Lecture Presentation

Chapter 4

Reactions in
Aqueous Solution

James F. Kirby
Quinnipiac University
Hamden, CT
© 2018 Pearson Education, Inc.
 General Properties of Aqueous
Solutions
• A solution is a homogeneous mixture of two
or more substances.
• A solution is made when one substance (the
solute) is dissolved in another (the solvent).
• The solute is the substance that is present in
the smallest amount.
• Solutions in which water is the solvent are
called aqueous solutions.

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 Solutions
• Solutions are defined as
homogeneous mixtures of
two or more pure
substances.
• The solvent is present in
greatest abundance.
• All other substances are
solutes.
• When water is the solvent,
the solution is called an
aqueous solution. Aqueous
Reactions

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 Aqueous Solutions
• Substances can dissolve in water by different ways:
– Ionic compounds dissolve by dissociation, where water surrounds
the separated ions.
– Molecular compounds interact with water, but most do NOT
dissociate.
– Some molecular substances react with water when they dissolve.
• All substances dissolve by solvation, surrounding of the solute by
solvent.

Aqueous
Reactions

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 Electrolytic Properties

• If a substance forms ions in solution, then

the substance is an electrolyte and the
solution conducts electricity. An example is
NaCl.
• If a substance does not form ions in solution,
then the substance is a nonelectrolyte and
the solution does not conduct electricity.
Examples are sucrose and water.

Aqueous
Reactions

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 Ionic Compounds in Water
• When an ionic compound dissolves in water,
the ions are said to dissociate; dissociation
(해리)
– This means that in solution, the solid no longer
exists as a well-ordered arrangement of ions in
contact with one another.
– Instead, each ion is surrounded by several water
molecules; it is called an aqueous ion denoted using
the abbreviation “aq”.
– These ions are said to be solvated (용매화).
– This tends to stabilize the ions in solution and
prevent cations and anions from recombining. Aqueous
Reactions

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 Molecular Compounds in Water

• When a molecular compound (e.g. CH3OH )

dissolves in water, the solution usually
consists of intact molecules dispersed
homogeneously in the solution.
• Therefore, there is nothing in the solution to
transport electric charge and the solution does
not conduct electricity and most molecular
compounds are nonelectrolytes.
• There are some important exceptions.
– For example, HCl(g) in water ionizes to form H+(aq)
Aqueous
and Cl–(aq). Reactions

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 Electrolytes and Nonelectrolytes

• An electrolyte is a substance that dissociates into

ions when dissolved in water.
• A nonelectrolyte may dissolve in water, but it
does not dissociate into ions when it does so.
Aqueous
Reactions

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 Electrolytes

• A strong electrolyte dissociates completely when

dissolved in water.
• A weak electrolyte only dissociates partially when
dissolved in water.
• A nonelectrolyte does NOT dissociate in water. Aqueous
Reactions

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 Strong Electrolytes Are…
• Strong acids
• Strong bases

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Aqueous
Reactions

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 Weak Electrolytes Are…
• Compounds whose aqueous solutions conduct
electricity poorly are called weak electrolytes.
– The predominant form of the solute is the un-ionized
molecule.
– A weak electrolyte only dissociates partially when
dissolved in water
• HC2H3O2(aq) ↔ H+(aq) + C2H3O2–(aq)
– The half-arrows in both directions means that the
reaction is significant in both directions.
– This balance produces a state of chemical
equilibrium.
Aqueous
Reactions

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Sample Exercise 4.1 Relating Relative Numbers of Anions
and Cations to Chemical Formulas
The accompanying diagram represents an aqueous solution of either MgCl2, KCl, or K2SO4. Which solution does the
drawing best represent?

Solution
Analyze We are asked to associate the charged spheres in the
diagram with ions present in a solution of an ionic substance.

Plan We examine each ionic substance given to determine the

relative numbers and charges of its ions. We then correlate these
ionic species with the ones shown in the diagram.

Solve The diagram shows twice as many cations as anions,

consistent with the formulation K2SO4.

Check Notice that the net charge in the diagram is zero, as it must
be if it is to represent an ionic substance.

Aqueous
Reactions

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Sample Exercise 4.1 Relating Relative Numbers of Anions
and Cations to Chemical Formulas
Continued

Practice Exercise 1
If you have an aqueous solution that contains 1.5 moles of HCl, how many moles of ions are in the solution?
(a) 1.0 (b) 1.5 (c) 2.0 (d) 2.5 (e) 3.0

Practice Exercise 2
If you were to draw diagrams representing aqueous solutions of (a) NiSO4, (b) Ca(NO3)2, (c) Na3PO4,
(d) Al2(SO4)3, how many anions would you show if each diagram contained six cations?

Aqueous
Reactions

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Solubility Guidelines for Ionic Compounds

• The solubility of a substance at a particular temperature

is the amount of that substance that can be dissolved in
a given quantity of solvent at that temperature.
• A substance with a solubility of less than 0.01 mol/L is
regarded as being insoluble.
• Experimental observations have led to empirical
guidelines for predicting solubility.
• Solubility guidelines for common ionic compounds in
water:
• Compounds containing alkali metal ions or ammonium ions are
soluble.
Aqueous
Reactions

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 Solubility of Ionic Compounds
• Not all ionic compounds dissolve in water.
• A list of solubility rules is used to decide what
combination of ions will dissolve.

Aqueous
Reactions

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 Precipitation Reactions
• Precipitation reactions occur when two solutions
containing soluble salts are mixed and an
insoluble salt is produced. The solid is called a
precipitate.

Aqueous
Reactions

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How to Predict Whether a Precipitate Forms
When Strong Electrolytes are Mixed

1) Note the ions present in the reactants.

2) Consider the possible cation-anion combinations.
3) Use Table 4.1 to determine if any of the
combinations is insoluble.

Aqueous
Reactions

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Sample Exercise 4.2 Using Solubility Rules
Classify these ionic compounds as soluble or insoluble in water: (a) sodium carbonate, Na2CO3, (b) lead
sulfate, PbSO4.

Solution
Analyze We are given the names and formulas of two ionic compounds and asked to predict whether they are soluble
or insoluble in water.

Plan We can use Table 4.1 to answer the question. Thus, we need to focus on the anion in each compound because the
table is organized by anions.

Solve
(a) According to Table 4.1, most carbonates
are insoluble. But carbonates of the alkali
metal cations (such as sodium ion) are an
exception to this rule and are soluble.
Thus, Na2CO3 is soluble in water.

