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Lecture Presentation

Chapter 4

Chemical
Quantities and
Aqueous
Reactions
Christian Madu, Ph.D.
Collin College
-----Revised by Wang
© 2014 Pearson Education, Inc.
Reaction Stoichiometry: How Much Carbon
Dioxide?

• The balanced chemical equations for fossil-


fuel combustion reactions provide the exact
relationships between the amount of fossil
fuel burned and the amount of carbon
dioxide emitted.

– 16 CO2 molecules are produced for every


2 molecules of octane burned.

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Quantities in Chemical Reactions

• The amount of every substance used and


made in a chemical reaction is related to
the amounts of all the other substances in
the reaction.
– Law of conservation of mass
– Balancing equations by balancing atoms
• The study of the numerical relationship
between chemical quantities in a chemical
reaction is called stoichiometry.

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Reaction Stoichiometry
• The coefficients in a chemical reaction
specify the relative amounts in moles of
each of the substances involved in the
reaction.
2 C8H18(l) + 25 O2(g)  16 CO2(g) + 18 H2O(g)

2 mol C8H18 : 25 mol O2 : 16 mol CO2 : 18 mol H2O

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Stoichiometry Calculation

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Making Molecules: Mole-to-Mole Conversions

Question:

Question species amt


Question species amt  Given species amt 
Givens pecies amt

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Making Molecules: Mass-to-Mass Conversions
Example 4.1 Stoichiometry
In photosynthesis, plants convert carbon dioxide and water into glucose
(C6H12O6) according to the reaction:

Suppose you determine that a particular plant consumes 37.8g of CO2 in one
week. Assuming that there is more than enough water present to react with all of
the CO2, what mass of glucose (in grams) can the plant synthesize from the
CO2?

6 moles 1 mole

(12.011+16.00×2)×6 (12.011×6+1.008×12+16.00×6)×1
=264.07 g =180.02 g
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Limiting Reactant, Theoretical Yield

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Limiting Reactant, Theoretical Yield

Limiting reactant
Excessive reactant
Theoretical yield
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Limiting Reactant, Theoretical Yield

Theoretical yield

Actual yield
actual yield
Percent yield  100%
theoretical yield
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Way to Determine Limiting Reactant

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Way to Determine Limiting Reactant
Question

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Way to Determine Limiting Reactant

P4(s) + 5O2(g)  …. P4(s) + 5O2(g)  ….


Based on
balanced A B A B
equation
1 mole 5 mole Based on
balanced
1 mole 5 mole
Given
0.50 mole 5.0 mole equation 123.97g 160.00 g
a 1
Given
1.2 g 5.0 g
  0.2 a 123.97
b 5   0.77481
b 160.00
a' 0.50
  0.10 a' 1.2
b' 5.0   0.24
b' 5.0
a a'
 A (i.e. P4) is limiting. a a'
b© 2014 Pearson
b' Education, Inc.  A (i.e. P4) is limiting.
b b'
Way to Calculate Theoretical Yield and
Percent Yield
Example 4.3 Limiting Reactant and Theoretical Yield
Ammonia, NH3, can be synthesized by the reaction:

a) Starting with 86.3 g NO and 25.6 g H2, find the theoretical


yield of ammonia in grams.
b) If the actual yield of ammonia is 42.0 g, what is the percent
yield of this reaction?

Based on balanced 2 mol 5 mol


equation
60.02 g 10.08 g
Given 86.3 g 25.6 g

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Way to Calculate Theoretical Yield and
Percent Yield
Example 4.3 Limiting Reactant and Theoretical Yield

Based on balanced 2 mol 5 mol 2 mol


equation 60.02 g 10.08 g 34.07 g
Given 86.3 g 25.6 g
Question species amt
a 60.02 Question species amt  Given species amt 
  5.954 Givens pecies amt
b 10.08 Yield calculation is based on limiting reactant.
a' 86.3
  3.37 34.07g NH3
b' 25.6 NH3 (g)  86.3g NO 
60.02g NO
a a'
  49.0 g NH3
b b' NO is limiting.
actual yield
Percent yield  100%
theoretical yield
42.0g
 100%  85.7%
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Question of NaCl dissolving water

Question:

Table salt (NaCl) dissolving in water.


