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Aqueous Reactions and


Solution Stoichiometry

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Aqueous
Reactions and
Solution
Stoichiometry

Introduction
General properties of aqueous solution
Precipitation reaction
Acid-base reaction
Oxidation-reduction reaction
Concentration of solution
Solution stoichiometry and chemical
analysis

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Introductio
n

Reactions are driven from reactants to products


by some energetic driving force that pushes
them along.
Driving forces of reactions:
Precipitation Reactions - solid precipitate forms and
drops out of solution.
Driving force = Removal of material from solution.

Acid-Base Neutralization - an acid reacts with a base


to produce a salt and water.
Driving force = formation of water.

Oxidation-Reduction (Redox) Reaction - transfer of


electrons between reactants.
Driving force = decrease in electrical potential.

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General
Properties of
Aqueous
Solution
a
homogeneous

Asolutionis
mixture.
A solution consists of

asolvent, the substance in which


something is dissolved, and
one or moresolutesthe substance(s)
dissolved in the solvent.

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General
Properties of
Aqueous
Solution

Solutes come in two varieties:


electrolytes and
nonelectrolytes

Solutions of electrolytes such as NaCl and


HNO3contain ions and thus conduct
electricity.
Solutions of nonelectrolytes such as sucrose
(C12H22O11) and methanol (CH3OH) do not
form ions in solution and thus do not
conduct electricity.

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General
Properties of
Aqueous
Solution

Electrolyte and Nonelectrolyte

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General
Properties of
Aqueous
Solution

General
Properties of
Aqueous
Solution
An electrolyte may be either
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astrong electrolyteor
aweak electrolyte.

A strong electrolyte exists in solution


completely (or almost completely) as
ions, while a weak electrolyte
produces only a small concentration
of ions when it dissolves in solution.

General
Properties of
Aqueous
Solution
Ionic compounds that are soluble in
waterdissociatecompletely
and
exist in solution entirely as ions.
Soluble ionic compounds are strong
electrolytes.
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General
Properties of
Aqueous
Solution
Molecular compounds such as sugar
and alcohol are nonelectrolytes.
They have no tendency to come
apart, and they exist in solution
entirely as aqueous molecules.
Some molecular compounds, most
notably acids and weak bases, are
electrolytes.
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General
Properties of
Aqueous
Solution
The acids HCl, HBr, HI, HNO3, HClO3,
HClO4, and H2SO4are molecular
compounds thationizein aqueous
solution and exist completely as ions.
For example, hydrogen chloride gas
dissolves in water and ionizes in
solution to give aqueous hydrogen
ion and aqueous chloride ion.
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General
Properties of
Aqueous
Solution
All of the seven acids listed above
are strong electrolytes.
They are also called strong acids.
In
both
instances
the
wordstrongdenotes
complete
ionization. (Strong bases are ionic
and are also strong electrolytes.)
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General
Properties of
Aqueous
Solution

Weak acids and weak bases make up a


group of molecular compounds that are
weak electrolytes.
Acetic acid (HC2H3O2) is a weak acid.
Although it ionizes in water, the reverse
process occurs more readily.
At any given time most of the acetic
acid exists as aqueous molecules in
solution.

General
Properties of
Aqueous
Solution
Weak acids are weak electrolytes.
To represent the equilibrium between
the molecular acid and its ionized
form, we use a double arrow in the
equation.
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General
Properties of
Aqueous
Solution
are
also
weak

Weak
bases
electrolytes.
Ammonia ionizes in water to produce
aqueous
ammonium
ions
and
aqueous hydroxide ions.
Section 4.1
Dissolving NaCl
Dissolving Sugar

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General
Properties of
Aqueous
Solution

Strong and Weak Electrolytes

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General
Properties of
Aqueous
Solution

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Precipitation
Reaction

Many chemical reactions occur in aqueous


solution.
Aprecipitation
reactionis
one
that
occurs in solution and results in the
formation of an insoluble product.
For example, an aqueous solution of the
soluble ionic compound, sodium sulfate, can
be mixed with an aqueous solution of the
soluble ionic compound, barium hydroxide.
The result is the formation of aprecipitate,
the insoluble ionic compound barium
sulfate.

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Precipitation
Reaction

Note that only one of the products of the


reaction is a solid.
Sodium hydroxide is soluble.
Many combinations of such solutions will not
result in a precipitation because they
produce no insoluble product.
Whether or not an ionic product of a
reaction in solution will precipitate from the
solution can be predicted using a set of
solubility guidelines.

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Precipitation
Reaction

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Precipitation
Reaction

Having learned that substances such


as sodium sulfate, barium hydroxide,
and sodium hydroxide are strong
electrolytes and exist entirely as ions
in solution, we are equipped to write
these chemical equations in a way
that better represents what actually
happens in solution.

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Precipitation
Reaction

The equation above is amolecular


equationin which none of the
species is represented as ionized.
A molecular equation shows the
complete chemical formulas for the
reactants and products.
We know, however, that several of
the species in the equation dissociate
completely in solution.