(b) Table 4.1 indicates that although most

sulfates are water soluble, the sulfate of
Pb2+ is an exception. Thus, PbSO4 is insoluble in water.

Aqueous
Reactions

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Sample Exercise 4.2 Using Solubility Rules
Continued

Practice Exercise 1
Which of the following compounds is insoluble in water?
(a) (NH4)2S (b) CaCO3 (c) NaOH (d) Ag2SO4 (e) Pb(CH3COO)2

Practice Exercise 2
Classify the following compounds as soluble or insoluble in water:
(a) cobalt(II) hydroxide, (b) barium nitrate, (c) ammonium phosphate.

Aqueous
Reactions

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 Common
Polyatomic Ions

Aqueous
Reactions

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 Solution Chemistry

• It is helpful to pay attention to exactly

what species are present in a reaction
mixture (i.e., solid, liquid, gas, aqueous
solution).
• If we are to understand reactivity, we
must be aware of just what is changing
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during the course of a reaction.

Aqueous
Reactions

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How do we recognize ionic compounds?

1. The ammonium (NH4+) cation, or

2. Any metal and a polyatomic anion, or
3. Any group 1 or 2 metal and a halide (X-)
oxide (O2-) or sulfide (S2-)

Or, composed of two polyatomic ions

Aqueous
Reactions

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Determining Ionic
Compounds

Aqueous
Reactions

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 Example

Determine which of the following substances

are ionic CCl4, CaCl2, Li, Co(NO3)2.
CCl4 ; Neither ammonium nor a metal, so not ionic…
CaCl2 ; ammonium isn’t present but a metal (Ca),
Ca is from Group 2, there is a halide Cl…Ionic
Li ; ammonium isn’t present but a metal (Li),
However, there is nothing.. Anion …Not ionic

Co(NO3)2 ; ammonium isn’t present but a metal (Co),

And there is a polyatomic anion (NO3)…Ionic
Aqueous
Reactions

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 Metathesis (Exchange) Reactions

• Metathesis comes from a Greek word that means

“to transpose(교환하다, 뒤바꾸다).”
• It appears as though the ions in the reactant
compounds exchange, or transpose, ions, as seen
in the given equation.

Aqueous
Reactions

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 Completing and Balancing
Metathesis Equations
• Steps to follow:
1) Use the chemical formulas of the reactants to
determine which ions are present.
2) Write formulas for the products: cation from
one reactant, anion from the other. Use
charges to write proper subscripts.
3) Check your solubility rules. If either product is
insoluble, a precipitate forms.
4) Balance the equation.
Aqueous
Reactions

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 Ways to Write Equations for
Metathesis Reactions
1) Molecular equation
2) Complete ionic equation
3) Net ionic equation

Aqueous
Reactions

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 Molecular Equation
• The molecular equation lists the reactants and
products without indicating the ionic nature of the
compounds. The only indication of the overall
reaction is the states of matter given.

Pb(NO3)2 (aq) + 2 KCl (aq) PbCl2 (s) + 2 KNO3(aq)

Aqueous
Reactions

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 Complete Ionic Equation
• In the complete ionic equation all strong
electrolytes (strong acids, strong bases, and
soluble ionic salts) are dissociated into their ions.
• This more accurately reflects the species that are
found in the reaction mixture.

Aqueous
Reactions

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 Net Ionic Equation
• To form the net ionic equation, cross out anything
that does not change from the left side of the
equation to the right.
• The ions crossed out are called spectator ions, K+
and NO3−, in this example.
• The remaining ions are the reactants that form the
product—an insoluble salt in a precipitation
reaction, as in this example.

Aqueous
Reactions

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 Net Ionic Equation
• To form the net ionic equation, cross out anything that does
not change from the left side of the equation to the right.
• The only things left in the equation are those things that
change (i.e., react) during the course of the reaction.
• Those things that didn’t change (and were deleted from the
net ionic equation) are called spectator ions:

Ag+(aq) + NO3−(aq) + K+(aq) + Cl−(aq) ¾®

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AgCl(s) + K+(aq) + NO3−(aq)

Ag+(aq) + Cl−(aq) ¾® AgCl(s)

Aqueous
Reactions

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 How to Write a Net Ionic Equation

1) Write a balanced molecular equation for the

reaction.
2) Rewrite the equation to show the ions that form
in solution when each soluble strong electrolyte
dissociates into its ions. Only strong
electrolytes dissolved in aqueous solution are
written in ionic form.
3) Identify and cancel spectator ions.

Aqueous
Reactions

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Sample Exercise 4.3 Predicting a Metathesis Reaction
(a) Predict the identity of the precipitate that forms when aqueous solutions of BaCl2 and K2SO4 are
mixed. (b) Write the balanced chemical equation for the reaction.

Solution
Analyze We are given two ionic reactants and asked to predict the insoluble product that they form.

Plan We need to write the ions present in the

reactants and exchange the anions between the
two cations. Once we have written the chemical
formulas for these products, we can use
Table 4.1 to determine which is insoluble in
water. Knowing the products also allows us to
write the equation for the reaction.

Solve
(a) The reactants contain Ba2+, Cl–, K+, and
SO42– ions. Exchanging the anions gives
us BaSO4 and KCl. According to Table 4.1, most compounds of SO42– are soluble but those of Ba2+ are not. Thus,
BaSO4 is insoluble and will precipitate from solution. KCl is soluble.
(b) From part (a) we know the chemical formulas of the products, BaSO4 and KCl. The balanced equation is

BaCl2(aq) + K2SO4(aq) BaSO4(s) + 2 KCl(aq)

Aqueous
Reactions

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Sample Exercise 4.3 Predicting a Metathesis Reaction
Continued

Practice Exercise 1
Yes or No: Will a precipitate form when solutions of Ba(NO3)2 and KOH are mixed?

Practice Exercise 2
(a) What compound precipitates when aqueous solutions of Fe2(SO4)3 and LiOH are mixed? (b) Write a balanced
equation for the reaction.

Aqueous
Reactions

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Sample Exercise 4.4 Writing a Net Ionic Equation
Write the net ionic equation for the precipitation reaction that occurs when aqueous solutions of
calcium chloride and sodium carbonate are mixed.

Solution
Analyze Our task is to write a net ionic equation for a precipitation reaction, given the names of the reactants present in
solution.

