CHAPTER 8

AQUEOUS REACTIONS AND SOLUTION STOICHIOMETRY

8.0 GENERAL PROPERTIES OF AQUEOUS SOLUTIONS

An aqueous solution is a solution that contains water. When an ionic compound such as
NaCl is dissolved in aqueous solution, the compound breaks up into its constituent ions and the
ions are surrounded by water molecules and are said to be hydrated. For NaCl dissolved in water,
it is written as Na+(aq) and Cl-(aq) because the compound no longer exist as compound, NaCl, in
solution but as separate ions surrounded by water molecules. The mixture is called a solution of
sodium chloride. Since ions exist in solution, they allow passage of electricity. A substance
whose aqueous solution allows passage of electricity due to the presence of ions is called an
electrolyte. Ionic compounds dissociate completely in aqueous solution and are said to be strong
electrolyte.

Some molecular compounds such as HCl reacts with water and dissociate completely. All
molecules of HCl are converted into ions and therefore HCl molecules essentially do not exist as
molecules in water but are transformed into hydronium ions and chloride ions as shown below

HCl + H2O H3O+ + Cl-

Substances that do not form ions in solution are called nonelectrolyte. They remain as
molecules even if they are dissolved in water. Some compounds such as acetic acid or ammonia
react with water and produce limited amount of ions. These compounds are called weak
electrolyte because their solutions are poor conductors of electricity. In the case of weak
electrolytes, they remain essentially as molecules and must be written as such. For acetic acid,
CH3COOH, dissolved in water, the following reaction occurs but to a very limited extent and
most of the molecules of acetic acid remain in their molecular form. They are written as
molecules, i.e. CH3COOH(aq).

CH3COOH + H2O === CH3COO- + H3O+

In the same manner, ammonia reacts with water as:

NH3 + H2O === NH4+ + OH-

but ammonia is written as NH3(aq) since most of it exist as molecules and not as ions.

8.1 AQUEOUS REACTIONS

There are several types of chemical reactions occurring in aqueous solutions and will be
discussed in the preceding sections.
8.1.1 PRECIPITATION REACTIONS

Some reactions occurring in aqueous solution produce compounds that are said to be
insoluble in water and they come out of solution as solid or precipitate. Given the reaction of
lead nitrate and potassium iodide:

Pb(NO3)2(aq) + 2KI(aq) PbI2(s) + 2KNO3(aq)

Based on the chemical equation, lead nitrate and potassium iodide are soluble in water
but when mixed, produce lead iodide that precipitates out of solution, and potassium nitrate that
remains in solution.

Another example is:

Ba(NO3)2(aq) + Na2SO4(aq) BaSO4(s) + 2NaNO3(aq)

The above reaction tells us that barium nitrate and sodium sulfate are soluble in water but
when mixed, produce barium sulfate that is insoluble in water and sodium nitrate which
remained in solution.
To determine which compounds are soluble in water and which ones are not, one must be
aware of solubility of compounds in water as shown in the table below:

8.1.2 SOLUBILITY GUIDELINES FOR COMMON IONIC COMPOUNDS IN WATER

Soluble Compounds Important Exceptions

-
Compounds containing NO3 None
C2H3O2- None
Cl- Compounds of Ag+, Hg22+, and Pb2+
Br- Compounds of Ag+, Hg22+, and Pb2+
I- Compounds of Ag+, Hg22+, and Pb2+
SO42- Compounds of Sr2+, Ba2+, Hg22+,and
Pg2+

Insoluble Compounds Important Exceptions

2-
Compounds containing S Compounds of NH4+, the alkali metal
cations, and Ca2+, Sr2+, and Ba2+
CO32- Compounds of NH4+, and the alkali
metal cations
PO43- Compounds of NH4+, and the alkali
metal cations
OH- Compounds of NH4+, the alkali metal
cations, and Ca2+, Sr2+, and Ba2+
8.2 IONIC EQUATIONS:

When barium nitrate reacts with sodium phosphate, they form an insoluble product. The
reaction can be properly represented by the following equation:

3Ba(NO3)2(aq) + 2Na3PO4(aq) Ba3(PO4)2(s) + 6NaNO3(aq)

