Chapter 4

Types of Chemical Reactions

and Solution Stoichiometry

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Chapter 4
Types of Chemical Reactions and Solution
Stoichiometry

:
N1127:
:07-3121101#2681
E-mail: [email protected]

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Chapter 4
Types of Chemical Reactions and Solution
Stoichiometry
4.1 Water, the Common Solvent
4.2 The Nature of Aqueous Solutions: Strong and Weak
Electrolytes
4.3 The Composition of Solutions
4.4 Types of Chemical Reactions
4.5 Precipitation Reactions
4.6 Describing Reactions in Solution
4.7 Stoichiometry of Precipitation Reactions
4.8 Acid–Base Reactions
4.9 Oxidation–Reduction Reactions
4.10 Balancing Oxidation–Reduction Equations
4.11
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Section 4.1
Water, the Common Solvent

 Aqueous Solutions: Water is the dissolving

medium, or solvent
 Liquid water is the collections of water
molecules.

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Section 4.1
Water, the Common Solvent

 One of the most important

substances on Earth.
 Can dissolve many different
substances.
 A polar molecule because
of its unequal charge
distribution.
Hydration occurs when salts
dissolve in water.

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Section 4.1
Water, the Common Solvent

Dissolution of a solid in a liquid

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Section 4.1
Water, the Common Solvent

 Ionic compounds (salts) dissolve in water, they

break up into the individual cations and anions.
 E. g. NH4NO3(s)  NH4+(aq) + NO3-(aq)
 The solubility of ionic compounds in water
varies greatly. They depend on the relative
attractions of the ions for each other and the
attractions of the ions for water molecules.
 Water can dissolve nonionic substances too.
E.g. ethanol Why? Fig. 4-3)

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Section 4.1
Water, the Common Solvent
Figure 4.3: (a) The ethanol molecule contains a polar O—H bond
similar to those in the water molecule. (b) The polar water
molecule interacts strongly with the polar O—H bond in ethanol.
This is a case of "like dissolving like."

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Section 4.2
The Nature of Aqueous Solutions:
Strong and Weak Electrolytes
Nature of Aqueous Solutions
 Solute – substance being dissolved.
 changes phase (if different from the solvent)
 is present in lesser amount (if the same phase as the
solvent)
 Solvent – liquid water.
 Electrolyte – substance that when dissolved in water
produces a solution that can conduct electricity.

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Section 4.2
The Nature of Aqueous Solutions:
Strong and Weak Electrolytes

Electrical conductivity: (the ability

to conduct an electric current)

Svante Arrhenius
Zumdahl, Zumdahl,
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Section 4.2
The Nature of Aqueous Solutions:
Strong and Weak Electrolytes
Electrolytes (14)
 Strong Electrolytes – conduct current very efficiently
(bulb shines brightly). Completely ionized in water.
 Weak Electrolytes – conduct only a small current (bulb
glows dimly). A small degree of ionization in water.
 Nonelectrolytes – no current flows (bulb remains unlit).
Dissolves but does not produce any ions.

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Section 4.2
The Nature of Aqueous Solutions:
Strong and Weak Electrolytes
Electrolyte behavior

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Section 4.2
The Nature of Aqueous Solutions:
Strong and Weak Electrolytes
Figure 4.4 - Electrical Conductivity of Aqueous Solutions

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Section 4.2
The Nature of Aqueous Solutions:
Strong and Weak Electrolytes
Strong Electrolyte

 (1) soluble salts Fig. 4-2 Fig. 4-5

 (2) strong acid, from Latin word acidus,
meaning “sour”
 (3) strong bases: contain OH-, containing
soluble ionic compounds, bitter, slippery
e.g. NaOH, KOH, Fig. 4-7).

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Section 4.2
The Nature of Aqueous Solutions:
Strong and Weak Electrolytes
Figure 4.5: When solid NaCl dissolves, the Na+ and Cl-
ions are randomly dispersed in the water.

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Section 4.2
The Nature of Aqueous Solutions:
Strong and Weak Electrolytes
Acids

Strong acids - acidus (sour), dissociate

completely to produce H+ in solution
Hydrochloric, nitric and sulfuric acid

Weak acids - dissociate to a slight extent to

give H+ in solution
acetic and formic acid
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Section 4.2
The Nature of Aqueous Solutions:
Strong and Weak Electrolytes

 Arrenius proposed that an acid is a substance that

produces H+ ions (protons) when it is dissolved in water.
 H2SO4, HNO3 HCl are aqueous solutions and the chemical
formulas should be written as H2SO4(aq), HNO3(aq), HCl(aq)
 A strong acid is one that completely dissociates into its
ions. Fig. 4-6
 Sulfuric acid is a special case. The formula H2SO4
indicates this acid can produce two H+ ions per molecule
when dissolved in water. However only the first H+ ion is
completely dissociated.