Plan We write the chemical formulas of the reactants and products and then determine which product is insoluble. We
then write and balance the molecular equation. Next, we write each soluble strong electrolyte as separated ions to
obtain the complete ionic equation. Finally, we eliminate the spectator ions to obtain the net ionic equation.

Solve Calcium chloride is composed of calcium ions, Ca2+, and chloride ions, Cl–; hence, an aqueous solution of the
substance is CaCl2(aq). Sodium carbonate is composed of Na+ ions and CO32– ions; hence, an aqueous solution of the
compound is Na2CO3(aq). In the molecular equations for precipitation reactions, the anions and cations appear to
exchange partners. Thus, we put Ca2+ and CO32–
together to give CaCO3 and Na+ and Cl– together
to give NaCl. According to the solubility
guidelines in Table 4.1, CaCO3 is insoluble and
NaCl is soluble. The balanced molecular equation is

CaCl2(aq) + Na2CO3(aq)
CaCO3(s) + 2 NaCl(aq)

Aqueous
Reactions

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Sample Exercise 4.4 Writing a Net Ionic Equation
Continued

In a complete ionic equation, only dissolved strong electrolytes (such as soluble ionic compounds) are written as
separate ions. As the (aq) designations remind us, CaCl2, Na2CO3, and NaCl are all dissolved in the solution.
Furthermore, they are all strong electrolytes. CaCO3 is an ionic compound, but it is not soluble. We do not write the
formula of any insoluble compound as its component ions. Thus, the complete ionic equation is

Ca2+(aq) + 2 Cl–(aq) + 2 Na+(aq) + CO32–(aq) CaCO3(s) + 2 Na+(aq) + 2 Cl–(aq)

The spectator ions are Na+ and Cl–. Canceling them gives the following net ionic equation:

Ca2+(aq) + CO32–(aq) CaCO3(s)

Check We can check our result by confirming that both the elements and the electric charge are balanced. Each side
has one Ca, one C, and three O, and the net charge on each side equals 0.

Comment If none of the ions in an ionic equation is removed from solution or changed in some way, all ions are
spectator ions and a reaction does not occur.

Aqueous
Reactions

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Sample Exercise 4.4 Writing a Net Ionic Equation
Continued

Practice Exercise 1
What happens when you mix an aqueous solution of sodium nitrate with an aqueous solution of barium chloride?
(a) There is no reaction; all possible products are soluble.
(b) Only barium nitrate precipitates.
(c) Only sodium chloride precipitates.
(d) Both barium nitrate and sodium chloride precipitate.
(e) Nothing; barium chloride is not soluble and it stays as a precipitate.

Practice Exercise 2
Write the net ionic equation for the precipitation reaction that occurs when aqueous solutions of silver nitrate and
potassium phosphate are mixed.

Aqueous
Reactions

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 Acids

• Acids as substances that ionize in aqueous

solution to form H+
• Because H+ consists of ONLY a proton, acids
are often called proton donors.

Aqueous
Reactions

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 Bases

• Bases are substances that react with, or accept,

H+ ions; they increase the concentration of OH–
when dissolved in water.
• Substances do NOT have to contain OH– to be
a base.

Aqueous
Reactions

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 Strong or Weak?

• Strong acids completely dissociate in water; weak

acids only partially dissociate.
• Strong bases dissociate to metal cations and
hydroxide anions in water; weak bases only
partially react to produce hydroxide anions.

Aqueous
Reactions

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 Strong or Weak Electrolyte?
1) Is the substance ionic or molecular? If it is ionic, it is a
strong electrolyte. (Solubility?)
2) Molecular: is it an acid or a base?
3) If it starts with H or ends in COOH, it is an acid. If it is NOT
on the list of strong acids, it is a weak acid. (Strong acid =
strong electrolyte; weak acid = weak electrolyte.)
4) Strong bases (Table 4.2) are strong electrolytes; NH3 is a
weak base (weak electrolyte).

Aqueous
Reactions

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Sample Exercise 4.5 Comparing Acid Strengths
The following diagrams represent aqueous solutions of acids HX, HY, and HZ, with water molecules omitted for
clarity. Rank the acids from strongest to weakest.

Solution
Analyze We are asked to rank three acids from strongest to weakest, based on schematic drawings of their solutions.

Plan We can determine the relative numbers of uncharged molecular species in the diagrams. The strongest acid is the
one with the most H+ ions and fewest undissociated molecules in solution. The weakest acid is the one with the largest
number of undissociated molecules.

Solve The order is HY > HZ > HX. HY is a strong acid because it is totally ionized (no HY molecules in solution),
whereas both HX and HZ are weak acids, whose solutions consist of a mixture of molecules and ions. Because HZ
contains more H+ ions and fewer molecules than HX, it is a stronger acid.
Aqueous
Reactions

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Sample Exercise 4.5 Comparing Acid Strengths
Continued

Practice Exercise 1
A set of aqueous solutions are prepared containing different acids at the same concentration: acetic acid, chloric acid,
and hydrobromic acid. Which solution(s) are the most electrically conductive? (a) chloric acid (b) hydrobromic acid
(c) acetic acid (d) both chloric acid and hydrobromic acid (e) all three solutions have the same electrical conductivity

Practice Exercise 2
Imagine a diagram showing 10 Na+ ions and 10 OH– ions. If this solution were mixed with the one pictured above for
HY, what species would be present in a diagram that represents the combined solutions after any possible reaction?

Aqueous
Reactions

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Sample Exercise 4.6 Identifying Strong, Weak, and Nonelectrolytes
Classify these dissolved substances as a strong electrolyte, weak electrolyte, or nonelectrolyte: CaCl2, HNO3,
C2H5OH (ethanol), HCOOH (formic acid), KOH.

Solution
Analyze We are given several chemical formulas and asked to classify each substance as a strong electrolyte, weak
electrolyte, or nonelectrolyte.

Plan The approach we take is outlined in Table 4.3. We can predict whether a substance is ionic or molecular based on
its composition. As we saw in Section 2.7, most ionic compounds we encounter in this text are composed of a metal
and a nonmetal, whereas most molecular compounds are composed only of nonmetals.

