution: the quantity of
a solute in a given quantity of solution (or
solvent).
n A concentrated solution contains a relatively
large amount of solute vs. the solvent (or
solution).
n A dilute solution contains a relatively small
concentration of solute vs. the solvent (or
solution).
n “Concentrated” and “dilute” aren’t very
quantitative .
Molar Concentration
Molarity (M), or molar concentration, is the amount
of solute, in moles, per liter of solution:
Formula:
o Molarity = moles of solute
liters of solution

o A solution that is 0.35 M sucrose contains 0.35

moles of sucrose in each liter of solution.
o Keep in mind that molarity signifies moles of
solute per liter of solution, not liters of solvent.
 Volumetric Flasks

Weigh 0.01000
Dissolve in water. How much Add more water
mol (1.580 g)
water? Doesn’t matter, as long as to reach the
KMnO4.
we don’t go over a liter. 1.000 liter mark.
Calculating Molarity
a. Given moles of solute and volume of
solution
Example 4.1 What is the molarity of a
solution prepared by dissolving 5.0 mol of
NaCl in enough water to make 2 L of
solution?
Sample Problem
b. Given mass of solute and volume of
solution
Example 4.2 What is the molarity of a solution
prepared by dissolving 50.75 g of AgNO3 in
enough water to make 1500 mL of solution?
Sample Problem
c. Calculating Mass from Molarity and Volume
Example 4.3 How many grams of sodium
carbonate are needed to prepare 0.250 L of
a 0.300 M solution?
Arrhenius’s Theory of Electrolytic Dissociation

o Why do some solutions

conduct electricity?
o Arrhenius’s theory:
n Certain substances dissociate
into cations and anions when
dissolved in water.
n These ions allow electricity to
flow.
Review: Ch 2
Ionic
Compounds

Electrolytes
dissociate
to produce
ions.
The more the electrolyte dissociates,
the more ions it produces.
 Types of Electrolytes
o A strong electrolyte
dissociates completely.
n A strong electrolyte is
present in solution almost
exclusively as ions.
n Strong electrolyte solutions
are good conductors.
n Ex: most ionic compounds
 Types of Electrolytes
o A weak electrolyte
dissociates partially.
n Weak electrolyte
solutions are poor
conductors.
n Different weak
electrolytes dissociate to
different extents.
n Ex: weak acids and bases
 Nonelectrolytes
o A nonelectrolyte does not
dissociate.
n A nonelectrolyte is
present in solution almost
exclusively as molecules.
n Nonelectrolyte solutions
do not conduct electricity.
n Ex: sugar, ethanol
Is it a strong electrolyte, a weak
electrolyte, or a nonelectrolyte?
o Strong electrolytes include:
How do we tell
n Strong acids & Strong bases whether an acid
(or base) is weak?
n Most water-soluble ionic compounds Memorize the
strong
o Weak electrolytes include: acids/bases!

n Weak acids and weak bases

n A few ionic compounds
o Nonelectrolytes include:
n Most molecular compounds
n Most organic compounds (most are molecular)
Ion Concentrations in Solution
A. Dissolution equations
-For a strong electrolyte
o write cations and anions as individual particles

NaCl(aq) à
MgSO4à
Na2SO4à
Ion Concentrations in Solution
A. Dissolution equations
-For a strong electrolyte
o write cations and anions as individual particles

NaCl(aq) à Na+ + Cl-

MgSO4à Mg+2 + SO42-
Na2SO4à 2Na+ + SO42-
Calculating Ion Concentrations in Solution

Multiply molarity (M) x COEFFICIENT

of each ion to find the ion concentration!

o EXAMPLE:
Na2SO4à 2Na+ + SO42-
.010 M 0.020 M 0.010 M
Example
Calculate the concentrations of all the ions present in
the following solutions:
a. 0.75M solution of NaCl

b. 1.5M solution of AlF3

c. 0.5M solution of Al2(CO3)3

Example

a. 0.75M solution of NaCl

NaCl(s) à Na+ + Cl-

b. 1.5M solution of AlF3

AlF3à Al +3 + 3F-

c. 0.5M solution of Al2(CO3)3

Al2(CO3) 3 à 2Al +3 + 3CO3 -2
 Chemical Reactions in Water
We will look at
DOUBLE REPLACEMENT REACTIONS
Pb(NO3) 2(aq) + 2 KI(aq) ----> PbI2(s) + 2 KNO3 (aq)

AX + BY AY + BX

The cations change places.