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Section 4.2
The Nature of Aqueous Solutions:
Strong and Weak Electrolytes

Figure 4.6:
HCl(aq) is
completely
ionized.

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Section 4.2
The Nature of Aqueous Solutions:
Strong and Weak Electrolytes

Figure 4.8: Acetic acid

(HC2H3O2) exists in
water mostly as
undissociated
molecules. Only a
small percentage of
the molecules are
ionized.
HC2H3O2 + H2O
H+(aq) + C2H3O2-(aq)
1% ionization (0.1M)
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Section 4.2
The Nature of Aqueous Solutions:
Strong and Weak Electrolytes
Bases

Strong bases - bitter, slippery, react

completely with water to give OH ions.
sodium hydroxide

Weak bases - react only slightly with water to

give OH ions.
ammonia

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Section 4.2
The Nature of Aqueous Solutions:
Strong and Weak Electrolytes

Figure 4.7: An
aqueous
solution of
sodium
hydroxide.

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Section 4.2
The Nature of Aqueous Solutions:
Strong and Weak Electrolytes

Figure 4.9: The

reaction of NH3 in
water.
NH3(aq) + H2O(l) 
NH4+(aq) + OH-(aq)
0.1M NH3 ionization
1%

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Section 4.3
The Composition of Solutions

Chemical Reactions of Solutions

 We must know(Stoichiometric Calculation):

 The nature of the reaction.
 The amounts of chemicals present in the solutions.

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Section 4.3
The Composition of Solutions

Molarity
 Molarity (M) = moles of solute per volume of solution in
liters:
moles of solute
M = Molarity =
liters of solution

6 moles of HCl
3 M HCl =
2 liters of solution

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Section 4.3
The Composition of Solutions

EXERCISE!

A 500.0-g sample of potassium phosphate is dissolved

in enough water to make 1.50 L of solution. What is
the molarity of the solution?

1.57 M

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Section 4.3
The Composition of Solutions

Concentration of Ions
 For a 0.25 M CaCl2 solution:
CaCl2 2+ + 2Cl–

 Ca2+: 1 × 0.25 M = 0.25 M Ca2+

 Cl–: 2 × 0.25 M = 0.50 M Cl–.

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Section 4.3
The Composition of Solutions

CONCEPT CHECK!

Which of the following solutions contains

the greatest number of ions?

a) 400.0 mL of 0.10 M NaCl.

b) 300.0 mL of 0.10 M CaCl2.
c) 200.0 mL of 0.10 M FeCl3.
d) 800.0 mL of 0.10 M sucrose.

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Section 4.3
The Composition of Solutions

Let’s Think About It

 Where are we going?
 To find the solution that contains the greatest
number of moles of ions.
 How do we get there?
 Draw molecular level pictures showing each solution.
Think about relative numbers of ions.
 How many moles of each ion are in each solution?

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Section 4.3
The Composition of Solutions

Notice
 The solution with the greatest number of ions is not
necessarily the one in which:
 the volume of the solution is the largest.
 the formula unit has the greatest number of ions.

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Section 4.3
The Composition of Solutions
Concentration
 The traditional description of solution’s
concentration (in terms of the form of
solute before it dissolves) may not
accurately reflect the true composition of
the solution. E.g. 0.1 M NaCl contains 0.1
mol/L Na+, 0.1 mol/L Cl- Ex. 4-3
 Molarity  moles or volumes of solute Ex.
4-4~4-5
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Section 4.3
The Composition of Solutions

Common Terms of Solution Concentration

Stock - routinely used solutions prepared in
concentrated form.
Concentrated - relatively large ratio of solute to
solvent. (5.0 M NaCl)
Dilute - relatively small ratio of solute to solvent.
(0.01 M NaCl)
Standard solution: a solution whose concentration
is accurately known. Fig. 4-10, Ex. 4-6
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Section 4.3
The Composition of Solutions

Dilution

 The process of adding water to a concentrated or stock

solution to achieve the molarity desired for a particular
solution.
 Dilution with water does not alter the numbers of
moles of solute present.
 Moles of solute before dilution = moles of solute after
dilution
M1V1 = M2V2

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Section 4.3
The Composition of Solutions
Figure 4.10: Steps involved in the preparation of a
standard aqueous solution.