Solve Two compounds fit the criteria for ionic compounds: CaCl2 and KOH. Because Table 4.3 tells us that all ionic
compounds are strong electrolytes, that is how we classify these two substances. The three remaining compounds are
molecular. Two of these molecular substances, HNO3 and HCOOH, are acids. Nitric acid, HNO3, is a common strong
acid, as shown in Table 4.2, and therefore is a strong electrolyte. Because most acids are weak acids, our best guess
would be that HCOOH is a weak acid (weak electrolyte), which is in fact the case. The remaining molecular
compound, C2H5OH, is neither an acid nor a base, so it is a nonelectrolyte.
Aqueous
Reactions

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Sample Exercise 4.6 Identifying Strong, Weak, and Nonelectrolytes
Continued

Comment Although ethanol, C2H5OH, has an OH group, it is not a metal hydroxide and therefore not a base. Rather,
ethanol is a member of a class of organic compounds that have C—OH bonds, which are known as alcohols.
(Section 2.9) Organic compounds containing the COOH group are called carboxylic acids (Chapter 16).
Molecules that have this group are weak acids.

Practice Exercise 1
Which of these substances, when dissolved in water, is a strong electrolyte? (a) ammonia (b) hydrofluoric acid
(c) folic acid (d) sodium nitrate (e) sucrose

Aqueous
Reactions

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Sample Exercise 4.6 Identifying Strong, Weak, and Nonelectrolytes
Continued

Practice Exercise 2
Consider solutions in which 0.1 mol of each of the following compounds is dissolved in 1 L of water: Ca(NO3)2
(calcium nitrate), C6H12O6 (glucose), NaCH3COO (sodium acetate), and CH3COOH (acetic acid). Rank the solutions
in order of increasing electrical conductivity, knowing that the greater the number of ions in solution, the greater the
conductivity.

Aqueous
Reactions

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 Neutralization Reactions
• Reactions between an acid and a base are called
neutralization reactions.
• When the base is a metal hydroxide, water and a salt (an
ionic compound) are produced.
• These equations can be written as molecular, complete
ionic, or net ionic equations.

Aqueous
Reactions

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 Neutralization Reactions with
Gas Formation
• Some metathesis reactions do not give the
product expected.
• In this reaction, the expected product (H2CO3)
decomposes to give a gaseous product (CO2):
• When a carbonate or bicarbonate reacts with an
acid, the products are a salt, carbon dioxide, and
water.
CaCO3(s) + 2 HCl(aq) CaCl2(aq) + CO2(g) + H2O(l)
NaHCO3(aq) + HBr(aq) NaBr(aq) + CO2(g) + H2O(l)
Aqueous
Reactions

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 Neutralization Reactions with
Gas Formation
• Similarly, when a sulfite reacts with an acid, the
products are a salt, sulfur dioxide, and water:
SrSO3(s) + 2HI(aq) ¾®SrI2(aq) + SO2(g) + H2O(l)

• This reaction gives the predicted product, but

you had better carry it out in the hood—the gas
produced has the odor of rotten eggs!
Na2S(aq) + H2SO4(aq) Na2SO4(aq) + H2S(g)

Aqueous
Reactions

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 Application of Neutralization Reactions:
Antacids

Aqueous
Reactions

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 Aqueous
Note that the ions exchange partners thus neutralization reactions between acids and metal Reactions
hydroxides are metathesis reactions
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Sample Exercise 4.7 Writing Chemical Equations for a Neutralization
Reaction
For the reaction between aqueous solutions of acetic acid (CH3COOH) and barium hydroxide, Ba(OH)2, write
(a) the balanced molecular equation, (b) the complete ionic equation, (c) the net ionic equation.

Solution
Analyze We are given the chemical formulas for an acid and a base and asked to write a balanced molecular equation, a
complete ionic equation, and a net ionic equation for their neutralization reaction.

Plan As Equation 4.11 and the italicized statement that follows it indicate, neutralization reactions form two products,
H2O and a salt. We examine the cation of the base and the anion of the acid to determine the composition of the salt.

Solve
(a) The salt contains the cation of the base (Ba2+) and the anion of the acid (CH3COO–). Thus, the salt formula is
Ba(CH3COO)2. According to Table 4.1, this compound is soluble in water. The unbalanced molecular equation for
the neutralization reaction is:

CH3COOH(aq) + Ba(OH)2(aq)
H2O(l) + Ba(CH3COO)2(aq)

Aqueous
Reactions

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Sample Exercise 4.7 Writing Chemical Equations for a Neutralization
Reaction
Continued

To balance this equation, we must provide two molecules of CH3COOH to furnish the two CH3COO– ions and to
supply the two H+ ions needed to combine with the two OH– ions of the base. The balanced molecular equation is:

2 CH3COOH(aq) + Ba(OH)2(aq) 2 H2O(l) + Ba(CH3COO)2(aq)

(b) To write the complete ionic equation, we identify the strong electrolytes and break them into ions. In this case
Ba(OH)2 and Ba(CH3COO)2 are both water-soluble ionic compounds and hence strong electrolytes. Thus, the
complete ionic equation is:

2 CH3COOH(aq) + Ba2+(aq) + 2OH–(aq) 2 H2O(l) + Ba2+(aq) + 2 CH3COO–(aq)

(c) Eliminating the spectator ion, Ba2+, and simplifying coefficients give the net ionic equation:

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

Check We can determine whether the molecular equation is balanced by counting the number of atoms of each kind on
both sides of the arrow (10 H, 6 O, 4 C, and 1 Ba on each side). However, it is often easier to check equations by
counting groups: There are 2 CH3COO groups, as well as 1 Ba, and 4 additional H atoms and 2 additional O atoms on
each side of the equation. The net ionic equation checks out because the numbers of each kind of element and the net
charge are the same on both sides of the equation.

Aqueous
Reactions

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Sample Exercise 4.7 Writing Chemical Equations for a Neutralization
Reaction
Continued

Practice Exercise 1
Which is the correct net ionic equation for the reaction of aqueous ammonia with nitric acid?
(a) NH4+(aq) + H+(aq) NH52+(aq)
(b) NH3(aq) + NO3–(aq) NH2–(aq) + HNO3(aq)
– +
(c) NH2 (aq) + H (aq) NH3(aq)
+
(d) NH3(aq) + H (aq) NH4+(aq)
(e) NH4+(aq) + NO3–(aq) NH4NO3(aq)

Practice Exercise 2
For the reaction of phosphorous acid (H3PO3) and potassium hydroxide (KOH), write (a) the balanced molecular
equation and (b) the net ionic equation. Note that phosphorous acid is a diprotic acid.

