Reactions

Aqueous
Solution
1.
SOME
CHEMICAL
OCCUR

in

WAYS
THAT
REACTIONS

Aqueous reactions can be grouped

into three general categories, each
with its own kind of driving force:
precipitation reactions,
acidbase
neutralization
reactions, and
oxidationreduction reactions.
Precipitation Reactions are
processes
in
which
soluble
reactants yield an insoluble solid
product. Most precipitations take
place when the anions and cations
of two ionic compounds change
partners. For example, an aqueous
solution of lead(II) nitrate reacts
with an aqueous solution of
potassium iodide to yield an
aqueous solution of potassium
nitrate plus an insoluble yellow
precipitate of lead iodide:
Pb(NO3)2(aq) + 2KI(aq)2KNO3(aq)
+ PbI(s)

AcidBase
Neutralization
Reactions are processes in which
an acid reacts with a base to yield
water plus an ionic compound
called a salt. Acids are compounds
that
produce
H+
ions
when
dissolved in water and bases as
compounds that produce OH- ions
when dissolved in water. Thus, the
driving
force
behind
a
neutralization
reaction
is
the
production of the stable covalent
water molecule by removal of ions
from solution. The reaction between

hydrochloric acid and aqueous

sodium hydroxide to yield water
plus aqueous sodium chloride is a
typical example:
HCl(aq) + NaOH(aq) H2O(l) +
NaCl(aq)

OxidationReduction
Reactions, are processes in which
one
or
more
electrons
are
transferred
between
reaction
partners (atoms, molecules, or
ions). The driving force is a
decrease in electrical potential,
analogous to what happens when a
live electrical wire is grounded and
electrons flow from the wire to the
ground. As a result of this transfer
of electrons, charges on atoms in
the various reactants change. When
metallic magnesium reacts with
iodine vapor, for instance, a
magnesium atom gives an electron
to each of two iodine atoms,
forming an Mg+2 ion and two I- ions.
The charge on the magnesium
changes from 0 to +2 and the
charge on each iodine changes
from 0 to-1:
Mg(s) + I2(g)MgI2(s)
PROBLEM Classify each of the
following processes as a
precipitation, acidbase
neutralization, or redox reaction:
*Ag(NO)3(aq) +KCl(aq)AgCl(s) +
KNO3(aq)
*2P(s) + 3Br2(l)2PBr3(l)
*Ca(OH)2(aq) + 2HNO3(aq)2H2O +
Ca(NO)3(aq)

2.ELECTROLYTES IN
AQUEOUS SOLUTION
# Both sugar (sucrose) and table
salt (NaCl) dissolve in water. The
solutions that result, though, are
quite different.

# When sucrose, a molecular

substance, dissolves in water, the
solution
that
results
contains
neutral
sucrose
molecules
surrounded by water.
# When NaCl, an ionic substance,
dissolves in water, the solution
contains
separate
Na+
ions
surrounded by water. Because of
the presence of the ions, the NaCl
solution conducts electricity, but
the sucrose solution does not.
C12H22O11(s) C12H22O11(aq)
NaCl(s) Na+(aq) + Cl-(aq)
ELECTROLYTES.-Substances such
as NaCl or KBr, which dissolve in
water
to
produce
conducting
solutions of ions, are called
electrolytes.
NONELECTROLYTES.-Substances
such as sucrose or ethyl alcohol,
which do not produce ions in
aqueous
solution,
are
called
nonelectrolytes.
Most
electrolytes
are
ionic
compounds,
but
some
are
molecular. Hydrogen chloride, for
example, is a molecular compound
when pure but dissociates to give
and ions when it dissolves in water.
Compounds that dissociate to a
large extent (70100%) into ions
when dissolved in water are said to
be
strong
electrolytes,
while
compounds that dissociate to only a
small extent are weak electrolytes.

PROBLEM- What is the total

molar concentration of ions in a
0.350 M solution of the strong
electrolyte Na2(SO4) assuming
complete dissociation?