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Section 4.3
The Composition of Solutions

CONCEPT CHECK!

A 0.50 M solution of sodium chloride in an open beaker sits on

a lab bench. Which of the following would decrease the
concentration of the salt solution?
a) Add water to the solution.
b) Pour some of the solution down the sink drain.
c) Add more sodium chloride to the solution.
d) Let the solution sit out in the open air for a couple of
days.
e) At least two of the above would decrease the
concentration of the salt solution.
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Section 4.3
The Composition of Solutions

EXERCISE!

What is the minimum volume of a 2.00 M NaOH

solution needed to make 150.0 mL of a 0.800 M
NaOH solution?

60.0 mL

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Section 4.3
The Composition of Solutions
E.g. How much stock solution was needed to
prepare 500 mL 1.00 M HC2H3O2 from 17.4 M
stock solution?
1L 1.00 mol HC2 H 3O2
500 mL solution
1000 mL L solution
0.500 mol HC2 H 3O 2

17.4 mol HC2 H 3O 2

V ( ) 0.500mol HC2 H 3O 2
L solution

 V = 0.0287L or 28.7 mL
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Section 4.3
The Composition of Solutions

Figure 4.11:
(a) A measuring pipet is
graduated and can be used
to measure various
volumes of liquid
accurately.
(b) a volumetric (transfer)
pipet is designed to
measure one volume
accurately.

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Section 4.3
The Composition of Solutions
Figure 4.12: Dilution Procedure (a) A measuring pipet is used to
transfer 28.7mL of 17.4 M acetic acid solution to a volumetric flask. (b)
Water is added to the flask to the calibration mark.
(c) The resulting solution is 1.00 M acetic acid.

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Section 4.4
Types of Chemical Reactions

 Precipitation Reactions
AgNO3(aq) + NaCl(aq) AgCl(s) + NaNO3(aq)
 Acid–Base Reactions
NaOH(aq) + HCl(aq) NaCl(aq) + H2O(l)
 Oxidation–Reduction Reactions
Fe2O3(s) + 2Al(s) 2Fe(l) + Al2O3(s)

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Section 4.5
Precipitation Reactions

Precipitation Reaction
 A double displacement reaction in which a solid forms
and separates from the solution.
 When ionic compounds dissolve in water, the
resulting solution contains the separated ions.
 Precipitate – the solid that forms.

 When two solutions are mixed, an insoluble substance

forms. The solid is called precipitate:
 K2CrO4(aq) + Ba(NO3)2(aq)  BaCrO4(s) Fig. 4-13

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Section 4.5
Precipitation Reactions

The Reaction of K2CrO4(aq) and Ba(NO3)2(aq)

 Ba2+(aq) + CrO42–(aq 4(s)

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Section 4.5
Precipitation Reactions
What is the equation for the chemical change? We must
know the reactants and the products and to predict the
identities of the products.

 1. What species are present in the mixed solutions?

Ba(NO3)2: Ba2+, NO3-, K+, CrO42-, No solid barium nitrate or
potassium chromate are present in the mixed solution.
Fig. 4-14
 2. We can represent the mixing solution in two ways.
 K2CrO4(aq) + Ba(NO3)2(aq)  products or
 Ba2+(aq) + 2NO3-(aq) + 2K+(aq) + CrO42-(aq) products Fig. 4-15
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Section 4.5
Precipitation Reactions
How ions combine to produce a yellow solid?

 Try to think about various possibilities and the

likelihood of each possibility and then make the
prediction.
 1. When ions form the solid compound the net
charge of the compound is zero.  K+ vs Ba2+ or
NO3- vs CrO42-
 2. Most ionic compounds contain anions and
cations only. E.g. NaCl, Na2CO3, so the possible
combinations are K2CrO4, KNO3, BaCrO4 , or
Ba(NO3)2
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Section 4.5
Precipitation Reactions

 Not K2CrO4 or Ba(NO3)2 (they are reactants)

 Maybe KNO3 and BaCrO4
 Experienced chemist knows that K+ and
NO3- are colorless and chromate is yellow.
The solid is BaCrO4. What happened to K+
and NO3- ions?
 The equation for the chemical change is
 K2CrO4(aq) + Ba(NO3)2(aq)  KNO3(aq) +
BaCrO4(s)
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Section 4.5
Precipitation Reactions

Precipitation of Silver Chloride

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Section 4.5
Precipitation Reactions

Figure 4.17: The reaction of KCl(aq) with AgNO3

to form AgCl(s).