 Definition
o Precipitate: insoluble product (solid formed in
a DR reaction)
o Example: PbI2 is a precipitate:
Pb(NO3) 2(aq) + 2 KI(aq) ---> PbI2(s) + 2 KNO3 (aq)
Precipitation Reactions
The “driving force” is the formation of an
insoluble compound — a precipitate.

Pb(NO3)2 (aq) + 2 KI (aq)

-----> 2 KNO3(aq) + PbI2(s)
Solubility Rules

See handout!!
Solubility Rules
Are the following compounds soluble or
insoluble?

NaNO3
Ba(OH)2
NaSO4
CaSO4
Use of Solubility Tables—See
Reference Booklet
s = soluble -- dissolves in water, is (aq)

i = ss = insoluble or slightly soluble--forms a

precipitate, is (s)
Water Solubility of Ionic Compounds
Common minerals are often formed with anions
that lead to insolubility:
sulfide fluoride carbonate oxide

Iron pyrite, a sulfide

Orpiment,
arsenic sulfide
Azurite, a copper
carbonate
 Net Ionic Equations

Pb(NO3)2 (aq) + 2 KI (aq)

-----> 2 KNO3(aq) + PbI2(s)

Net ionic equation (See handout!)

Pb2+(aq) + 2 I-(aq) ---> PbI2(s)
Sample Problem
Predict whether or not the following pairs of
reactants will form precipitates. Then write
the double replacement reaction, the full
ionic equation, and the net ionic equation.
o a. CuCl2 and (NH4)2SO4
o b. Ba(NO3)2 and Na2CO3
o c. MgCl2 and AgNO3
Acids and
Bases
 Properties of Acids
Taste sour
React with indicators: turn blue litmus red turn
phenolphthalein colorless
React with certain metals to form H2

Corrosive to metals and skin (strong acids)

Neutralize bases
to form water and
salts
 Properties of Bases
Taste bitter
Feel slippery
React with indicators:
turn red litmus blue
turn phenolphthalein pink
Corrosive to skin (strong bases)
Neutralize acids to form
water and salts
Arrhenius Definitions of Acids and Bases

o Acids produce H+ in water solution

o Bases produce OH- in water solution

Examples: HCl à H+ + Cl-

NaOH à Na+ + OH-
Arrhenius Definitions:
Acids produce H+ in water solution
Bases produce OH- in water solution
Arrhenius definitions are limited!!!
o Not all bases contain OH-
o H+ does not exist by itself in
aqueous systems
Definition: Hydronium Ion
In aqueous solution, H+ does NOT exist!
Note: In problems, [H+] = [H3O+]
H+ + H2O à H3 O+

(hydronium ion)
STRONG ACIDS = STRONG ELECTROLYTES
An acid ----> H+ in water

SIX strong acids are

HCl hydrochloric
HBr hydrobromic
HI hydroiodic
H2SO4 sulfuric HNO3
HClO4 perchloric
HNO3 nitric
Strong Acids/Bases
Strong Acids: THERE ARE ONLY SIX!

HCl, HBr, HI, HNO3, HClO4, H2SO4

Strong acids are 100% ionized in solution! (Use

single arrow; no equilibrium established)

HNO3 à H+ + NO3-
Reactions of Acids and Bases:
Strong and Weak Acids
o Strong acids are strong electrolytes;
completely ionized in water.
In water: HCl(aq) → H+(aq) + Cl–(aq)

No HCl in
solution, only H+
and Cl– ions.
 Strong Bases
Strong Bases: Group I metals + OH -; some Group II
metals + OH –

Some examples: NaOH, LiOH, Sr(OH)2

Strong bases are 100% ionized in solution! (Use single

arrow; no equilibrium established)

Sr(OH)2 à Sr2+ + 2 OH -
Common Strong Acids
and Strong Bases- memorize!!!