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Precipitation
Reaction

We
convert
the
equation
to
acomplete
ionic
equationby
identifying the strong electrolytes
and representing them as separated
ions.
The equation above becomes

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Precipitation
Reaction

The ionic equation reveals that two


of the species in solution (sodium ion
and hydroxide ion) do not undergo
any change in the course of the
reaction.

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Precipitation
Reaction

Ions that are present but play no role


in the reaction are calledspectator
ions.
Eliminating the spectator ions from
both sides of the equation gives
thenet ionic reaction.

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Precipitation
Reaction

The net ionic equation for the


combination of aqueous sodium
sulfate
and
aqueous
barium
hydroxide is the same as the net
ionic equation for any combination of
a soluble sulfate and a soluble
barium compound.

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Precipitation
Reaction

To predict the outcome when combining


aqueous solutions of ionic compounds:
1. Identify the cation and anion in each reactant.
2. Combine the cation from the first reactant with
the anion of the second to get the first product.
3. Combine the anion from the first reactant with
the cation of the second to get the second
product.
4. Determine whether the products are aqueous or
solid by consulting the solubility guidelines.

Precipitation Reaction

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Acid-Base
Reaction

Anacidis
a molecular substance that ionizes to form
a hydrogen ion (H+) and
increases the concentration of aqueous
H+ions when it is dissolved in water.

Because a hydrogen atom consists of a


proton and an electron,
H+ is simply a proton;
therefore, an acid can also be thought of as
a substance that can donate a proton.

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Acid-Base
Reaction

Hydrogen chloride ionizes in water,


increasing the aqueous concentration
of H+.
Strong acids are those that ionize
completely in water. Strong acids are
also strong electrolytes.
Hydrochloric acid is one of seven
strong acids.

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Acid-Base
Reaction

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Acid-Base
Reaction

Weak acids are those that ionize


partially in water.
Weak
acids
are
also
weak
electrolytes.
Acetic acid is an example of a weak
acid.

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Acid-Base
Reaction

Introduction to Aqueous Acids

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Acid-Base
Reaction

Abaseis a substance that increases


the
concentration
of
aqueous
OHions when it is dissolved in water.
Bases can be either ionic or
molecular substances.

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Acid-Base
Reaction

A base can be thought of as a


substance that can accept a proton;
in other words, bases are substances
that react with H+ions.
Ammonia ionizes in water, accepting
a proton from water and increasing
the
aqueous
concentration
of
OHion.

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Acid-Base
Reaction

A strong base is an ionic compound


that dissociates completely in water.
Group 1A hydroxides, such as sodium
hydroxide, and heavy Group 2A
hydroxides,
such
as
calcium
hydroxide, are strong bases.

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Acid-Base
Reaction

Weak
bases
are
molecular
compounds that ionize only partially
in water.
Ammonia is an example of a weak
base.
Introduction to Aqueous Bases

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Acid-Base
Reaction

An acid and a base can react with


one another to form a molecular
compound and asalt.
The combination of hydrochloric acid
and
sodium
hydroxide
is
a
familiarneutralization reaction.

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Acid-Base
Reaction

The molecular compound produced


by the reaction is water, and the salt
is sodium chloride.

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Acid-Base
Reaction

The molecular compound produced


by the reaction of an acid and a base
can also be a gas.
Aqueous hydrochloric acid reacts
with aqueous sodium sulfide (a weak
base) to produce hydrogen sulfide (a
gaseous molecular compound) and
sodium chloride.

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Acid-Base
Reaction

OxidationReduction
Reaction
In addition to precipitation and
neutralization reactions, aqueous
ions can participate inoxidationreduction reactions.
Oxidation-reduction reactions involve
the transfer of electrons from one
chemical species to another.
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OxidationReduction
Reaction
A piece of calcium metal, for
example, dissolves in aqueous acid.
Electrons from the calcium metal
have been transferred to the
hydrogen ions.
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OxidationReduction
Reaction
The
calcium
has
undergoneoxidation(loss
of
electrons), and the hydrogen ion has
undergonereduction(gain
of
electrons).
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OXD-Red1
OXD-Red2

OxidationReduction
Reaction
In order to determine whether a
reaction is an oxidation-reduction
reaction, we compare theoxidation
numbers(or oxidation states) of
each element on both sides of the
equation.
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OxidationReduction
Reaction

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OxidationReduction
Reaction

Oxidation numbers can be assigned using


the following rules.
1. Any atom in its elemental form has an
oxidation state of zero. No exceptions.
2. Any monatomic ion has an oxidation state
equal to its charge. No exceptions.
3. Oxygen almost always has an oxidation
state of minus 2. Exceptions include the
elemental forms of oxygen (O2and O3) in
which its oxidation state is zero, the
peroxide ion (O22) in which its oxidation
state is minus 1, and the superoxide ion
(O2) in which its oxidation state is minus
.