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Section 4.5
Precipitation Reactions

Precipitates
 Soluble – solid dissolves in solution; (aq) is used in
reaction equation.
 Insoluble – solid does not dissolve in solution; (s) is used
in reaction equation.
 Insoluble and slightly soluble are often used
interchangeably.

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Section 4.5
Precipitation Reactions
Simple Rules for Solubility
1. Most nitrate (NO3 ) salts are soluble.
2. Most alkali metal (group 1A) salts and NH4+ are soluble.
3. Most Cl , Br , and I salts are soluble (except Ag+, Pb2+,
Hg22+).
4. Most sulfate salts are soluble (except BaSO4, PbSO4,
Hg2SO4, CaSO4).
5. Most OH are only slightly soluble (NaOH, KOH are
soluble, Ba(OH)2, Ca(OH)2 are marginally soluble).
6. Most S2 , CO32 , CrO42 , PO43 salts are only slightly
soluble, except for those containing the cations in Rule 2.
Zumdahl,
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Section 4.5
Precipitation Reactions

CONCEPT CHECK!

Which of the following ions form compounds with

Pb2+ that are generally soluble in water?

a) S2–
b) Cl–
c) NO3–
d) SO42–
e) Na+

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Section 4.6
Describing Reactions in Solution

Formula Equation (Molecular Equation)

 Gives the overall reaction stoichiometry but not
necessarily the actual forms of the reactants and
products in solution.
 Reactants and products generally shown as compounds.
 Use solubility rules to determine which compounds are
aqueous and which compounds are solids.

AgNO3(aq) + NaCl(aq) AgCl(s) + NaNO3(aq)

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Section 4.6
Describing Reactions in Solution

Complete Ionic Equation

 All substances that are strong electrolytes are
represented as ions.
Ag+(aq) + NO3 (aq) + Na+(aq) + Cl (aq)
AgCl(s) + Na+(aq) + NO3 (aq)

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Section 4.6
Describing Reactions in Solution

Net Ionic Equation

 Includes only those solution components undergoing a change.
 Show only components that actually react.

Ag+(aq) + Cl (aq) AgCl(s)

 Spectator ions are not included (ions that do not participate

directly in the reaction).
Ag+(aq) + NO3 (aq) + Na+(aq) + Cl (aq)
AgCl(s) + Na+(aq) + NO3 (aq)
 Na+ and NO3 are spectator ions.
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Section 4.6
Describing Reactions in Solution
CONCEPT CHECK!
Write the correct formula equation, complete ionic
equation, and net ionic equation for the reaction
between cobalt(II) chloride and sodium hydroxide.
Formula Equation:
CoCl2(aq) + 2NaOH(aq) Co(OH)2(s) + 2NaCl(aq)

Complete Ionic Equation:

Co2+(aq) + 2Cl (aq) + 2Na+(aq) + 2OH (aq)
Co(OH)2(s) + 2Na+(aq) + 2Cl (aq)
Net Ionic Equation:
Co2+(aq) + 2OH (aq)
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Co(OH)2(s)
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Section 4.7
Stoichiometry of Precipitation Reactions

Solving Stoichiometry Problems for Reactions in

Solution

1. Identify the species present in the combined solution,

and determine what reaction occurs.
2. Write the balanced net ionic equation for the reaction.
3. Calculate the moles of reactants.
4. Determine which reactant is limiting.
5. Calculate the moles of product(s), as required.
6. Convert to grams or other units, as required.
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Section 4.7
Stoichiometry of Precipitation Reactions

CONCEPT CHECK! (Part I) Start'

10.0 mL of a 0.30 M sodium phosphate (Na3PO4)
solution reacts with 20.0 mL of a 0.20 M lead(II)
nitrate (Pb(NO3)2) solution (assume no volume
change).
 What precipitate will form?
lead(II) phosphate, Pb3(PO4)2
 What mass of precipitate will form?
1.1 g Pb3(PO4)2

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Section 4.7
Stoichiometry of Precipitation Reactions
Let’s Think About It
 Where are we going?
 To find the mass of solid Pb3(PO4)2 formed.
 How do we get there?
 What are the ions present in the combined solution?
 What is the balanced net ionic equation for the reaction?
 What are the moles of reactants present in the solution?
 Which reactant is limiting?
 What moles of Pb3(PO4)2 will be formed?
 What mass of Pb3(PO4)2 will be formed?
2PO43- + 3Pb2+  Pb3(PO4)2
10.0*0.30 20.0*0.20 20.0*0.20*1/3*(207*3+31*2+16*8)/1000
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Section 4.7
Stoichiometry of Precipitation Reactions

CONCEPT CHECK! (Part II)

10.0 mL of a 0.30 M sodium phosphate solution reacts

with 20.0 mL of a 0.20 M lead(II) nitrate solution
(assume no volume change).