3. AQUEOUS REACTIONS
AND NET IONIC EQUATIONS
Molecular Equation

Pb(NO3)2(aq) + 2KI(aq)2KNO3(aq)
+ PbI2(s)
lead nitrate, potassium iodide, and
potassium nitrate are strong
electrolytes that dissolve in water
to yield solutions of ions. Thus, its
an ionic equation,
Pb2+(aq) + 2(NO3)-(aq) + 2K+(aq) + 2I+
(aq) 2K (aq) +2(NO3) (aq) + PbI2(aq)
An Ionic Equation
Pb2+(aq) + 2(NO3)-(aq) +2K+(aq)
+2I-(aq)2K+(aq) + 2(NO3)-(aq) +
PbI2(s)
(NO3)- and K+ ions undergo no
change during the reaction.
Instead, they appear on both sides
of the reaction arrow and act as
spectator ions, whose only role is to
balance the charge.
Net Ionic Equation,
Pb2+(aq) + 2I-(aq) PbI2(s)

****
4. OXIDATIONREDUCTION
(REDOX) REACTIONS

Magnesium metal burns in air

with an intense white light to
form solid magnesium oxide.
Red phosphorus reacts with
liquid bromine to form liquid
phosphorus tribromide.
Purple aqueous permanganate
-

ion, MnO4 reacts with aqueous

Fe+2 ion to yield Fe+3 and pale
pink Mn+2. These all are
oxidationreduction reactions
2Mg +O2 2MgO
2P + 3Br2 2PBr3
MnO- +5Fe+2 + 8H+ Mn+2 +
5Fe+3 + 4H2O
4Fe+3O22Fe2O3 Rusting of iron:
n
an oxid of Fe
Fe2O3 + 3C 4Fe +CO2
Manufacture of iron: a reduction of
Fe2O3

Oxidation is now defined as the

loss of one or more electrons by a
substanceelement, compound, or
ion.
Reduction is the gain of one or
more electrons by a substance.
Thus, an oxidationreduction
reaction, or redox reaction, is a
process in which electrons are
transferred from one substance to
another.
How can you tell when a redox
reaction is taking place?---we
assign to each atom in a substance
a value called an oxidation
number (or oxidation state), which
indicates whether the atom is
neutral, electron-rich, or electronpoor. By comparing the oxidation
number of an atom before and after
reaction, we can tell whether the
atom has gained or lost electrons
1. An atom in its elemental state
has an oxidation number of 0.
2. An atom in a monatomic ion has
an oxidation number identical to its
charge
3. An atom in a polyatomic ion or
in a molecular compound usually
has the same oxidation number it
would have if it were a monatomic
ion
a. Hydrogen can be either +1 or
-1 When bonded to a metal, such
as Na or Ca, hydrogen has an
oxidation number of -1. When
bonded to a nonmetal, such as C,
N, O, or Cl, hydrogen has an
oxidation number of +1.
b. Oxygen usually has an
oxidation number of -2 The
major exception is in compounds
called peroxides, which contain
either the O22- ion or an O-O

covalent bond in a molecule. Each

oxygen atom in a peroxide has an
oxidation number of -1.
c. Halogens usually have an
oxidation number of -1
The
major
exception
is
in
compounds of chlorine, bromine, or
iodine in which the halogen atom is
bonded to oxygen. In such cases,
the oxygen has an oxidation
number of -2 and the halogen has a
positive oxidation number. In Cl 2O
for example, the O atom has an
oxidation number of -2 and each Cl
atom has an oxidation number of
+1.
Cl-O-Cl H-O-Br
4. The sum of the oxidation
numbers is 0 for a neutral
compound and is equal to the net
charge for a polyatomic ion.

5.IDENTIFYING REDOX RXNS

The substance that causes a
reduction by giving up electrons
the iron atom in the reaction of Fe
with O2 and the carbon atom in the
reaction of C with Fe2O3 is called a
reducing agent. The substance
that causes an oxidation by
accepting electronsthe oxygen
atom in the reaction of Fe with O 2
and the iron atom in the reaction of
C with Fe2O3is called an oxidizing
agent. The reducing agent is itself
oxidized when it gives up electrons,
and the oxidizing agent is itself
reduced when it accepts electrons.
REDUCING AGENT
Causes reduction
Loses one or more electrons
Undergoes oxidation
Oxidation number of atom
increases
OXIDIZING AGENT

 Causes oxidation
Gains one or more electrons
Undergoes reduction
Oxidation number of atom
decreases
Titanium, for example, can react
with chlorine to yield either TiCl3 or
TiCl4. Because a chloride ion has a
-1 oxidation number, the titanium
atom inTiCl3
must have a+3
oxidation number and the titanium
atom in TiCl4 must be +4.