This is a chemical process or a physical process?

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Solution Concentration and Solution
Stoichiometry

• When table salt is mixed with water, it seems to


disappear or become a liquid, the mixture is
homogeneous.
– The salt is still there, as you can tell from the taste or simply
boiling away the water.
• Homogeneous mixtures are called solutions.

• A solution could be liquid, gas, or solid.

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Solution Concentration and Solution
Stoichiometry

Solute: the component changed its state.


Solution
Solvent: the component did not change its state.

When both components did not change state,


Solute: the component with less mass percent.
Solution
Solvent: the component with higher mass content.

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Solution Concentration --- Mass Percent

solute mass (g) in the solution


Solute mass percent  100%
Solution mass(g)

Question:

You dissolved 10 g sugar in 100 g water, while your sister


dissolved 120 g sugar in 2200 g water.

Which solution is sweeter (i.e., which solution has a higher


sugar mass percent?)

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Solution Concentration: Molarity

• A common way to express solution


concentration is molarity (M).
– Molarity is the amount of solute (in moles)
divided by the volume of solution (in liters).

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Preparing 1 L of a 1.00 M NaCl Solution

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Using Molarity in Calculations

If you known any two of the three factors,


You shall be able to figure out the third.

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Using Molarity in Calculations
Example 4.5 Calculating Solution Concentration
If you dissolve 25.5 g KBr in enough water to make 1.75 L of solution,
what is the molarity of the solution?

KBr molar mass: 119.00 g/mol


1 mole KBr
KBr moles  25.5 g KBr   0.214 mole KBr
119.00 g KBr
KBr moles
KBr molarity 
Solution v olume (L)
0.214 mole KBr
  0.122M
1.75 L

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Using Molarity in Calculations
Example 4.6 Using Molarity in Calculations
How many liters of a 0.125 M NaOH solution contain 0.255 mol of NaOH?

solute amount (in mol)


volume of solution (in L) 
Molarity (M)

Question
A student prepared a solution by dissolving 26.88 g KCl in water. The
solution mass was 502.0 g and the solution density is 1.05 g/ml. What is KCl
molarity of this solution?

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Solution Dilution
• Often, solutions are stored as concentrated
stock solutions.
• To make solutions of lower concentrations
from these stock solutions, more solvent
is added.
– Before and after dilution, the amount of solute
doesn’t change, just the volume of solution:
moles solute in solution 1 = moles solute in solution 2
• The concentrations and volumes of the stock
and new solutions are inversely proportional:
M1∙V1 = M2∙V2
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Preparing 3.00 L of 0.500 M CaCl2 from a
10.0 M Stock Solution

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Solution Dilution
Example 4.7 Solution Dilution
To what volume should you dilute 0.200 L of a 15.0 M NaOH solution to
obtain a 3.00 M NaOH solution?

M1∙V1 = M2∙V2

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Solution Molarity in Stoichiometry

Example 4.8 Solution Stoichiometry


What volume (in L) of 0.150 M KCl solution will completely react with
0.150 L of a 0.175 M Pb(NO3)2 solution according to the following
balanced chemical equation?

Based on balanced
equation: 2 mol 1 mol
Given:
xmol 0.150L  0.175M
Question species amt
Question species amt  Given species amt 
Givens pecies amt

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Types of Aqueous Solutions and Solubility

• Consider two familiar aqueous solutions:


salt water and sugar water.
– Salt water is a homogeneous mixture of NaCl
and H2O.
– Sugar water is a homogeneous mixture of
C12H22O11 and H2O.
• As you stir either of these two substances
into the water, it seems to disappear.
– How do solids such as salt and sugar dissolve
in water?

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What Happens When a Solute Dissolves?