The above equation is called the molecular equation. Since Ba(NO3)2, Na3PO4 , and
NaNO3 are all soluble in water, they must be written as ions in solution while the insoluble
Ba3(PO4)2 must be written in molecular form:

3Ba2+(aq) + 6NO3-(aq) + 6Na+(aq) +2 PO43-(aq) Ba3(PO4)2(s) + 6Na+(aq) +6NO3-(aq)

The above equation is the complete ionic equation for the above precipitation reaction.
Notice that sodium ion and nitrate ion exist on both sides of the equation and must be eliminated.
What remained is called the net ionic equation as given below:

3Ba2+(aq) + 2 PO43-(aq) Ba3(PO4)2(s)

The net ionic equation shows which species actually takes part in the chemical reaction
and the product that was formed. Those ions appearing on both sides of the equation do not take
part in the reaction and are said to be spectator ions.

8.3 ACID-BASE REACTIONS

Acids are substances that ionize in aqueous solution producing hydrogen ions, H +, and
thereby increasing H+ concentration in aqueous solution. Since a hydrogen atom consists of a
proton and an electron, H+ is simply a proton and the acids are said to be proton-donors. There
are two kinds of acid according to their ability to dissociate into ions in aqueous solution. They
are strong acids and weak acids. Strong acids dissociate completely in solution producing
equivalent amount of H+ with that of the original amount of acid while the weak acids dissociate
only partially in solution giving small amount of ions. Examples of strong acids are hydrogen
halides such HCl, HBr, and HI. Other strong acids are HNO 3, HClO3, and H2SO4. Weak acids
include acetic acid, oxalic acid and other organic acids, carbonic acid, etc.

Bases, on the other hand, are substances that ionize in aqueous solution producing
hydroxide ions, OH-. As in acids, there are strong and weak bases. Strong bases completely
dissociate in solution while weak bases partially dissociate in solution. It can also be said that
bases are substances that accept H+ from a proton-donor or an acid and the process is called acid-
base reaction. Examples of strong bases are NaOH, KOH, Ca(OH) 2, Ba(OH)2 and Sr(OH)2.
Weak bases include NH3, carbonates, amines, and carboxyates.

If a solution of HCl and NaOH are mixed together, they react and produce water and the
salt, NaCl.
 HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)

Though one is familiar that NaCl is the common salt on the table, salt, in chemical term,
is an ionic compound whose cation comes from the base, and whose anion comes from the acid
that reacted. The acid HCl and the base NaOH are said to neutralize each other so that an acid-
base reaction is called a neutralization reaction.

Another example of an acid-base reaction is that of Al(OH)3 and HCl

Al(OH)3(s) + 3HCl(aq) AlCl3(aq) + 3H2O(l)

The aluminum hydroxide acts as the base while HCl acts the acid producing water and
salt. In this case, the salt is AlCl3. If we take the net ionic equation of the two acid-base reactions,
we end up with identical equations, that is,

H+(aq) + OH-(aq) H2O(l) and 3H+(aq) + 3OH-(aq) 3 H2O(l)

The coefficients in the second equation is immaterial since the equation can be reduced
further by dividing all the terms in the equation by 3 giving the first equation which is the
formation of water from H+(aq) and OH-(aq).
There are, however, basic species other than hydroxide and water is not always produced
in an acid-base reaction as in the following example:
2HCl(aq) + (NH4)2S(aq) H2S(g) + 2NH4Cl(aq)
In this case, the salt, NH4Cl, and a gas, H2S, is produced.
Another example of acid-base reaction not producing water is given below:
HCl(aq) + Na2CO3(aq) NaCl(aq) + NaHCO3(aq)
It appears that both products of the above reaction are salts but NaHCO 3 is a known weak
base that can further react with acidic species
HCl(aq) + NaHCO3(aq) NaCl(aq) + H2CO3(aq)