 What is the concentration of nitrate ions left in

solution after the reaction is complete?
0.27 M

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Section 4.7
Stoichiometry of Precipitation Reactions

Let’s Think About It

 Where are we going?
 To find the concentration of nitrate ions left in solution after
the reaction is complete.
 How do we get there?
 What are the moles of nitrate ions present in the combined
solution?
 What is the total volume of the combined solution?

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Section 4.7
Stoichiometry of Precipitation Reactions

CONCEPT CHECK! (Part III)

10.0 mL of a 0.30 M sodium phosphate solution reacts

with 20.0 mL of a 0.20 M lead(II) nitrate solution
(assume no volume change).

 What is the concentration of phosphate ions

left in solution after the reaction is complete?
0.011 M

2PO43- + 3Pb2+  Pb3(PO4)2

10.0*0.30 20.0*0.20 (10.0*0.30-20.0*0.20*2/3)/30.0
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Section 4.7
Stoichiometry of Precipitation Reactions

Let’s Think About It

 Where are we going?
 To find the concentration of phosphate ions left in solution
after the reaction is complete.
 How do we get there?
 What are the moles of phosphate ions present in the solution
at the start of the reaction?
 How many moles of phosphate ions were used up in the
reaction to make the solid Pb3(PO4)2?
 How many moles of phosphate ions are left over after the
reaction is complete?
 What is the total volume of the combined solution?
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Section 4.7
Stoichiometry of Precipitation Reactions

You have two 500.0-mL aqueous solutions.

Solution A is a solution of silver nitrate (170),
and solution B is a solution of potassium
chromate (K2CrO4, 194). The masses of the
solutes in each of the solutions are the same.
When the solutions are added together, a
blood red precipitant is formed. After the
reaction has gone to completion, you dry the
solid and find that it has a mass of 331.8
grams.

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Section 4.7
Stoichiometry of Precipitation Reactions

 a) Calculate the concentration (molarity)

of the potassium ions in the original
potassium chromate (194) solution.
 b) Calculate the concentration (molarity)
of the chromate ions in the final solution.

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Section 4.7
Stoichiometry of Precipitation Reactions

Let’s Think About It

 To solve this problem we need to know:

 the initial concentrations, before a reaction

has taken place, of all ions that appear in the
final solution
 the balanced equation for the reaction that
has taken place. In this case, it makes sense to
use the net ionic equation.
 which reactant, if either, is limiting.
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Section 4.8
Acid-Base Reactions

Arrhenius’s acid
Arrhenius’s base

Acid–Base Reactions (Brønsted–Lowry)

 Acid—proton donor
 Base—proton acceptor
 For a strong acid and base reaction:
H+(aq) + OH–(aq) H2O(l)

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64
Section 4.8
Acid-Base Reactions
 HCl mixed with NaOH: There are H+, Cl-,
Na+, OH- ions in the solution. Predicting
from Tab. 4-1 that there is not any
precipitate forming in the solution.
 H+(aq) + OH-(aq)  H2O(l)
 Mixing HC2H3O2(aq) with KOH
 Species in solution before any reaction occurs:
HC2H3O2(aq) , K+, OH-
 Net ionic equation: OH-(aq) + HC2H3O2(aq) 
H2O(l) + C2H3O2-(aq)
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Section 4.8
Acid-Base Reactions

Neutralization of a Strong Acid by a Strong Base

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Section 4.8
Acid-Base Reactions

Performing Calculations for Acid–Base Reactions

1. List the species present in the combined solution before

any reaction occurs, and decide what reaction will occur.
2. Write the balanced net ionic equation for this reaction.
3. Calculate moles of reactants.
4. Determine the limiting reactant, where appropriate.
5. Calculate the moles of the required reactant or product.
6. Convert to grams or volume (of solution), as required.

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Section 4.8
Acid-Base Reactions

 Neutralization reaction: acid – base

reaction, When just enough base is added
to react exactly with the acid in a solution,
we say the acid has been neutralized.
 Acid – Base Titrations
Volumetric analysis: determining the
amounts of certain substances by titration.
Indicator

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Section 4.8
Acid-Base Reactions

Acid–Base Titrations

 Titration – delivery of a measured volume of a solution

of known concentration (the titrant) into a solution
containing the substance being analyzed (the analyte).
 Equivalence point – enough titrant added to react
exactly with the analyte.
 Endpoint – the indicator changes color so you can tell
the equivalence point has been reached.