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Solute and Solvent Interactions in a Sodium
Chloride Solution

Lots of separated ions


existing in water
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Sugar Dissolved in Water

No ions existing
in water
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Electrolyte and Nonelectrolyte Solutions

• Materials that dissolve


in water to form a
solution that conducts
electricity are called
electrolytes.

• A solution of salt (an electrolyte) • Materials that dissolve


conducts electrical current.
in water to form a
solution that does not
• A solution of sugar (a
nonelectrolyte) does not. conduct electricity are
called nonelectrolytes.

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Electrolyte and Nonelectrolyte Solutions

• Ionic substances such as


sodium chloride that completely
dissociate into ions when they
dissolve in water are strong
electrolytes.

• In contrast to sodium chloride,


sugar is a molecular compound.

• Most molecular compounds


(except for acids), dissolve in
water as intact molecules.

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Binary Acids
• Acids are molecular compounds that ionize when
they dissolve in water.
– The molecules are pulled apart by their attraction for
the water.
– When acids ionize, they form H+ cations and also anions.
• The percentage of molecules that ionize varies from
one acid to another.
• Acids that ionize virtually 100% are called
strong acids. Complete process
HCl(aq)  H+(aq) + Cl−(aq)
• Acids that only ionize a small percentage are called
weak acids. Incomplete process
HF(aq)  H+(aq) + F−(aq)
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Strong and Weak Electrolytes
• Strong electrolytes are materials that dissolve
completely as ions.
– Ionic compounds and strong acids
– Solutions conduct electricity well
• Weak electrolytes are materials that dissolve
mostly as molecules, but partially as ions.
– Weak acids
– Solutions conduct electricity, but not well
• When compounds containing a polyatomic ion
dissolve, the polyatomic ion stays together.
HC2H3O2(aq)  H+(aq) + C2H3O2−(aq)

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Classes of Dissolved Materials

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Dissociation and Ionization
• When ionic compounds dissolve in water, the
anions and cations are separated from each
other. This is called dissociation.
Na2S(aq)  2 Na+(aq) + S2–(aq)
• When compounds containing polyatomic ions
dissociate, the polyatomic group stays together
as one ion.
Na2SO4(aq)  2 Na+(aq) + SO42−(aq)
• When strong acids dissolve in water, the
molecule ionizes into H+ and anions.
(ionization)
H2SO4(aq)  2 H+(aq) + SO42−(aq)
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The Solubility of Ionic Compounds

?
Ionic compound  dissolving in water  dissociation into ions

No all ionic compounds can dissolve in water.


However, all dissolving portion can 100% dissociate into ions.

• In general, a compound is termed soluble if


it dissolves in water.
• And insoluble if it does not.

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Solubility of Salts

• If we mix solid AgNO3 with


water, it dissolves and
forms a strong electrolyte
solution.
• Silver chloride (AgCl), on
the other hand, is almost
completely insoluble.
– If we mix solid AgCl with
water, virtually all of it
remains as a solid within
the liquid water.

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When Will a Salt Dissolve?

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When Will a Salt Dissolve?
Example 4.9 Predicting whether an Ionic Compound Is Soluble
Predict whether each compound is soluble or insoluble.
a. PbCl2 b. CuCl2 c. Ca(NO3)2 d. BaSO4

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Precipitation Reactions

• Precipitation reactions are reactions in


which a solid forms when we mix two
solutions.
– Reactions between aqueous solutions of ionic
compounds produce an ionic compound that
is insoluble in water.
– The insoluble product is called a precipitate.

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Precipitation of Lead(II) Iodide

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Predicting Precipitation Reactions

insoluble

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Predicting Precipitation Reactions

Question:

Cd(NO3)2(aq) + Na2S(aq)  any precipitation?

