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CHEM 1103
CHAPTER 4
REACTIONS IN AQUEOUS SOLUTIONS

General Properties of Aqueous

Solutions
• Solution
• Homogeneous mixture of two or more substances
• May be gaseous (such as air), solid (such as brass), or liquid (such
as saltwater)
• Solvent
• Substance present in the largest amount
• Solute
• Substance present in a smaller amount

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General Properties of Aqueous

Solutions
• Electrolytes
• Substance that dissolves in water to yield a solution that conducts
electricity
• Nonelectrolytes
• Substance that dissolves in water to yield a solution that does not
conduct electricity
• The difference between an aqueous solution that
conducts electricity and one that does not is the presence
or absence of ions
C12H22O11  s 
H2O
C12H22O11  aq
NaCl  s 
H2O
Na +  aq + Cl  aq

General Properties of Aqueous

Solutions
• Dissociation
• Process by which an ionic compound, upon dissolution, breaks
apart into its constituent ions
• Ionization
• Process by which a molecular compound forms ions when it
dissolves

HCl  g  
H2O
H  aq  Cl  aq

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General Properties of Aqueous

Solutions
• 2 important classes of molecular compounds that are
electrolytes
• Acids
• Compound that dissolves in water to produce hydronium ions or
hydrogen ions (H3O+ ,H+)
• HCl (aq) + H2O (l) → H+ (aq) + Cl- (aq)
• Molecular bases
• Compound that dissolves in water to produce hydroxide ions (OH–)
• NH3 (g) + H2O (l) → NH4+ (aq) + OH- (aq)

General Properties of Aqueous

Solutions
• Strong Electrolytes
• Electrolyte that dissociates completely
• All water-soluble ionic compounds dissociate completely upon
dissolving
• All water-soluble ionic compounds are strong electrolytes
• Weak Electrolytes
• Compound that produces ions upon dissolving but exists in
solution predominantly as molecules that are not ionized
• Most of the molecular compounds that are electrolytes are weak
electrolytes
• Most acids (except those listed in Table 4.1)

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General Properties of Aqueous

Solutions
TABLE 4.1 The Strong Acids
Acid Ionization Equation
Hydrochloric acid HCl(aq)→H+(aq)+Cl−(aq)
Hydrobromic acid HBr(aq)→H+(aq)+Br−(aq)
Hydroiodic acid HI(aq)→H+ (aq)+I−(aq)
Nitric acid HNO3(aq)→H+(aq)+NO3−(aq)
Chloric acid HCIO3(aq)→H+(aq)+CIO3−(aq)
Perchloric acid HCIO4(aq)→H+(aq)+CIO4−(aq)
Sulfuric acid* H2SO4(aq)→H+(aq)+HSO4−(aq)
HSO4−(aq)⇆H+(aq)+SO42−(aq)

General Properties of Aqueous

Solutions
• Weak Electrolytes
• Ammonia molecule does not ionize by breaking apart into ions. It
does so by ionizing a water molecule.

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General Properties of Aqueous

Solutions

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General Properties of Aqueous

Solutions
• Identifying Electrolytes
• Determine whether the compound is ionic or molecular
• Ionic
• An ionic compound contains a cation (which is either a metal ion or the ammonium ion)
and an anion (which may be atomic or polyatomic)
• A binary compound that contains a metal and a nonmetal is almost always ionic
• Any ionic compound that dissolves in water is a strong electrolyte
• Molecular
• If a compound does not contain a metal cation or the ammonium cation, it is molecular
• In this case, you will need to determine whether or not the compound is an acid
• Acids generally can be recognized by the way their formulas are written, with the
ionizable hydrogens written first

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General Properties of Aqueous

Solutions

SAMPLE PROBLEM 4.1

Classify each of the following compounds as a
nonelectrolyte, a weak electrolyte, or a strong electrolyte:
• methanol (CH3OH)
• sodium hydroxide (NaOH)
• ethylamine (C2H5NH2)
• hydrofluoric acid (HF)

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Precipitation Reactions
• Precipitate
• Insoluble solid product that separates from a solution
• Precipitation reaction
• A chemical reaction in which a precipitate forms

Precipitation Reactions
• Hydration
• When an ionic substance
dissolves in water, the water
molecules remove individual
ions from the three-
dimensional solid structure
and surround them

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Precipitation Reactions
• Solubility
• Maximum amount of solute that will dissolve in a given quantity of
solvent at a specific temperature
• Not all ionic compounds dissolve in water.