MEMORIZE the strong acids and know

how to recognize the strong bases!
 Weak Acids/Bases

o Weak acids are not fully ionized in water.

o Weak organic acids contain the –COOH group
o One of the best known is acetic acid =
CH3COOH
 Weak Acids/Bases
o Weak bases are not fully ionized in water.(use
double arrow; equilibrium established)
o One of the best known weak bases is ammonia
o NH3(aq) + H2O(liq) Û NH4+(aq) + OH-(aq)
ACID-BASE THEORIES
oThe most general theory for common
aqueous acids and bases is the
BRØNSTED - LOWRY theory
DEFINITIONS:
o ACIDS DONATE H+ IONS
o BASES ACCEPT H+ IONS
 ACID-BASE THEORIES
The Brønsted definition means NH3 is a
BASE in water — and water is itself an
ACID NH + H O NH + + OH-
3 2 4
Base Acid Acid Base
BRØNSTED - LOWRY theory:

ACIDS DONATE H+ IONS

BASES ACCEPT H+ IONS
Conjugate Pairs

•NH3 / NH4+ is a conjugate pair — related by

the gain or loss of H+
•Every acid has a conjugate base, formed
when H+ is removed from the acid.
•Every base has a conjugate acid, formed when
H+ is added to the base.
Conjugate Pairs

Generalized equation:
HB (aq) + A (aq) Û HA (aq) + B- (aq)
Conjugate Pairs
Sample Problem
Example Write the Bronsted Lowry equations
for the weak acid HNO2 and the weak base
NH3, identifying the conjugate acid-base pairs
in each equilibrium.
Sample Problem
Example Write the Bronsted Lowry equations
for the weak acid HCO3 - and the weak base
NH3, identifying the conjugate acid-base pairs
in each equilibrium.
Amphiprotic or Amphoteric
Substances
Some substances can function as both an ACID OR
a BASE, depending on what they are reacted
with. (can donate OR accept H+)
They are called amphiprotic or amphoteric

E.g.,
H2O + H2O Û H3O+ + OH-
Water dissociation constant, or the ion
product constant of water
OH-

H3O+

For any sample of water molecules:

H2O (liq) + H2O (liq) Û H3O+ (aq) + OH- (aq)
Kw = [H3O+] [OH-] = 1.00 x 10-14
(at 25 oC)
Neutral, Acid and Basic Solution
Neutral solution:
[H+] = [OH-] = 1.0 x 10-7 M

Acid solution:
[H+] > [OH-]; [H+] > 1.0 x 10-7 M

Basic solution:
[H+] < [OH-]; [OH-] > 1.0 x 10-7 M
Sample Problem
Example 15.4 A sample of tap water has a [H+]
= 2.8 x 10-6 M. What is the [OH-]?
 The pH Scale
A common way to express acidity and basicity
is with pH (the “power of hydrogen”)
pH = - log [H3O+]
In a neutral solution,
[H3O+] = [OH-] = 1.00 x 10-7 at 25 oC
pH = -log (1.00 x 10-7) = - (-7) = 7
The pH Scale: pH = - log [H3O+]
 Size of pH

Basic solution pH > 7

Neutral pH = 7
Acidic solution pH < 7

Big number = Basic

pH of Common Substances
pOH Definition
pOH = - log [OH-]

pH + pOH = 14.0
The pH Scale
Sample Problem
Example Calculate the pH, pOH and [OH-] of
an acid solution whose [H+] is 1.8 x 10-4 M.

Strategy:
1. Calculate pH using formula and [H+].
2. Calculate pOH from pH.
3. Can calculate [OH-] from pOH or by using
Kw and [H+].
pH to [H+] Calculations

If the pH of Coke is 3.12, it is acidic.

Because pH = - log [H3O+] then
log [H3O+] = - pH
Take antilog and get
[H3O+] = 10-pH
[H3O+] = 10-3.12 =
7.6 x 10-4 M
Strong Acids
Strong Acids dissociate completely in aqueous
solution:

E.g. HCl à H+ + Cl-

2.0 M 2.0 M 2.0 M

In a strong acid, [H+] can be calculated from the

molarity of the acid.
Sample Problem
Example Calculate the [H+], pH, and [OH-] of a 0.15M
solution of the strong acid, HNO3.