8.4 REDUCTION-OXIDATION REACTIONS

Also known as redox reaction, this type of reaction involves transfer of electron(s) from
one species to another. Given the following equation,
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
It can be said that zinc lost 2 electrons and in the process, has become an ion such that it
becomes soluble in solution. The copper, on the other hand, gained 2 electrons and has become a
neutral species, and has become insoluble in solution resulting in its precipitation. Zinc is the
source of electrons for this reaction and is called the reducing agent. The process of losing
electrons is called oxidation while the process of gaining electrons is called reduction. Copper is
the recipient of the electrons lost by zinc and is called the oxidizing agent. Zinc, being the
reducing agent is oxidized and copper, being the oxidizing agent, is reduced. Notice that the
number of electrons lost is equal to the number of electrons gained. This is true for all redox
reaction because electrons do not vanish or transformed into other subatomic species when a
redox reaction takes place.
To determine if a chemical reaction involves redox reaction, an artificial assignment of
charge for each atom involved in the reaction is used. The hypothetical charge assigned to the
atom using a set of rules is called the oxidation number of the atom or its oxidation state.
Reduction is said to have occurred if there is a decrease in oxidation number of the atom while
oxidation is said to have occurred if the oxidation number of the atom increased.

8.4.1 RULES IN ASSIGNING OXIDATION NUMBERS

1. For an atom in its elemental form, the oxidation number assigned is zero. Therefore, the
oxidation numbers of hydrogen atoms in a hydrogen molecule is zero. For carbon atom in
graphite or diamond form, it has an oxidation number of zero as well.
2. For a monatomic ion, the oxidation number is equal to its charge. Thus, for all alkali
ions, their oxidation number is +1, and for all alkaline earth ions, their oxidation number
is +2. For ferric ion, its oxidation number of iron is +3. For cupric ion, the oxidation
number of cupper is +2.
3. The assigned oxidation number for oxygen in a compound is -2 except for peroxide, O22-.
For hydrogen in a compound, the oxidation number is +1. For fluorine, the assigned
oxidation number is -1.
4. The sum of oxidation numbers of all atoms in a neutral compound is zero. The sum of
oxidation number in a polyatomic ion is equal to its charge. For example, the oxidation
number of carbon in carbon dioxide, CO2, is +4 since the oxidation number of oxygen in
this compound is -2 and there are two oxygen per molecule of carbon dioxide. The sum
of their oxidation numbers must be equal to zero since carbon dioxide is a neutral
compound. For carbon in carbonate ion, CO 32-, its oxidation number is +4 since the sum
of all oxidation numbers of one carbon atom and three oxygen atoms must be equal to the
charge of the carbonate which is -2.
Example 8.1
Given the following reaction, let us determine if it is a redox reaction.
Zn(s) + 2H+(aq) Zn2+(aq) + H2(g)
Solution
The oxidation number of metallic zinc is zero and +2 for its ion. There is an increase in
the oxidation number of zinc during the reaction and therefore, it is oxidized. For hydrogen, its
oxidation number in the ion is +1 and zero for its gas. There is a decrease in the oxidation
number of hydrogen and therefore, it is reduced.
8.4.2 THE ACTIVITY SERIES
Metals tend to lose electrons to form cations. But some metals are more reactive than
others. Take the case of the following reactions:
Zn(s) + Fe2+(aq) Zn2+(aq) + Fe(s)
Zn2+(aq) + Fe(s) no reaction
Fe(s) + Cu2+(aq) Fe2+(aq) + Cu(s)
Fe2+(aq) + Cu(s) no reaction
It is evident from the above reactions that zinc is more reactive than iron but iron is more
reactive than copper. This arrangement of metal reactivity is what is known as the activity series
and can be expanded to include all metals as shown below:
Activity Series: Decreasing reactivity from left to right
Li>K>Ba>Ca>Na>Mg>Al>Mn>Zn>Cr>Fe>Co>Ni>Sn>Pb>H2>Cu>Ag>Hg>Pt>Au
From the series, it can easily be determined if magnesium metal can reduce aluminum ion
or if lithium metal can reduce sodium ion as the activity series also gives the strength of a metal
to reduce ions of other metals. The series given above is arranged in decreasing reducing
strength.

8.5 CONCENTRATION OF SOLUTIONS

Concentration of a solution is the amount of solute that is dissolved in the given amount
of solvent or solution. There are many ways to express the concentration of solution as the
amount of solute can take the form of mass in grams or milligrams or in terms of the number of
moles of solute. The amount of solvent or solution can be specified in terms of volume in liters
or milliliters or in terms of mass in kilograms.