Aqueous
Reactions

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 Oxidation-Reduction Reactions

• Loss of electrons is oxidation.

• Gain of electrons is reduction.
• One cannot occur without the other.
Aqueous
• The reactions are often called redox reactions. Reactions

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 Oxidation Numbers

• Electrons are not explicitly shown in chemical

equations.
• Oxidation numbers (or oxidation states) help
up keep track of electrons during chemical
reactions.
• To determine if an oxidation–reduction
reaction has occurred, we assign an oxidation
number to each element in a neutral
compound or charged entity.
Aqueous
Reactions

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 Rules to Assign Oxidation Numbers

1) Atoms in their elemental form have an

oxidation number of zero.
2) The oxidation number of a monatomic ion is
the same as its charge.

Aqueous
Reactions

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 Rules to Assign Oxidation Numbers

3) Nonmetals usually have negative oxidation

numbers, although they sometimes can be
positive:
– Oxygen: usually −2, except in the peroxide ion, where
it is −1.
– Hydrogen: usually +1 when bonded to a nonmetal and
−1 when bonded to a metal.
– Fluorine: –1. Other halogens: usually –1, unless
combined with oxygen (oxyanions), where they will be
positive.

Aqueous
Reactions

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 Rules to Assign Oxidation Numbers

4) The sum of the oxidation numbers in a neutral

compound is zero;
5) The sum of the oxidation numbers in a
polyatomic ion is the charge on the ion.
(Remember to count EVERY atom, no matter
how large the subscript, when assigning
oxidation numbers!)
6) The oxidation of an element is evidenced by an
increase in its oxidation number; reduction is
accompanied by a decrease in an oxidation
number. Aqueous
Reactions

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Sample Exercise 4.8 Determining Oxidation Numbers
Determine the oxidation number of sulfur in (a) H2S, (b) S8, (c) SCl2, (d) Na2SO3, (e) SO42–.

Solution
Analyze We are asked to determine the oxidation number of sulfur in two molecular species, in the elemental form, and
in two substances containing ions.

Plan In each species, the sum of oxidation numbers of all the atoms must equal the charge on the species. We will use
the rules outlined previously to assign oxidation numbers.

Solve
(a) When bonded to a nonmetal, hydrogen has an oxidation number of +1. Because the H2S molecule is neutral, the
sum of the oxidation numbers must equal zero. Letting x equal the oxidation number of S, we have 2(+1) + x = 0.
Thus, S has an oxidation number of –2.
(b) Because S8 is an elemental form of sulfur, the oxidation number of S is 0.
(c) Because SCl2 is a binary compound, we expect chlorine to have an oxidation number of –1. The sum of the
oxidation numbers must equal zero. Letting x equal the oxidation number of S, we have x + 2(–1) = 0.
Consequently, the oxidation number of S must be +2.
(d) Sodium, an alkali metal, always has an oxidation number of +1 in its compounds. Oxygen commonly has an
oxidation state of –2. Letting x equal the oxidation number of S, we have 2(+1) + x + 3(–2) = 0. Therefore, the
oxidation number of S in this compound (Na2SO3) is +4.
(e) The oxidation state of O is –2. The sum of the oxidation numbers equals –2, the net charge of the SO42– ion. Thus,
we have x + 4(–2) = –2. From this relation we conclude that the oxidation number of S in this ion is +6.

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Sample Exercise 4.8 Determining Oxidation Numbers
Continued

Comment These examples illustrate that the oxidation number of a given element depends on the compound in which
it occurs. The oxidation numbers of sulfur, as seen in these examples, range from –2 to +6.

Practice Exercise 1
In which compound is the oxidation state of oxygen –1?
(a) O2 (b) H2O (c) H2SO4 (d) H2O2 (e) KCH3COO

Practice Exercise 2
What is the oxidation state of the boldfaced element in
(a) P2O5, (b) NaH, (c) Cr2O72–, (d) SnBr4, (e) BaO2?

Aqueous
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 Displacement Reactions
• In displacement reactions, ions oxidize an
element. (H+ oxidizes Mg below.)
• The ion is displaced (replaced) in solution.
(Mg replaces – reduces - H+ below.)

A + BX → AX + B

Aqueous
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Sample Exercise 4.9 Writing Equations for Oxidation-Reduction
Reactions
Write the balanced molecular and net ionic equations for the reaction of aluminum with hydrobromic acid.

Solution
Analyze We must write two equations—molecular and net ionic—for the redox reaction between a metal and an acid.

Plan Metals react with acids to form salts and H2 gas. To write the balanced equations, we must write the chemical
formulas for the two reactants and then determine the formula of the salt, which is composed of the cation formed by
the metal and the anion of the acid.

Solve The reactants are Al and HBr. The cation formed by Al is Al3+, and the anion from hydrobromic acid is Br–. Thus,
the salt formed in the reaction is AlBr3. Writing the reactants and products and then balancing the equation gives the
molecular equation:

2 Al(s) + 6 HBr(aq) 2 AlBr3(aq) + 3 H2(g)

Both HBr and AlBr3 are soluble strong electrolytes. Thus, the complete ionic equation is

2 Al(s) + 6 H+(aq) + 6 Br–(aq) 2 Al3+(aq) + 6 Br–(aq) + 3 H2(g)

Because Br– is a spectator ion, the net ionic equation is

2 Al(s) + 6 H+(aq) 2 Al3+(aq) + 3 H2(g)

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Sample Exercise 4.9 Writing Equations for Oxidation-Reduction
Reactions
Continued

Comment The substance oxidized is the aluminum metal because its oxidation state changes from 0 in the metal to +3
in the cation, thereby increasing in oxidation number. The H+ is reduced because its oxidation state changes from +1 in
the acid to 0 in H2.

Practice Exercise 1
Which of the following statements is true about the reaction between zinc and copper sulfate? (a) Zinc is oxidized, and
copper ion is reduced. (b) Zinc is reduced, and copper ion is oxidized. (c) All reactants and products are soluble strong
electrolytes. (d) The oxidation state of copper in copper sulfate is 0. (e) More than one of the previous choices are true.

Practice Exercise 2
(a) Write the balanced molecular and net ionic equations for the reaction between magnesium and cobalt(II) sulfate.
(b) What is oxidized, and what is reduced in the reaction?