Strategy:
1. Write the disassociation equation and calculate
[H+].
2. Calculate pH from [H+].
3. Use Kw to find [OH-].
Strong Bases
Strong Bases dissociate completely in aqueous
solution:

E.g. Sr(OH)2 à Sr+2 + 2OH-

0.5 M 0.5 M 1.0 M

In a strong base, [OH-] can be calculated from

the molarity of the base.
 Sample Problem
Example State the pH, pOH, [H+], and [OH-] of a solution
made by dissolving 0.0500 mol of Ba(OH)2 - a strong
base - in 5.00 L of water.
Strategy:
1. Calculate molarity of Ba(OH)2.
2. Write disassociation equation; calculate molarity of OH-.

3. Calculate pOH from [OH-].

4. Calculate pH from pOH.

5. Calculate [OH-] from Kw.

Neutralization Reactions and
Titration for Strong Acids and Bases

1. Definitions
n titration
n titrant
n indicator
n endpoint
n equivalence point
Acid-Base Indicators and Acid-Base
Titrations for Strong Acids and Bases

1. Neutralization reactions
n Neutralization is the (usually complete)
reaction of an ACID + BASE
n The products of this neutralization are a
“salt” (ionic compound) + water
n It is a double replacement reaction.
n Example: HCl + NaOH à H2O + NaCl
Definitions
A titration is a carefully controlled
neutralization reaction.

A buret is used in a titration.

Why? To determine the concentration of an

unknown acid or base.
 Definitions
The titrant is the substance of known concentration
used to determine the unknown concentration of
the other substance.

An indicator--substance that changes color at a

certain pH—is added to tell us when the
neutralization is complete.
Example: Phenolphthalein undergoes a color change
between pH 8 and 10
clear in acid
Light pink in neutral
Dark pink in base
Definitions
The equivalence point, is the point in the
titration where the neutralization is
complete:
[H3O+] = [OH-]
The endpoint is the point where the
indicator changes color.
If indicator chosen correctly, two points
are identical!
Acid–Base Titration
Strong acid and base titration
Chemical reaction:

ACID + BASE à SALT + WATER

HCl + NaOH à NaCl + H2O

A double replacement reaction!
Acid–Base Reactions:
Example
HCl + NaOH à H2O + NaCl
o In the reaction above, the HCl, NaOH, and NaCl
all are strong electrolytes and dissociate
completely.
o The actual reaction occurs between ions.

H+ + Cl– + Na+ + OH– à H2O + Na+ + Cl–

H+ + OH– à H2O Na+ and Cl–
arereaction.
A net ionic equation shows the species actually involved in the spectator
ions.
Strong acid and base titration
Short-cut equation:
(# H+)MAVA = (# OH-) MBVB
Where #H+ and #OH- are obtained from
the formula
Volumes can be in mL or L, but must
be same units on both sides of
equation!
Procedure for Titration

At the equivalence point (end point):

Total mols of H+ Total mols of OH-

from the acid = from the base

*Remember: (conc)(vol in L) =
moles
Sample Problem
Example How many milliliters of 0.0195 M HCl
are required to titrate 25.00 mL of 0.0365 M
KOH?
Sample Problem
Example How many milliliters of 0.0108 M
Ba(OH)2 are required to titrate 25.00 mL of
0.0213 M HCl?
 Reactions Involving
Oxidation and Reduction
o Oxidation: Loss of electrons
o Reduction: Gain of electrons
o Both oxidation and reduction must occur
simultaneously.
n A species that loses electrons must lose them to
something else (something that gains them).
n A species that gains electrons must gain them from
something else (something that loses them).
o Historical: “oxidation” used to mean “combines with
oxygen”; the modern definition is much more general.
Oxidation Numbers
o An oxidation number is the charge on an ion, or a
hypothetical charge assigned to an atom in a molecule
or polyatomic ion.
o Examples: in NaCl, the oxidation number of Na is +1,
that of Cl is –1 (the actual charge).
o In CO2 (a molecular compound, no ions) the oxidation
number of oxygen is –2, because oxygen as an ion
would be expected to have a 2– charge.
o The carbon in CO2 has an oxidation number of +4
(Why?)
 Identifying Oxidation–Reduction
Reactions
In a redox reaction, the oxidation number of a
species changes during the reaction.
n Oxidation occurs when the oxidation number
increases (species loses electrons).
n Reduction occurs when the oxidation number
decreases (species gains electrons).
n If any species is oxidized or reduced in a reaction,
that reaction is a redox reaction.
n The two processes occur at the same time
A Redox Reaction: Mg + Cu2+ à Mg2+ + Cu
Electrons are transferred from … the products are Cu
Mg metal to Cu2+ ions and … metal and Mg2+ ions.
Oxidizing and Reducing Agents
o An oxidizing agent causes another substance to be
oxidized.
o The oxidizing agent is reduced.
o A reducing agent causes another substance to be
reduced.
o The reducing agent is oxidized.