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Section 4.8
Acid-Base Reactions
The following requirements must be met for a
titration to be successful:
1. The exact reaction between titrant and analyte must
be known.
2. The stoichiometric point must be marked accurately
3. The volume of the titrant required to reach the
stoichiometric point must be known accurately.
When the analyte is an acid or a base, the titrant
is a strong base or a strong acid. This procedure is
called acid – base titration. Fig. 4-18

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Section 4.8
Acid-Base Reactions Titration
Figure 4.18a:
The titration of
an acid with a
base. When the
analyte is an
acid or a base,
the titrant is a
strong base or a
strong acid. This
procedure is
called acid –
base titration.Zumdahl,
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65
Section 4.8
Acid-Base Reactions
Ex. 4-14
A student carries out an experiment to standardize
(determine the exact concentration of) sodium hydroxide
solution. To do this, the student weighs out a 1.3009-g
sample of potassium hydrogen phthalate (KHC8H4O4, often
abbreviated KHP). KHP (molar mass 204.22 g/mol)has one
acidic hydrogen. The student dissolves the KHP in distilled
water, adds phenolphthalein as an indicator, and titrates
the resulting solution with the sodium hydroxide solution
to the phenolphthalein end point. The difference between
the of final and initial buret readings indicates that 41.20
mL of the sodium hydroxide solution is required to react
exactly with the 1.3009 g KHP. Calculate the concentration
of the sodium hydroxide solution.
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Section 4.8
Acid-Base Reactions Let’s Think About It
 Where are we going?
 To find the concentration of NaOH solution.
 What do we know?
 1.3009 g KHC8H4O4 (KHP), molar mass (204.22 g/mol)
 41.20 mL NaOH solution to neutralize KHP
 The chemical reaction HC8H4O4- (aq) + OH-  C8H4O42- + H2O
 How do we get there?
 What are the ions present in the combined solution? What is
the reaction?
 What is the balanced net ionic equation for the reaction?
 What are the moles of H+ present in the solution?
 How much OH– is required to react with all of the H + present?
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73
Section 4.9
Oxidation-Reduction Reactions

Redox Reactions

 Many important substances are ionic. E.g. NaCl

produced by 2Na(s) + Cl2(g)  2NaCl(s)

 Reactions in which one or more electrons are

transferred.
 CH4(g) + 2O2(g)  CO2(g) + 2H2O(g) + energy

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Section 4.9
Oxidation-Reduction Reactions

Reaction of Sodium and Chlorine

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Section 4.9
Oxidation-Reduction Reactions

Rules for Assigning Oxidation States

1. Oxidation state of an atom in an element = 0
2. Oxidation state of monatomic ion = charge of the ion
3. Oxygen = 2 in covalent compounds (except in
peroxides where it = 1)
4. Hydrogen = +1 in covalent compounds
5. Fluorine = 1 in compounds
6. Sum of oxidation states = 0 in compounds
7. Sum of oxidation states = charge of the ion in ions

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Section 4.9
Oxidation-Reduction Reactions

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Section 4.9
Oxidation-Reduction Reactions

Rules for Assigning Oxidation States

 Oxidation states (oxidation numbers): keep

track of electrons in redox reactions particular
those involving covalent substances.
Covalent bond: atoms share electrons
 Actual charges on ions: n+, n-
 Oxidation numbers: +n, -n
 Fe3O4: O: -2, Fe: 8/3 or 2Fe3+ and 1Fe2+
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Section 4.9
Oxidation-Reduction Reactions

EXERCISE!

Find the oxidation states for each of the elements in

each of the following compounds:

 K2Cr2O7 K = +1; Cr = +6; O = –2

 CO32- C = +4; O = –2
 MnO2 Mn = +4; O = –2
 PCl5 P = +5; Cl = –1
 SF4 S = +4; F = –1
 HClO4 H = +1; Cl = +7, O = -2

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79
Section 4.9
Oxidation-Reduction Reactions
Redox Characteristics
 Transfer of electrons
 2Na(s) + Cl2(g)  2NaCl(s)
 Transfer may occur to form ions
 Oxidation – increase in oxidation state (loss of electrons);
reducing agent
 Reduction – decrease in oxidation state (gain of
electrons); oxidizing agent
 Oxidation CH4(g) + 2O2(g)  CO2(g) + 2H2O(g)
 State -4+1 0 +4 -2 +1 -2
 No ionic compound forms but still have electrons
transferred.
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Section 4.9
Oxidation-Reduction Reactions

Redox Reactions

Figure 4.20: A
summary of an
oxidation-
reduction process,
in which M is
oxidized and X is
reduced.