Solubility Guidelines for Ionic Compounds in Water

Water-Soluble Compounds Insoluble Exceptions
Compounds containing an alkali metal cation
(Li+, Na+, K+, Rb+, Cs+) or the ammonium ion
(NH4+)

Compounds containing the nitrate ion (NO3−),

acetate ion (C2H3O2−), or chlorate ion (ClO3−)

Compounds containing the chloride ion (Cl−),

Compounds containing Ag+ , Hg22+, or Pb2+
bromide ion (Br−), or iodide ion (I−)
Compounds containing Ag+ , H22+ , Pb2+, Ca2+,
Compounds containing the sulfate ion (SO42−)
Sr2+, or Ba2+
Water-Insoluble Compounds Soluble Exceptions
Compounds containing the carbonate ion Compounds containing Li+, Na+, K+, Rb+, Cs+, or
(CO32−), phosphate ion (PO43−), chromate ion NH4+
(CrO42−), or sulfide ion (S2−)
Compounds containing the hydroxide ion (OH−) Compounds containing Li+, Na+, K+, Rb+, Cs+, or
Ba2+

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SAMPLE PROBLEM 4.2

Classify each of the following compounds as soluble or
insoluble in water:
(a) AgNO3
(b) CaSO4
(c) K2CO3

Precipitation Reactions
• Molecular Equations
• Chemical equation written with all compounds represented by
their chemical formulas, making it look as though they exist in
solution as molecules or formula units

Pb NO3 2aq  2 NaI aq  2 NaNO3aq  PbI2  s

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Precipitation Reactions
• Ionic Equations
• Chemical equation in which any compound that exists
completely or predominantly as ions in solution is
represented as those ions

2Na  aq  SO24  aq  Ba2  aq  2OH  aq 

2Na  aq  2OH  aq  BaSO4  s

Precipitation Reactions
• Net Ionic Equations
• Chemical equation that includes only the species that are
actually involved in the reaction
• Spectator ions
• Ions that appear on both sides of the equation arrow
• Do not participate in the reaction
2Na

 aq  S024  aq  Ba2  aq  2OH  aq 
2Na  aq  2OH  aq  BaSO4  s
 

Ba2  aq  SO24  aq  BaSO4  s 

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Precipitation Reactions
• Net Ionic Equations
• Write and balance the molecular equation, predicting the products
by assuming that the cations trade anions
• Write the ionic equation by separating strong electrolytes into
their constituent ions
• Write the net ionic equation by identifying and canceling spectator
ions on both sides of the equation

SAMPLE PROBLEM 4.3

Write the molecular, ionic, and net ionic equations for the
reaction that occurs when aqueous solutions of lead acetate
[Pb(C2H3O2)2], and calcium chloride (CaCl2), are combined.

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Acid-Base Reactions
TABLE 4.4 Strong Acids and Strong Bases
Strong Acids Strong Bases
HCl LiOH
HBr NaOH
HI KOH
HN03 RbOH
HC103 CsOH
HClO4 Ca(OH)2
H2S04 Sr(OH)2
Ba(OH)2

Acid-Base Reactions
• Arrhenius Acids and Bases
• An acid is a substance that ionizes in water to produce H+ ions
• A base is a substance that ionizes (or dissociates, in the case of an
ionic base) in water to produce OH– ions
• Brønsted Acids and Bases
• More inclusive definition
• Brønsted acid is a proton donor
• Brønsted base is a proton acceptor
• In this context, the word proton refers to a hydrogen atom that has
lost its electron—also known as a hydrogen ion (H+)
• Brønsted definitions of acids and bases are not restricted to
   
species in aqueous solution HCl g  NH g  NH Cl s
3 4 

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Acid-Base Reactions

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Acid-Base Reactions
• Most of the strong acids are monoprotic acids
• Each acid molecule has one proton to donate
• Acids such as H2SO4 are diprotic acids
• Each acid molecule has two protons that it can donate
• There are also triprotic acids
• Those with three protons, such as phosphoric acid (H3PO4)
• Polyprotic acids
• Acids with more than one proton to donate

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Acid-Base Reactions
• H2SO4 is strong only in its first ionization in water
• H2SO4(aq)→H+(aq)+HSO4−(aq)
• HSO4−(aq)⇆H+(aq)+SO42−(aq)
• For all other polyprotic acids, each ionization is
incomplete
• H3PO4(aq)⇄H+(aq)+H2PO4−(aq)
• H2PO4−(aq)⇄H+(aq)+HPO42−(aq)
• HPO42−(aq)⇄H+(aq)+PO43−(aq)

H PO  > H
3 4

  H2PO4  > HPO24  > PO34 

Acid-Base Reactions
• Acid-Base Neutralization
• Reaction between an acid and a base
• In general, an aqueous acid- base reaction produces water and a
salt, which is an ionic compound made up of the cation from a
base and the anion from an acid
• HCl(aq)+NaOH(aq)⟶H2O(l)+NaCl(aq)