OxidationReduction
Reaction
Oxidation numbers can be assigned
using the following rules.
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4. Hydrogen almost always has an


oxidation state of plus 1.

Exceptions
include
elemental
hydrogen (H2) in which its oxidation
state is zero and metal hydrides (such
as NaH) in which its oxidation state is
minus 1.

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OxidationReduction
Reaction

Oxidation numbers can be assigned using


the following rules.
5. Fluorine almost always has an oxidation
state of minus 1.

The only exception is that of elemental fluorine


(F2), which has an oxidation state of zero. The
other halogens usually have oxidation states of
minus 1 also. The exceptions are the elemental
halogens, in which their oxidation states are
zero, and compounds or polyatomic ions in
which chlorine, bromine, or iodine are
combined with fluorine or oxygen. In these
cases the halogens (other than fluorine) can
have positive oxidation states.

OxidationReduction
Reaction
Oxidation numbers can be assigned
using the following rules.
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6. The sum of oxidation states must


equal the overall charge on the
species; i.e., the sum of oxidation
states in a molecule must equal
zero, and the sum of oxidation
states in a polyatomic ion must
equal the charge on the polyatomic
ion.

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OxidationReduction
Reaction

OxidationReduction
Reaction
Some common oxidation-reduction
reactions are those between metals
and acids or metals and salts.
Calcium being oxidized by acid is one
example.
Magnesium is also oxidized in acidic
solution.
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OxidationReduction
Reaction
Metals can also be oxidized by
dissolved salts. Nickel metal is
oxidized by a solution of copper
sulfate.
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OxidationReduction
Reaction
ickel metal, however, isnotoxidized
by a solution of calcium sulfate.
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OXD-Red2

OxidationReduction
Reaction
Whether or not such a reaction will
occur can be predicted using
theactivity series.
A metal solid will be oxidized
(dissolved) by the ions of any metal
that occurs below it on the series.
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OxidationReduction
Reaction

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OxidationReduction
Reaction

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OxidationReduction
Reaction

Redox chemistry of zinc and tin


Formation of silver crystals

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OxidationReduction
Reaction

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OxidationReduction
Reaction

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Concentration of
Solution

One important feature of a solution is


itsconcentration.
A solution containing a large amount of solute
is said to be "concentrated,"
while a solution containing a relatively small
amount of solute is said to be "dilute."

These are simply relative terms, though,


and a more quantitative expression of a
solution's
concentration
often
is
necessary.

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Concentration of
Solution

The most commonly used expression


of concentration ismolarity.
Symbolized with a capitalM, molarity
is the ratio of the number of moles of
solute to the number of liters of
solution.
Solution Formation from a Solid

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Concentration of
Solution

Because electrolytes such as the


compounds in the Molarity activity
ionize or dissociate in water, it is
necessary to consider stoichiometry
when determining the concentrations
of individual ions in an aqueous
solution.
Sodium carbonate, for example,
dissociates in solution to give sodium
ions and carbonate ion.

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Concentration of
Solution

Because each unit of sodium carbonate yields


two units of sodium ion and one unit of
carbonate ion, the concentration of sodium
ions and carbonate ions will not be equal.
If we were to mix up a 1 L solution containing
0.1
mole
of
sodium
carbonate,
the
concentration of sodium carbonate would be
0.1M.
The concentration of carbonate ion would be
0.1Malso.
The concentration of sodium ion would be
twice that much, or 0.2M.

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Concentration of
Solution

Dissolution of KMnO4
Dissolution of Mg(OH)2

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Concentration of
Solution

There is a particular method by


which solutions are prepared using
solid solutes.
This method ensures that the small
volume change associated with
mixing solvent and solute does not
affect the accuracy of the calculated
molarity.

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Concentration of
Solution

In practice, many solutions are made


from concentrated stock solutions
rather than from solids.
The amount of concentrated stock
solution necessary to make up a
given
volume
of
the
desired
concentration is determined using
the equation

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Concentration of
Solution

Solution Formation by Dilution

Solution
Stoichiometry
and Chemical
Analysis
Many of the reactions that take place
in aqueous solution are useful in
chemical
analyses,
such
astitrations.
Titration
involves
the
carefully
metered addition of astandard
solutionof one reactant to a flask
containing an unknown quantity of
the other
reactant.
Acid-Base Titration
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Concentration of
Solution

The point in the titration at which


stoichiometric amounts of reactants
have been combined is called
theequivalence point.
For many reactions, the equivalence
point is not an obvious occurrence,
and so we add anindicatorto the
flask.

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Concentration of
Solution

An indicator is a compound that


changes coloratorvery nearthe
equivalence point.
The point at which the indicator
changes color is called theend point.

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Concentration of
Solution

The titration simulation allows you to


experiment
with
a
variety
of
unknown
acids,
standard
base
concentrations, choice of indicator,
and base addition increments.

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