75
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Section 4.9
Oxidation-Reduction Reactions

CONCEPT CHECK!

Which of the following are oxidation-reduction

reactions? Identify the oxidizing agent and the
reducing agent.

a)Zn(s) + 2HCl(aq) ZnCl2(aq) + H2(g)

b)Cr2O72-(aq) + 2OH-(aq) 2CrO42-(aq) + H2O(l)
c)2CuCl(aq) CuCl2(aq) + Cu(s)
d)O3(g) + NO(g) O2(g) + NO2(g)

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Section 4.10
Balancing Oxidation-Reduction Equations
Balancing Oxidation–Reduction Reactions by Oxidation
States
1. Write the unbalanced equation.
2. Determine the oxidation states of all atoms in the
reactants and products.
3. Show electrons gained and lost using “tie lines.”
4. Use coefficients to equalize the electrons gained and
lost.
5. Balance the rest of the equation by inspection.
6. Add appropriate states.
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Section 4.10
Balancing Oxidation-Reduction Equations

E xample
 Balance the reaction between solid zinc and aqueous
hydrochloric acid to produce aqueous zinc(II) chloride
and hydrogen gas.

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Section 4.10
Balancing Oxidation-Reduction Equations

1. What is the unbalanced equation?

 Zn(s) + HCl(aq) Zn2+(aq) + Cl–(aq) + H2(g)

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Section 4.10
Balancing Oxidation-Reduction Equations

2. What are the oxidation states for each atom?

 Zn(s) + HCl(aq) Zn2+(aq) + Cl–(aq) + H2(g)
0 +1 –1 +2 –1 0

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Section 4.10
Balancing Oxidation-Reduction Equations

3. How are electrons gained and lost?

1 e– gained (each atom)

 Zn(s) + HCl(aq) Zn2+(aq) + Cl–(aq) + H2(g)

0 +1 –1 +2 –1 0

2 e– lost

 The oxidation state of chlorine remains unchanged.

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Section 4.10
Balancing Oxidation-Reduction Equations
4. What coefficients are needed to equalize the electrons
gained and lost?
1 e– gained (each atom) × 2

 Zn(s) + HCl(aq) Zn2+(aq) + Cl–(aq) + H2(g)

0 +1 –1 +2 –1 0

2 e– lost

 Zn(s) + 2HCl(aq) Zn2+(aq) + Cl–(aq) + H2(g)

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Section 4.10
Balancing Oxidation-Reduction Equations
5. What coefficients are needed to balance the remaining
elements?

 Zn(s) + 2HCl(aq) Zn2+(aq) + 2Cl–(aq) + H2(g)

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Section 4.10
Balancing Oxidation-Reduction Equations

Balancing Oxidation–Reduction Reactions

by half – reaction method

Ce4+(aq) + Sn2+(aq)  Ce3+(aq) + Sn4+(aq)

 Ce4+  Ce3+

 Sn2+  Sn4+

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Section 4.10
Balancing Oxidation-Reduction Equations

Balancing by Half-Reaction Method

1. Write separate reduction, oxidation

reactions.

2. For each half-reaction:

a. Balance elements (except H, O)
b. Balance O using H2O
c. Balance H using H+
d. Balance charge using electrons
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Section 4.10
Balancing Oxidation-Reduction Equations

Balancing by Half-Reaction Method (continued)

3. If necessary, multiply by integer to

equalize electron count.

4. Add half-reactions.

5. Check that elements and charges are

balanced.

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Section 4.10
Balancing Oxidation-Reduction Equations
in Acidic Solution

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Section 4.10
Balancing Oxidation-Reduction Equations

Half-Reaction Method - Balancing in Base

1. Balanced as in acid.

2. Add OH that equals H+ ions (both

sides!)

3. Form water by combining H+, OH .

4. Check elements and charges for balance.

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Section 4.10
Balancing Oxidation-Reduction Equations

in Basic Solution
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Section 4.10
Balancing Oxidation-Reduction Equations
Balancing Oxidation-Reduction Reactions

 Cr2O72-(aq) + SO32-(aq)
Cr3+(aq) + SO42-(aq)

 How can we balance this equation?

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Section 4.10
Balancing Oxidation-Reduction Equations

Method of Half Reactions

Cr2O72-(aq) Cr3+(aq)
SO32-(aq) + SO42-(aq)

How many electrons are involved in each half

reaction?

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Section 4.10
Balancing Oxidation-Reduction Equations
Method of Half Reactions (cont.)