Aqueous
Reactions

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 Metal/Acid Displacement Reactions

• Elements higher on the activity series are more

reactive.
• They will exist as ions.
Aqueous
• The element below will exist as the element. Reactions
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 The Activity Series
• We can list metals in order of decreasing ease
of oxidation: This list is an activity series.
• The metals at the top of the activity series are
called active metals.
• The metals at the bottom of the activity series
are called noble metals.
• A metal in the activity series can only be
oxidized by a metal ion below it.

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 Activity Series and Hydrogen

• The elements
above hydrogen will
react with acids to
produce hydrogen
gas. Elements
below will NOT
react!
• A reactive metal is
oxidized to a cation.

Aqueous
Reactions

© 2018 Pearson Education, Inc.

Sample Exercise 4.10 Determining If an Oxidation-Reduction
Reaction Will Occur
Will an aqueous solution of iron(II) chloride oxidize magnesium metal? If so, write the balanced molecular and net
ionic equations for the reaction.

Solution
Analyze We are given two substances—an aqueous salt, FeCl2, and a metal, Mg—and asked if they react with
each other.

Plan A reaction occurs if the reactant that is a metal in its

elemental form (Mg) is located above the reactant that is a
metal in its oxidized form (Fe2+) in Table 4.5. If the reaction
occurs, the Fe2+ ion in FeCl2 is reduced to Fe, and the Mg is
oxidized to Mg2+.

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Sample Exercise 4.10 Determining If an Oxidation-Reduction
Reaction Will Occur
Continued

Solve Because Mg is above Fe in the table, the reaction occurs. To write the formula for the salt produced in
the reaction, we must remember the charges on common ions. Magnesium is always present in compounds as Mg2+; the
chloride ion is Cl–. The magnesium salt formed in the reaction is MgCl2, meaning the balanced molecular equation is

Mg(s) + FeCl2(aq) MgCl2(aq) + Fe(s)

Both FeCl2 and MgCl2 are soluble strong electrolytes and can be written in ionic form, which shows us that Cl– is a
spectator ion in the reaction. The net ionic equation is

Mg(s) + Fe2+ (aq) Mg2+ (aq) + Fe(s)

The net ionic equation shows that Mg is oxidized and Fe2+ is reduced in this reaction.

Check Note that the net ionic equation is balanced with respect to both charge and mass.

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© 2018 Pearson Education, Inc.

Sample Exercise 4.10 Determining If an Oxidation-Reduction
Reaction Will Occur
Continued

Practice Exercise 1
Which of these metals is the easiest to oxidize? (a) gold (b) lithium (c) iron (d) sodium (e) aluminum

Practice Exercise 2
Which of the following metals will be oxidized by Pb(NO3)2: Zn, Cu, Fe?

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© 2018 Pearson Education, Inc.

 Concentrations of Solutions - Molarity
• Two solutions can contain the same compounds but
be quite different because the proportions of those
compounds are different.
• Molarity (molar conc.) is one way to measure the
concentration of a solution.
• By knowing the molarity of a quantity of liters of
solution, we can easily calculate the number of moles
(and, by using molar mass, the mass) of solute.

moles of solute
Molarity (M) =
volume of solution in liters
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Sample Exercise 4.11 Calculating Molarity
Calculate the molarity of a solution made by dissolving 23.4 g of sodium sulfate (Na2SO4) in enough water to form
125 mL of solution.

Solution
Analyze We are given the number of grams of solute (23.4 g), its chemical formula (Na2SO4), and the volume of the
solution (125 mL) and asked to calculate the molarity of the solution.

Plan We can calculate molarity using Equation 4.31. To do so, we must convert the number of grams of solute to moles
and the volume of the solution from milliliters to liters.

Solve
The number of moles of Na2SO4 is obtained by using its molar mass:

Converting the volume of the solution to liters:

Thus, the molarity is:

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© 2018 Pearson Education, Inc.

Sample Exercise 4.11 Calculating Molarity
Continued

Check Because the numerator is only slightly larger than the denominator, it is reasonable for the answer to be a little
over 1 M. The units (mol/L) are appropriate for molarity, and three significant figures are appropriate for the answer
because each of the initial pieces of data had three significant figures.

Practice Exercise 1
What is the molarity of a solution that is made by dissolving 3.68 g of sucrose (C12H22O11) in sufficient water to form
275.0 mL of solution? (a) 13.4 M (b) 7.43 × 10–2 M (c) 3.91 × 10–2 M (d) 7.43 × 10–5 M (e) 3.91 × 10–5 M

Practice Exercise 2
Calculate the molarity of a solution made by dissolving 5.00 g of glucose (C6H12O6) in sufficient water to form exactly
100 mL of solution.

Aqueous
Reactions

© 2018 Pearson Education, Inc.

Sample Exercise 4.12 Calculating Molar Concentrations of Ions
What is the molar concentration of each ion present in a 0.025 M aqueous solution of calcium nitrate?

Solution
Analyze We are given the concentration of the ionic compound used to make the solution and asked to determine the
concentrations of the ions in the solution.

Plan We can use the subscripts in the chemical formula of the compound to determine the relative ion concentrations.

Solve Calcium nitrate is composed of calcium ions (Ca2+) and nitrate ions (NO3–), so its chemical formula is Ca(NO3)2.
Because there are two NO3– ions for each Ca2+ ion, each mole of Ca(NO3)2 that dissolves dissociates into 1 mol of Ca2+
and 2 mol of NO3–. Thus, a solution that is 0.025 M in Ca(NO3)2 is 0.025 M in Ca2+ and 2 × 0.025 M = 0.050 M in
NO3–:

Check The concentration of NO3– ions is twice that of Ca2+ ions, as the subscript 2 after the NO3– in the chemical
formula Ca(NO3)2 suggests.

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Sample Exercise 4.12 Calculating Molar Concentrations of Ions
Continued

Practice Exercise 1
What is the ratio of the concentration of potassium ions to the concentration of carbonate ions in a 0.015 M solution of
potassium carbonate? (a) 1:0.015 (b) 0.015:1 (c) 1:1 (d) 1:2 (e) 2:1

Practice Exercise 2
What is the molar concentration of K+ ions in a 0.015 M solution of potassium carbonate?

Aqueous
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© 2018 Pearson Education, Inc.

Sample Exercise 4.13 Using Molarity to Calculate Grams of
Solute
How many grams of Na2SO4 are required to make 0.350 L of 0.500 M Na2SO4?