6. THE ACTIVITY SERIES OF

THE ELEMENTS
Iron metal reacts with aqueous

copper(II) ioLn, for example, to

give iron(II) ion and copper metal
Fe + Cu2+Fe2+ + Cu
Similarly, magnesium metal reacts
with
aqueous
acid
to
yield
magnesium ion and hydrogen gas:
Mg + 2 H+ Mg2+ + H2
Whether a reaction occurs between
a given ion and a given element
depends on the relative ease with
which the various species gain or
lose electronsthat is, on how
easily each species is reduced or
oxidized.
Activity series, which ranks the
elements in order of their reducing
ability in aqueous solution. Those
elements at the top give up
electrons readily and are stronger
reducing agents, whereas those
elements at the bottom give up
electrons less readily and are
weaker reducing agents. As a
result, any element higher in the
activity series will reduce the ion of
any element lower in the activity
series. Because copper is above

silver, for example, copper metal

can give electrons to Ag+ions:
Cu +2Ag+ Cu+2 + 2Ag
Conversely, because gold is below
silver in the activity series, gold
metal does not give electrons toAg+
ions:
Au + 3Ag+ Au+3 + 3Ag Does
not occur
The position of hydrogen in the
activity
series
is
particularly
important because it indicates
which metals react with aqueous
acid (H+) to release H2 gas. The
metals at the top of the seriesthe
alkali metals of group 1A and
alkaline earth metals of group 2A
are such powerful reducing agents
that they react even with pure
water, in which the concentration of
H+ is very low:
2Na(s) +2H2O(l) 2Na+ (aq) +2OH(aq) +H2(g)
By contrast, the metals in the
middle of the series react with
aqueous acid but not with water,
and the metals at the bottom of the
series react with neither aqueous
acid nor water:
Fe + 2H+Fe2+ + H2
Cu + H+ No reaction

7.BAANCING REDOX
REACTIONS:
THE
OXIDATION-NUMBER
METHOD
The key to the oxidation-number
method
of
balancing
redox
equations is to realize that the net
change in the total of all oxidation
numbers must be zero. That is, any
increase in oxidation number for

the oxidized atoms must be

matched
by
a
corresponding
decrease in oxidation number for
the reduced atoms.
Take the reaction of potassium
permanganate(KMnO4) with sodium
bromide in aqueous acid, for
example.
An
aqueous
acidic
solution
of
the
purple
permanganate anion (MnO4-)
is
reduced by Br to yield the nearly
colorless Mn+2 ion, while Bris
oxidized to Br2 The unbalanced net
ionic equation for the process is
MnO4- + Br- Mn2+ + Br2
Unbalanced
Step 1. Write the unbalanced net
ionic equation.
Step 2. Balance the eq. for all
atoms other than H and O.
Step 3. Assign oxidation numbers
to all atoms
Step 4. Decide which atoms have
changed O.N., and by how much.
Step 5. Make the total increase in
oxidation number for oxidized
atoms equal to the total decrease
in oxidation number for reduced
atoms.
Step 6. Balance the equation for O
by adding water to the side with
less O, and then balance for H by
adding H2O to the side with less H.
The procedure is exactly the same
as that used for balancing a
reaction in acidic solution, but OH ions are added as the final step to
neutralize any H+ ions that appear
in the equation.[basic solutions
contain negligibly small amounts of
H+ but large amounts of OH-.]

8. BALANCING REDOX
REACTIONS:
THE
HALF-REACTION
METHOD
An alternative to the oxidationnumber method for balancing redox
reactions is the half-reaction
method. The key to this method is
to realize that the overall reaction
can be broken into two parts, or
half reactions. One half-reaction
describes the oxidation part of the
process, and the other half-reaction
describes the reduction part. Each
half is balanced separately, and the
two halves are then added to
obtain the final equation.
Step.1 Write the unbalanced net
ionic equation
Step.2 Decide which atoms are
oxidized and which are reduced,
and write the two unbalanced halfreactions.
Step.3 Balance both half-reactions
for all atoms except O and H.
Step.4 Balance each half-reaction
for O by adding water to the side
with less O, and balance for H by
adding H2O to the side with less H.
Step.5 Balance each half-reaction
for charge by adding electrons to
the side with greater positive
charge, and then multiply by
suitable factors to make the
electron count the same in both
half-reactions
Step.6 Add the two balanced halfreactions together, and cancel
electrons and other species that
appear on both sides of the
equation.