H  aq   Cl  aq   Na  aq   OH  aq  

H2O  l   Na  aq   Cl   aq 

H  aq   OH  aq   H2O  l 

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Oxidation-Reduction Reactions
• Redox Reaction
• Chemical reaction in which electrons are transferred from one
reactant to another
• Zn(s)+Cu2+(aq)⟶Zn2+(aq)+Cu(s)
• Zinc atoms are oxidized (they lose electrons)
• Copper ions are reduced (they gain electrons)

Oxidation-Reduction Reactions
• Redox half-reactions:

Zn  s  Zn2  aq   2e-

Cu2  aq   2e  Cu  s 
Zn  s  Cu2+  aq   2e   Zn2  aq   Cu  s  2e
• Oxidation • Reducing Agent
• Loss of electrons • Zn (donates electrons)
• Causing Cu2+ to be reduced
• Reduction
• Gain of electrons • Oxidizing Agent
• Cu2+ (accepts electrons)
• Causing Zn to be oxidized

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Oxidation-Reduction Reactions
H2(g)+F2(g)⟶2HF(g)
• Fluorine does not gain an electron and hydrogen does not
lose one
• Experimental evidence shows, however, that there is a
partial transfer of electrons from H to F
• Oxidation Numbers (Oxidation State)
• Provide us with a way to “balance the books” with regard to
electrons in a chemical equation
• Charge an atom would have if electrons were transferred
completely

Oxidation-Reduction Reactions
H2  g   F2  g   2HF  g 
0 0 1 1
N2  g   3H2  g   2NH3  g 
0 0 3 1
• Elements that show an increase in oxidation number—
hydrogen in the preceding examples— are oxidized
• Elements that show a decrease in oxidation number—
fluorine and nitrogen—are reduced

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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
In NaCl Na = +1 and Cl = −1
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
(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 of their compounds.
Na = +1 in NaCl
(b) Group II metals have an oxidation state of +2 in all of their compounds.
Mg = +2 in MgCl2

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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SAMPLE PROBLEM 4.5

Determine the oxidation number of each atom in the
following compounds and ion:
a) SO2
b) NaH
c) CO32–
d) N2O5

Oxidation-Reduction Reactions
• Oxidation of Metals in Aqueous Solutions

• Displacement Reaction
• Zinc displaces, or replaces, copper in the dissolved salt by being
oxidized from Zn to Zn2+
• Copper is displaced from the salt (and removed from solution) by
being reduced from Cu2+ to Cu
• Chloride (Cl–), which is neither oxidized nor reduced, is a
spectator ion in this reaction

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Oxidation-Reduction Reactions
• Balancing Simple Redox Equations (Half-Reaction Method)
+
C r  s  N i2   a q   C r 3   a q   N i  s 
Cr  s  Cr 3  aq  3e  Ni2  aq  2e  Ni  s

2 Cr  s  Cr3  aq  3e   3 Ni2  aq  2e  Ni  s  

2Cr  s  2Cr3  aq  6e

 3Ni2   aq  6e  3Ni  s 


2Cr  s  3Ni2  aq  2Cr 3  aq  3Ni  s

SAMPLE PROBLEM 4.6

Write the net ionic equation and indicate which element is
oxidized and which is reduced:
a) Fe(s)+PtCl2(aq)⟶?
b) Cr(s)+AuCl3(aq)⟶?

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SAMPLE PROBLEM 4.74.7-1

• Balance the equation and indicate which element is
oxidized and which is reduced:
a) Cr(s)+Pb(C2H3O2 )2(aq)⟶?

b) Sn(s)+HI(aq)⟶?

Oxidation-Reduction Reactions
• Combination Reactions

• Decomposition

• Combustion

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Oxidation-Reduction Reactions

Concentration of Solutions
• Concentration
• Amount of solute
dissolved in a given
quantity of solvent or
solution
• Molarity (M)
• Number of moles of
solute per liter of
solution
moles solute
Molarity 
liters solution

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SAMPLE PROBLEM 4.8

For an aqueous solution of glucose (C6H12O6), determine the
molarity of 2.00 L of a solution that contains 50.0 g of
glucose, the volume of this solution that would contain 0.250
mol of glucose, and the number of moles of glucose in 0.500
L of this solution.

Extra Sample Problem

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?

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Concentration of Solutions
• Dilution
• Process of preparing a less concentrated solution from a more
concentrated one
• moles of solute before Dilution = moles of solute after Dilution
moles of solute
moles of solute   liters of solution
liters of solution
• M c × Lc = M d × Ld
• Mc × mLc = Md × mLd

SAMPLE PROBLEM 4.9

What volume of 12.0 M HCl, a common laboratory stock
solution, must be used to prepare 250.0 mL of 0.125 M HCl?