Solution
Analyze We are given the volume of the solution (0.350 L), its concentration (0.500 M), and the identity of the solute
Na2SO4 and asked to calculate the number of grams of the solute in the solution.

Plan We can use the definition of molarity (Equation 4.31) to determine the number of moles of solute, and then
convert moles to grams using the molar mass of the solute.

Solve Calculating the moles of Na2SO4 using the molarity and volume of solution gives

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Reactions

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Sample Exercise 4.13 Using Molarity to Calculate Grams of
Solute
Continued

Because each mole of Na2SO4 has a mass of 142.1 g, the required number of grams of Na2SO4 is

Check The magnitude of the answer, the units, and the number of significant figures are all appropriate.

Practice Exercise 1
What is the concentration of ammonia in a solution made by dissolving 3.75 g of ammonia in 120.0 L of water?
(a) 1.84 × 10–3 M (b) 3.78 × 10–2 M (c) 0.0313 M (d) 1.84 M (e) 7.05 M

Practice Exercise 2
(a) How many grams of Na2SO4 are there in 15 mL of 0.50 M Na2SO4? (b) How many milliliters of 0.50 M Na2SO4
solution are needed to provide 0.038 mol of this salt?

Aqueous
Reactions

© 2018 Pearson Education, Inc.

 Mixing a Solution
• To create a solution of a known molarity, weigh out a
known mass (and, therefore, number of moles) of the
solute.
• Then add solute to a volumetric flask, and add solvent to
the line on the neck of the flask.

Aqueous
Reactions

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 Dilution
• One can also dilute a more concentrated
solution by
– Using a pipet to deliver a volume of the solution to a
new volumetric flask, and
– Adding solvent to the line on the neck of the new
flask.

Aqueous
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 Dilution

The molarity of the new solution can be

determined from the equation

Mc × Vc = Md × Vd,

where Mc and Md are the molarity of the

concentrated and dilute solutions, respectively,
and Vc and Vd are the volumes of the two
solutions.

[Remember: M × V (in L) = moles!]

Aqueous
Reactions

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Sample Exercise 4.14 Preparing a Solution by Dilution
How many milliliters of 3.0 M H2SO4 are needed to make 450 mL of 0.10 M H2SO4?

Solution
Analyze We need to dilute a concentrated solution. We are given the molarity of a more concentrated solution (3.0 M)
and the volume and molarity of a more dilute one containing the same solute (450 mL of 0.10 M solution). We must
calculate the volume of the concentrated solution needed to prepare the dilute solution.

Plan We can calculate the number of moles of solute, H2SO4, in the dilute solution and then calculate the volume of the
concentrated solution needed to supply this amount of solute. Alternatively, we can directly apply Equation 4.33. Let’s
compare the two methods.

Solve Calculate the moles of H2SO4 in the dilute solution:

Calculate the volume of the concentrated solution that contains 0.045 mol H2SO4:
Converting liters to milliliters gives 15 mL.

Aqueous
Reactions

© 2018 Pearson Education, Inc.

Sample Exercise 4.14 Preparing a Solution by Dilution
Continued

If we apply Equation 4.33, we get the same result:

Either way, we see that if we start with 15 mL of 3.0 M H2SO4 and dilute it to a total volume of 450 mL, the desired
0.10 M solution will be obtained.

Check The calculated volume seems reasonable because a small volume of concentrated solution is used to prepare a
large volume of dilute solution.

Comment The first approach can also be used to find the final concentration when two solutions of different
concentrations are mixed, whereas the second approach, using Equation 4.33, can be used only for diluting a
concentrated solution with pure solvent.

Practice Exercise 1
What volume of a 1.00 M stock solution of glucose must be used to make 500.0 mL of a 1.75 × 10–2 M glucose
solution in water?
(a) 1.75 mL (b) 8.75 mL (c) 48.6 mL (d) 57.1 mL (e) 28,570 mL

Aqueous
Reactions

© 2018 Pearson Education, Inc.

Sample Exercise 4.14 Preparing a Solution by Dilution
Continued

Practice Exercise 2
(a) What volume of 2.50 M lead(II) nitrate solution contains 0.0500 mol of Pb2+? (b) How many milliliters of 5.0 M
K2Cr2O7 solution must be diluted to prepare 250 mL of 0.10 M solution? (c) If 10.0 mL of a 10.0 M stock solution of
NaOH is diluted to 250 mL, what is the concentration of the resulting stock solution?

Aqueous
Reactions

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 Solution Stoichiometry and Chemical
Analysis
• Recognize that there are two different types of units:
• laboratory units (the macroscopic units that we measure in lab)
• chemical units (the microscopic units that relate to moles).
• Always convert the laboratory units into chemical units
first.
– Convert grams to moles using molar mass.
– Convert volume or molarity into moles using M = mol/L.
• Use the stoichiometric coefficients to move between
reactants and products.
© 2012 Pearson Education, Inc.

– This step requires the balanced chemical equation.

• Convert the chemical units back into the laboratory units.
– Convert moles to grams using molar mass.
– Convert moles to molarity or volume using M = mol/L. Aqueous
Reactions

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 Stoichiometry Applied to Solutions

Aqueous
Reactions

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Sample Exercise 4.15 Using Mass Relations in a Neutralization
Reaction
How many grams of Ca(OH)2 are needed to neutralize 25.0 mL of 0.100 M HNO3?

Solution
Analyze The reactants are an acid, HNO3, and a base, Ca(OH)2. The volume and molarity of HNO3 are given, and we
are asked how many grams of Ca(OH)2 are needed to neutralize this quantity of HNO3.

Plan Following the steps outlined by the green arrows in Figure 4.17, we use the molarity and volume of the HNO3
solution (substance B in Figure 4.17) to calculate the number of moles of HNO3. We then use the balanced equation to
relate moles of HNO3 to moles of Ca(OH)2 (substance A). Finally, we use the molar mass to convert moles to grams of
Ca(OH)2:

Solve
The product of the molar concentration of a solution and its volume in liters gives
the number of moles of solute:

Aqueous
Reactions

© 2018 Pearson Education, Inc.

Sample Exercise 4.15 Using Mass Relations in a Neutralization
Reaction
Continued

Because this is a neutralization reaction, HNO3 and Ca(OH)2 react to form H2O and the salt containing Ca2+ and NO3–:

2 HNO3(aq) + Ca(OH)2(s) 2 H2O(l) + Ca(NO3)2(aq)

Thus, 2 mol HNO3 1 mol Ca(OH)2. Therefore,

Check The answer is reasonable because a small volume of dilute acid requires only a small amount of base to
neutralize it.