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Representing Aqueous Reactions
Molecular equation:
2 KOH(aq) + Mg(NO3)2(aq)  2 KNO3(aq) + Mg(OH)2(s)

If soluble, use ions to represent: Complete ionic


2 K+ + 2OH-(aq) + Mg2+(aq) + 2NO3-(aq) equation
 2 K+(aq) + NO3-(aq) + Mg(OH)2(s)

Cancel all ions appear at both sides:


2K+ + 2OH-(aq) + Mg2+(aq) + 2NO3-(aq)
 2K+(aq) + 2NO3-(aq) + Mg(OH)2(s)
Those ions cancelled are called spectator ions. They actually did not
participate the reaction.

Left over:
2OH-(aq) + Mg2+(aq)  Mg(OH)2(s) Net ionic equation
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Ionic Equation
• Rules of writing the complete ionic equation:
– Aqueous strong electrolytes are written as ions.
• Soluble salts, strong acids, strong bases
– Insoluble substances, weak electrolytes, and
nonelectrolytes are written in molecule form.
• Solids, liquids, and gases are not dissolved,

Example 4.12 Writing Complete Ionic and Net Ionic Equations


Write complete ionic and net ionic equations for each reaction.

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Examples

• Write the ionic and net ionic equation for each


of the following:
1. K2SO4(aq) + 2 AgNO3(aq)  2 KNO3(aq) + Ag2SO4(s)
2 K+(aq) + SO42−(aq) + 2 Ag+(aq) + 2 NO3−(aq)
 2 K+(aq) + 2 NO3−(aq) + Ag2SO4(s)
2 Ag+(aq) + SO42−(aq)  Ag2SO4(s)

2. Na2CO3(aq) + 2 HCl(aq)  2 NaCl(aq) + CO2(g) + H2O(l)


2 Na+(aq) + CO32−(aq) + 2 H+(aq) + 2 Cl−(aq)
 2 Na+(aq) + 2 Cl−(aq) + CO2(g) + H2O(l)
CO32−(aq) + 2 H+(aq)  CO2(g) + H2O(l)
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Acid–Base and Gas-Evolution Reactions

• Two other important classes of reactions


that occur in aqueous solution are
1. acid–base reactions, and
2. gas-evolution reactions.

• Acid–base Reaction:
– An acid–base reaction is also called a
neutralization reaction.

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Acid–Base Reactions
Arrhenius Definitions:
• Acid: Substance that produces H+
HCl(aq) H+(aq) + Cl–(aq)
– Some acids—called polyprotic acids
• One molecule acid can ionize out more than one
proton sequentially.
• For example, sulfuric acid, H2SO4 is a diprotic acid.
• It is strong in its first ionizable proton, but weak in its
second.
• Base: Substance that produces OH ions in
aqueous solution
NaOH(aq) Na+(aq) + OH–(aq)
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Acid–Base Reactions
• Also called neutralization reactions
because the acid and base neutralize each
other’s properties
2 HNO3(aq) + Ca(OH)2(aq)  Ca(NO3)2(aq) + 2 H2O(l)

What is its net ionic equation?

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Acid–Base Reactions
• Also called neutralization reactions
because the acid and base neutralize
each other’s properties
2 HNO3(aq) + Ca(OH)2(aq)  Ca(NO3)2(aq) + 2 H2O(l)
• The net ionic equation for an acid–base
reaction is
H+(aq) + OH(aq)  H2O(l)
– as long as the salt that
forms is soluble in water.

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Acids and Bases in Solution
• Acids ionize in water to form H+ ions.
HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq)
– hydronium ion, H3O+.
– Most chemists use H+ and H3O+ interchangeably.

• Bases dissociate in water to form OH ions.


– Bases, such as NH3, that do not contain OH ions,
produce OH by pulling H off water molecules.

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Some Common Acids and Bases

Must know which is strong, which is weak.