Mg + Cu2+ à Mg2+ + Cu

What is the oxidizing agent? What is the reducing

agent?
Examples of redox reactions:
o Displacement of an element by another element
o Combustion
o Extraction of metal from ores
o Metabolic reactions in living organisms
o Manufacturing chemicals
o Mg(s) + Ca 2+(aq) à Mg 2+ (aq) + Ca(s)
n Ox: Mg(s) à Mg 2+ (aq) +2e-
n Red: Cu 2+ (aq) + 2e- à Cu(s)
 Oxidation–Reduction Equations

o Redox equations must be balanced according to both

mass and electric charge.
o For now, our main goals will be to:
n Identify oxidation–reduction reactions.
n Balance certain simple redox equations by inspection.
n Recognize, in all cases, whether a redox equation is
properly balanced.
 Rules for Assigning Oxidation Numbers
Neutral Species
For an isolated atom, a molecule, or a formula unit—the
oxidation numbers is 0. ex: Cl2, Fe
Monatomic Ions (Groups 1, 2, 17)
Group 1 elements all have an oxidation number of +1
Group 2 elements all have an oxidation number of +2.
Fluorine always has an oxidation number or -1.
Oxygen
In most compounds, oxygen has an oxidation number of –2.
Sum of oxidation numbers for
neutral and charged species:
Hydrogen è +1 when bonded to a nonmetal, -1 when
bonded to a metal
o The sum of the oxidation numbers of all atoms (or
ions) in a neutral compound = 0.
o The sum of the oxidation numbers of all atoms in a
polyatomic ion = charge on the polyatomic ion.
ex: CaCl2
Example: Assign oxidation numbers to the elements in
the following species:
CaC2O4 Cr2O72-

N2O N2O4

ClO1- ClO41-
6. Identifying redox reactions
o Look for changes in oxidation numbers

Al (s) + Fe2O3(s) à 2 Fe (l) + Al2O3

0 3+ 2- 0 3+ 2-
 Example 4.7 Identify the element reduced, the element
oxidized, the reducing agent and the oxidizing agent:

A) Fe2+(aq) + Cr2O72-(aq) + H+(aq) à

Fe3+(aq) + Cr3+(aq) + H2O(l)

B) 3 Cl2 (g) + 2 Cr(OH)3 (aq) + 10 OH- à

2CrO4-(aq) + 6Cl-(aq) + 8H2O(l)

Applications of Oxidation
and Reduction
o Analytical Chemistry
o KMnO4 is the most commonly used oxidizing
agent in chemical laboratories.

o 5Fe2+(aq) + MnO4-(aq) + 8H+(aq) à

5Fe3+(aq)+ Mn2+ (aq) + 4H2O (l)
Oxidation and Reduction in Organic Chem.
After a while the
Potassium Initially the alcohol is oxidized
dichromate solution turns the to a ketone, and the
orange of Cr2O72– Cr2O72– is reduced
to Cr3+

Ethanol
Applications of Oxidation
and Reduction
o In industry: to produce iron, steel, other
metals, and consumer goods.

o In foods and nutrition: redox reactions “burn”

the foods we eat; antioxidants react with
undesirable free radicals.
Applications of Oxidation
and Reduction
Everyday life: to clean (bleach) our clothes, sanitize
our swimming pools (“chlorine”), and to whiten
teeth (peroxide).