Practice Exercise 1
How many milligrams of sodium sulfide are needed to completely react with 25.00 mL of a 0.0100 M aqueous solution
of cadmium nitrate, to form a precipitate of CdS(s)? (a) 13.8 mg (b) 19.5 mg (c) 23.5 mg (d) 32.1 mg (e) 39.0 mg

Practice Exercise 2
(a) How many grams of NaOH are needed to neutralize 20.0 mL of 0.150 M H2SO4 solution? (b) How many liters
of 0.500 M HCl(aq) are needed to react completely with 0.100 mol of Pb(NO3)2(aq), forming a precipitate of PbCl2(s)?

Aqueous
Reactions

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 Titration
• A titration is an analytical technique in which one
can calculate the concentration of a solute in a
solution.

Aqueous
Reactions

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 Titrations
• A common way to determine the concentration
of a solution is via titration.
• We determine the concentration of one
substance by allowing it to undergo a specific
chemical reaction, of known stoichiometry, with
a substance with known concentration
(standard solution).
• Monoprotic acids and bases react with each
other in a stoichiometric ratio of 1:1.

Aqueous
Reactions

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 Titration
• The reaction is complete at the equivalence
point, which is based on the seen end point
(color change).

Aqueous
Reactions

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Sample Exercise 4.16 Determining Solution Concentration by an
Acid–Base Titration
One commercial method used to peel potatoes is to soak them in a NaOH solution for a short time and then remove the
potatoes and spray off the peel. The NaOH concentration is normally 3 to 6 M, and the solution must be analyzed
periodically. In one such analysis, 45.7 mL of 0.500 M H2SO4 is required to neutralize 20.0 mL of NaOH solution.
What is the concentration of the NaOH solution?

Solution
Analyze We are given the volume (45.7 mL) and molarity (0.500 M) of an H2SO4 solution (the standard solution) that
reacts completely with 20.0 mL of NaOH solution. We are asked to calculate the molarity of the NaOH solution.

Plan Following the steps given in Figure 4.19, we use the H2SO4
volume and molarity to calculate the number of moles of H2SO4.
Then we can use this quantity and the balanced equation for the
reaction to calculate moles of NaOH. Finally, we can use moles
of NaOH and the NaOH volume to calculate NaOH molarity.

Solve
The number of moles of H2SO4 is the product of the volume and
molarity of this solution:

Aqueous
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Sample Exercise 4.16 Determining Solution Concentration by an
Acid–Base Titration
Continued

Acids react with metal hydroxides to form water and a salt. Thus, the balanced equation for the neutralization
reaction is:

H2SO4(aq) + 2 NaOH(aq) 2 H2O(l) + Na2SO4(aq)

According to the balanced equation, 1 mol H2SO4 2 mol NaOH. Therefore,

Knowing the number of moles of NaOH in 20.0 mL of solution allows us to calculate the molarity of this solution:

Aqueous
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Sample Exercise 4.16 Determining Solution Concentration by an
Acid–Base Titration
Continued

Practice Exercise 1
What is the molarity of an HCl solution if 27.3 mL of it neutralizes 134.5 mL of 0.0165 M Ba(OH)2?
(a) 0.0444 M (b) 0.0813 M (c) 0.163 M (d) 0.325 M (e) 3.35 M

Practice Exercise 2
What is the molarity of a NaOH solution if 48.0 mL neutralizes 35.0 mL of 0.144 M H2SO4?

Aqueous
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Sample Exercise 4.17 Determining the Quantity of Solute by Titration
The quantity of Cl– in a municipal water supply is determined by titrating the sample with Ag+. The precipitation
reaction taking place during the titration is

Ag+(aq) + Cl–(aq) AgCl(s)

(a) How many grams of chloride ion are in a sample of the water if 20.2 mL of 0.100 M Ag+ is needed to react with
all the chloride in the sample? (b) If the sample has a mass of 10.0 g, what percentage of Cl– does it contain?

Solution
Analyze We are given the volume (20.2 mL) and molarity (0.100 M) of a solution of Ag+ and the chemical equation for
reaction of this ion with Cl–. We are asked to calculate the number of grams of Clin the sample and the mass percentage
of Cl– in the sample.

Plan (a) We can use the procedure outlined by the green arrows in
Figure 4.17. We begin by using the volume and molarity of Ag+ to
calculate the number of moles of Ag+ used in the titration. We then
use the balanced equation to determine the moles of Cl– in the
sample and from that the grams of Cl–. (b) To calculate the
percentage of Cl– in the sample, we compare the number
of grams of Cl– in the sample with the original mass of
the sample, 10.0 g.

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Sample Exercise 4.17 Determining the Quantity of Solute by Titration
Continued

Solve
(a) Calculate the number of moles of Ag+ used in the titration.

From the balanced equation we see that 1 mol Ag+ 1 mol Cl–. Using this information and the molar
mass of Cl, we have:

(b) Calculate the percentage of Cl– used in the sample.

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Sample Exercise 4.17 Determining the Quantity of Solute by Titration
Continued

Practice Exercise 1
A mysterious white powder is found at a crime scene. A simple chemical analysis concludes that the powder is a
mixture of sugar and morphine (C17H19NO3), a weak base similar to ammonia. The crime lab takes 10.00 mg of the
mysterious white powder, dissolves it in 100.00 mL water, and titrates it to the equivalence point with 2.84 mL of a
standard 0.0100 M HCl solution. What is the percentage of morphine in the white powder?
(a) 8.10%
(b) 17.3%
(c) 32.6%
(d) 49.7%
(e) 81.0%

Practice Exercise 2
A sample of an iron ore is dissolved in acid, and the iron is converted to Fe2+. The sample is then titrated with
47.20 mL of 0.02240 M MnO4– solution. The oxidation-reduction reaction that occurs during titration is

MnO4–(aq) + 5 Fe2+(aq) + 8 H+(aq) Mn2+(aq) + 5 Fe3+(aq) + 4 H2O(l)

(a) How many moles of MnO4 were added to the solution? (b) How many moles of Fe2+ were in the sample?
–

(c) How many grams of iron were in the sample? (d) If the sample had a mass of 0.8890 g, what is the percentage of
iron in the sample?

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