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Predict the Product of the Reactions

1. HCl(aq) + Ba(OH)2(aq) 
(H+ + Cl−) + (Ba2+ + OH−) → (H+ + OH−) + (Ba2+ + Cl−)

HCl(aq) + Ba(OH)2(aq) → H2O(l) + BaCl2


2 HCl(aq) + Ba(OH)2(aq)  2 H2O(l) + BaCl2(aq)

2. H2SO4(aq) + LiOH(aq) 
(H+ + SO42−) + (Li+ + OH−) → (H+ + OH−) + (Li+ + SO42−)
H2SO4(aq) + LiOH(aq) → H2O(l) + Li2SO4
H2SO4(aq) + 2 LiOH(aq)  2 H2O(l) + Li2SO4(aq)

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Acid–Base Titrations

• In a titration, a
substance in a solution
of known concentration
is reacted with another
substance in a solution
of unknown
concentration.
• At the endpoint, the
reactants are in their
stoichiometric ratio.

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Acid–Base Titrations
• In acid–base titrations, a chemical is
added that changes color at endpoint.
– The chemical is called an
indicator.
• At the endpoint of an acid–base
titration, the number of moles of H+
equals the number of moles of OH.
– This is also known as the
equivalence point.

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Acid–Base Titrations
Example 4.14 Acid–Base Titration

The titration of a 10.00 mL sample of an HCl solution of unknown


concentration requires 12.54 mL of a 0.100 M NaOH solution to reach the
equivalence point. What is the concentration of the unknown HCl solution
in M?

HCl(aq) + NaOH(aq)  NaCl(aq) + H2O(l)


1 mol 1 mol
x mol (12.54/1000)L×0.100M
=1.25×10-3 mol
Question species amt
Question species amt  Given species amt 
Givens pecies amt

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Acid–Base and Gas-Evolution Reactions

• Gas-evolution reactions
– In a gas-evolution reaction, a gas forms,
resulting in bubbling.

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Gas-Evolving Reactions

• Some reactions form a gas directly from the


ion exchange.
K2S(aq) + H2SO4(aq)  K2SO4(aq) + H2S(g)

• Other reactions form a gas by the


decomposition of one of the ion exchange
products into a gas and water.
NaHCO3(aq) + HCl(aq)  NaCl(aq) + H2CO3(aq)
H2CO3(aq)  H2O(l) + CO2(g)
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Gas-Evolution Reaction

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Types of Compounds That Undergo Gas-
Evolution Reactions

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Oxidation–Reduction Reactions

• The reactions in which electrons are


transferred from one reactant to the other
are called oxidation-reduction reactions.
– These are also called redox reactions.
– Many redox reactions involve the reaction of a
substance with oxygen.
– 4 Fe(s) + 3 O2(g)  2 Fe2O3(s) (rusting)
– 2 C8H18(l) + 25 O2(g) 16 CO2(g) + 18 H2O(g)
(combustion)
– 2 H2(g) + O2(g)  2 H2O(g)

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Combustion as Redox
2 H2(g) + O2(g)  2 H2O(g)

Insert Figure 4.22 on Pg. 176

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Redox without Combustion
2 Na(s) + Cl2(g)  2 NaCl(s)

Insert Figure 4.24 on Pg. 177

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Redox Reactions of Metals with Nonmetals

• Consider the following reactions:


4 Na(s) + O2(g) → 2 Na2O(s)
2 Na(s) + Cl2(g) → 2 NaCl(s)
• The reactions involve a metal reacting with
a nonmetal.
• In addition, both reactions involve the
conversion of free elements into ions.
4 Na(s) + O2(g) → 2 Na+2O2– (s)
2 Na(s) + Cl2(g) → 2 Na+Cl–(s)

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Redox Reaction between nonmetals
• The transfer of electrons does not need to be a
complete transfer (as occurs in the formation of
an ionic compound) for the reaction to qualify as
oxidation–reduction.
– For example, consider the reaction between
hydrogen gas and chlorine gas:
H2(g) + Cl2(g) 2 HCl(g)
• When hydrogen bonds to chlorine, the electrons
are unevenly shared.