 Cr2O72-(aq) 2Cr3+(aq)

 SO32-(aq) SO42-(aq)

 How can we balance the oxygen atoms?

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Section 4.10
Balancing Oxidation-Reduction Equations

Method of Half Reactions (cont.)

Cr2O72-(aq) 2Cr3+(aq) + 7H2O

H2O + SO32-(aq) SO42-(aq)

How can we balance the hydrogen atoms?

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Section 4.10
Balancing Oxidation-Reduction Equations

Method of Half Reactions (cont.)

 This reaction occurs in an acidic solution.

 14H+ + Cr2O72-(aq) 2Cr3+(aq) + 7H2O

 H2O +SO32-(aq) SO42-(aq) + 2H+

 How can we balance the electrons?

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Section 4.10
Balancing Oxidation-Reduction Equations

Method of Half Reactions (cont.)

14H+ + 6e- + Cr2O72-(aq)
2Cr3+(aq) + 7H2O

3[H2O +SO32-(aq) SO42-(aq) + 2e- + 2H+]

Cr2O72-(aq) + 3SO32-(aq) + 8H+(aq)

2Cr3+(aq) + 3SO42-(aq) + 4H2O(l)

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Section 4.10
Balancing Oxidation-Reduction Equations

Method of Half Reactions (cont.)

SO32-(aq) SO42-(aq)
H2O + SO32-(aq) SO42-(aq)
H2O + SO32-(aq) SO42-(aq) + 2H+
H2O + SO32-(aq) SO42-(aq) + 2H+ + 2e-
14H+ + 6e- + Cr2O72-(aq) 2Cr3+(aq) + 7H2O
3x (H2O + SO32-(aq) SO42-(aq) + 2H+ + 2e-)
Cr2O72-(aq) + 3SO32-(aq) + 8H+(aq)
2Cr3+(aq) + 3SO42-(aq) + 4H2O(l)
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Section 4.10
Balancing Oxidation-Reduction Equations

Balance the following oxidation-reduction reactions

that occur
5
in acidic solution.
+
2

- 2

itit ⑮
ClO-(aq) + I-(aq) Cl-(aq) + I3-(aq)
En
Br-(aq) + MnO4-(aq) Br2(l) + Mn2+(aq)

CH3OH(aq) + Cr2O72-(aq)
CH2O(aq) + Cr3+(aq)
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Section 4.11
Simple Oxidation-Reduction Titrations

The most frequently used oxidizing agents

Potassium permanganate KMnO4

Potassium dichromate K2Cr2O7
cerium hydrogen sulfate Ce(HSO4)4

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Section 4.11
Simple Oxidation-Reduction Titrations

The most common used oxidizing agents-MnO4-

The different reactions that MnO4- may undergo

MnO4-(aq) + 8H+(aq) + 5e- Mn2+(aq) + 4H2O(l)--- acidic

solution
MnO4-(aq) + 2H2O(l) + 3e- MnO2(s) + 4OH-(aq) --- neutral
solution
MnO4-(aq) + e- MnO42-(aq)--- basic solution

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Section 4.11
Simple Oxidation-Reduction Titrations
Ex. 4-20
Iron ores often involve a mixture of oxides and contain both
Fe2+ and Fe3+ ions. Such an ore can be analyzed for its iron
content by dissolving it in acidic solution, reducing all the iron
to Fe2+ ions, and then titrating with a standard solution of
potassium permanganate. In the resulting solution, MnO4- is
reduced to Mn2+, and Fe2+ is oxidized to Fe3+. A sample of iron
ore weighing 0.3500 g was dissolved in acidic solution, and all
the iron was reduced. Then the solution was titrated with a
1.621x10-2 M KMnO4 solution. The titration required 41.56
mL of the permanganate solution to reach the light purple
(pink) endpoint. Determine the mass percent of iron in the
iron ore.
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Section 4.11
Simple Oxidation-Reduction Titrations
Solution
Where are we going?
We are asked to determine the mass percent of iron in an iron
ore.

p
How do we get there?
mass of iron
Mass percent of iron 100%
mass of iron ore
MnO4-(aq) + 8H+(aq) + 5Fe2+(aq) Mn2+(aq) + 5Fe3+(aq) + 4H2O(l)
The number of moles of MnO4– is &0.04156x1.621x10-2 = 6.737x10-4
-4 5 mol Fe 2 55.85g Fe
6.737 10 mol MnO 4 0.1881 g Fe
1 mol MnO 4 1 mol Fe
0.1881
The mass percent of iron in the iron ore is 100% 53.74%
0.3500
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