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SAMPLE PROBLEM 4.10

Starting with a 2.00-M stock solution of hydrochloric acid,
four standard solutions (1 to 4) are prepared by sequentially
diluting 10.00 mL of each solution to 250.00 mL. Determine
a) the concentrations of all four standard solutions
b) the number of moles of HCl in each solution

Concentration of Solutions
• Solution Stoichiometry
Na2 SO4  s  
H2O
2Na  aq   SO24  aq 
• A solution that is 0.35 M in Na2SO4 is actually 0.70 M in
Na+ and 0.35 M in SO42−
• Square brackets around a chemical species can be read
as “the concentration of” that species
• For example, [Na+] is read as “the concentration of
sodium ion”

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SAMPLE PROBLEM 4.11

Using square-bracket notation, express the concentration of
a) chloride ion in a solution that is 1.02 M in AlCl3
b) nitrate ion in a solution that is 0.451 M in Ca(NO3)2
c) Na2CO3 in a solution in which [Na+] = 0.124 M

Aqueous Reactions and Chemical

Analysis
• Gravimetric Analysis
• Analytical technique based on the measurement of mass
SAMPLE PROBLEM 4.12
A 0.8633-g sample of an ionic compound containing chloride
ions and an unknown metal cation is dissolved in water and
treated with an excess of AgNO3. If 1.5615 g of AgCl
precipitate forms, what is the percent by mass of Cl in the
original compound?

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Aqueous Reactions and Chemical

Analysis
• Acid-Base Titrations
• Solution of accurately known concentration (standard solution) is added
gradually to another solution of unknown concentration, until the
chemical reaction between the two solutions is complete
• If we know the volumes of the standard and unknown solutions used in
the titration, along with the concentration of the standard solution, we
can calculate the concentration of the unknown solution
• Example
• Solution of the strong base sodium hydroxide can be used as the
standard solution in a titration, but it must first be standardized, because
sodium hydroxide in solution reacts with carbon dioxide in the air,
making its concentration unstable over time
• We can standardize the sodium hydroxide solution by titrating it against
an acid solution of accurately known concentration

Aqueous Reactions and Chemical

Analysis
• Equivalence Point
• Point in the titration where the acid
has been completely neutralized
• Usually signaled by the endpoint,
where an indicator causes a sharp
change in the color of the solution
• Indicators
• Substances that have distinctly
different colors in acidic and basic
media
• HC8H4O4− (aq) + OH− (aq) →
C8H4O42− (aq) + H2O(l)

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SAMPLE PROBLEM 4.13

In a titration experiment, a student finds that 25.49 mL of an
NaOH solution is needed to neutralize 0.7137 g of KHP. What
is the concentration (in M) of the NaOH solution?

SAMPLE PROBLEM 4.14

What volume (in mL) of 0.203 M sodium hydroxide solution
is need to neutralize 25.0 mL if a 0.188 M sulfuric acid
solution?

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SAMPLE PROBLEM 4.15

A 0.1216-g sample of a monoprotic acid is dissolved in 25 mL
water, and the resulting solution is titrated with 0.1104 M
NaOH solution. A 12.5-mL volume of the base is required to
neutralize the acid. Calculate the molar mass of the acid.

Aqueous Reactions and Chemical

• Redox Titration Analysis
• Quantitative-analysis method
• Involves the use of an oxidation-reduction reaction, with one
reactant being delivered via a burette
• In one common type of redox titration, the titrant is a solution of
potassium permanganate, which serves as both the oxidizing agent
and the indicator
2MnO4  aq   5C2O24  aq   16H  aq  
2Mn2  aq   10CO2  aq   8H2O  aq 

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SAMPLE PROBLEM 4.16

The vitamin C (ascorbic acid, C H O ) content of Gatorade
and other sports beverages can be measured by titration
with iodine solution. The reaction can be represented with
the equation
• I2 (aq) + C6H8O6 (aq) → 2I− (aq) + C6H6O6 (aq) + 2H+ (aq)
• Determine the mass of vitamin C (in mg) contained in a
350-mL bottle of Gatorade if a 25.0-mL sample requires
29.25 mL of 0.00125 M l solution to reach the endpoint.

Areas to Study for Weekly Quizzes

• Chapter 4 Summary
• Chapter 4 Key Words
• Checkpoint Questions
• 4.1.1, 4.1.2, 4.1.3, 4.1.4
• 4.2.1, 4.2.2, 4.2.3, 4.2.4, 4.2.5, 4.2.6
• 4.3.1, 4.3.2, 4.3.3, 4.3.4, 4.3.5, 4.3.6
• 4.4.1, 4.4.2, 4.4.3
• 4.5.1, 4.5.2, 4.5.3, 4.5.4
• 4.6.1, 4.6.2, 4.6.3, 4.6.4, 4.6.5, 4.6.6

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