+ 2

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Oxidation and Reduction
• Atoms that lose electrons are being oxidized,
while atoms that gain electrons are being
reduced.
2 Na(s) + Cl2(g) → 2 Na+Cl–(s)
Na → Na+ + 1 e– (oxidation)
Cl2 + 2 e– → 2 Cl– (reduction)

Agent losing electron, oxidation reaction, reducing agent


Agent gaining electron, reduction reaction, oxidizing agent

Remember

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Oxidation States

• We need a quantitative method for determining


how the electrons are transferred.
• Chemists assign a number to each element in a
reaction called an oxidation state that allows
them to determine the electron flow in the
reaction.
– Even though they look like them, oxidation states
are not ion charges!
• Oxidation states are imaginary charges assigned
based on a set of rules.
• Ion charges are real, measurable charges.

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Rules for Assigning Oxidation States

The following rules are in order of priority:


1. Free elements have an oxidation state = 0.
– Na = 0 and Cl2 = 0 in 2 Na(s) + Cl2(g)
2. Monatomic ions have an oxidation state
equal to their charge.
– Na = +1 and Cl = −1 in NaCl
3. (a) The sum of the oxidation states of all
the atoms in a compound is 0.
– Na = +1 and Cl = −1 in NaCl, (+1) + (−1) = 0

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Rules for Assigning Oxidation States

3. (b) The sum of the oxidation states of all the


atoms in a polyatomic ion equals the charge on
the ion.
– N = +5 and O = −2 in NO3–, (+5) + 3(−2) = −1
4. (a) Group I metals have an oxidation state of
+1 in all their compounds.
– Na = +1 in NaCl
4. (b) Group II metals have an oxidation state of
+2 in all their compounds.
– Mg = +2 in MgCl2

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Rules for Assigning Oxidation States
5. In their compounds, nonmetals have
oxidation states according to the
table below.
– Nonmetals higher on the table take priority.

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Rules for Assigning Oxidation States

Example 4.16 Assigning Oxidation States


Assign an oxidation state to each atom in each element, ion, or compound.
a. Cl2 b. Na+ c. KF d. CO2 e. SO42− f. K2O2

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Identifying Redox Reactions
• Oxidation: An increase in oxidation state
• Reduction: A decrease in oxidation state

Agent losing electron, OS increasing, oxidation reaction,


reducing agent
Agent gaining electron, OS decreasing, reduction reaction,
oxidizing agent
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Identifying Redox Reactions and Balancing
Question:
Sn(s) + HNO3(aq)  SnO2(s) + NO2(g) + H2O(g)
(a) What is oxidized and what is reduced in the following reaction?
(b) Balance this reaction equation.

Increasing, be oxidized

0 +1 +5 -2 +4 -2 +4 -2 +1 -2
Sn(s) + HNO3(aq)  SnO2(s) + NO2(g) + H2O(g)

Decreasing, be reduced

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Identifying Redox Reactions and Balancing
Question:
Sn(s) + HNO3(aq)  SnO2(s) + NO2(g) + H2O(g)
(a) What is oxidized and what is reduced in the following reaction?
(b) Balance this reaction equation.
Increase 4

0 +1 +5 -2 +4 -2 +4 -2 +1 -2
Sn(s) + HNO3(aq)  SnO2(s) + NO2(g) + H2O(g)

Decreasing 1
Increase 4 ×1
0 +1 +5 -2 +4 -2 +4 -2 +1 -2
Sn(s)+4HNO3(aq)  SnO2(s)+4NO2(g) + H2O(g)

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Identifying Redox Reactions and Balancing
Question:
Sn(s) + HNO3(aq)  SnO2(s) + NO2(g) + H2O(g)
(a) What is oxidized and what is reduced in the following reaction?
(b) Balance this reaction equation.

Increase 4 ×1
0 +1 +5 -2 +4 -2 +4 -2 +1 -2
Sn(s)+4HNO3(aq)  SnO2(s)+4NO2(g)+2H2O(g)

Decreasing 1×4

Sn(s)+4HNO3(aq)  SnO2(s)+4NO2(g)+2H2O(g)

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