8.5.1 MOLARITY
Molarity, M, of a solution is the number of moles of solute in a liter of solution
moles solute
M=
volume ∈liters of solution

A solution that is 1.0 molar (1.0M) in NaCl contains 1.00 mole of NaCl in every liter
solution.
Example 8.2
If 4.00 grams of NaOH (FW= 40g/mol) is dissolved in 100.00mL solution, find the
number of moles and its molarity.
Solution
4.00 grams NaOH
moles NaOH =
40 grams/mole
¿ 0.10 mole
0.10 mole
M=
0.10000 L
mol
¿ 1.0 ∨1.0 M
L

8.6 CONCENTRATION OF ELECTROLYTES

The concentration of the ions when an ionic compound is dissolved in aqueous solution
depends on the chemical formula of the compound. If a solution is 1.0M in MgCl2, it is 1.0M in
Mg2+ but 2.0M in Cl- since for every mole of MgCl2, it gives 2 moles of Cl- as it dissociates in
water yet the volume of solution remains the same.

MgCl2(aq) Mg2+ + 2Cl-

1mole 1mole 2moles

M Mg2+ ¿
Mg 2 +¿=1.0 mole ¿¿
1.0 liter solution

¿ 1.0 M

M Cl−¿
Cl−¿=2.0 mole ¿¿
1.0 liter solution

¿ 2.0 M

8.7 INTERCONVERTING MOLARITY, MOLES, AND VOLUME

Since
moles
M=
VL
 then
moles=MV L
and
moles
V L=
M

Molarity can also be expressed in terms of millimoles/milliliter of solution:

mmole
M=
V ml

Example 8.3
Given 10.00mL of 1.0M CuCl2, calculate the number of moles.
Solution
CuCl2 is simply moles CuCl2 = MVL
= (1.0M)(0.01000L)
= 0.010 moles or 10 millimoles.
The number of moles of Cl- is twice that of the compound and is equal to 0.020 moles or 20
millimoles.

8.8 DILUTION
Dilution is the process of preparing less concentrated solution from a more concentrated
solution by simply adding more solvent. Since the number of moles of solute is not changing,
the number of moles of solute before dilution is equal to the number of moles of solute after
dilution:
molesi = molesf molesi = initial number of moles
molesf = final number of moles

The number of moles initially can be expressed in terms of the original concentration of
solution and its volume, i.e.

molesi = MiVi

and the final number of moles can be expressed in terms of the desired final concentration of
solution and the desired final volume of solution., i.e.,
molesf = MfVf
 where Mi = initial or original concentration of solution
Vi = initial volume of solution
Mf = desired final concentration of solution
Vf = desired final volume of solution

The equation can now be expressed in terms of concentrations and volumes:

MiVi = MfVf

Example 8.4

Suppose one is to prepare 500.00 mL of 1.00M HCl from concentrated solution that is
12.0M HCl. Solve for the initial volume, Vi:

Solution

M f V f ( 1.00 M )( 0.500 L )
V i= =
Mi ( 12.0 M )

¿ 0.0417 L

This means that it requires 0.0417 liters of concentrated HCl to be diluted to a volume of
0.500 liters by just adding water to prepare a 1.00M solution.

8.9 SOLUTION STOICHIOMETRY

If one is to analyze a sample of an antacid containing NaHCO3 and some other impurities
or binder. One can do so by the process of titration or titrimetric analysis.

Let us presume that we have 0.5000 grams of antacid containing NaHCO 3 (FW = 84).
The antacid is then grinded and dissolved in pure water with a chemical indicator. A standard
solution of 0.1000M HCl called titrant is slowly added dropwise using a burette until there is a
change in color of solution. At this point, the volume of the titrant added is measured (assume
20.00mL). This color transition is called the endpoint of titration and it approximates the
equivalence point where the titrant and the analyte are said to be chemically equivalent. The
analyte is the solution containing the substance being analyzed.

The chemical equation for the reaction between titrant and analyte is:

HCl(aq) + NaHCO3(aq) NaCl(aq) + H2CO3(aq)

 From the equation, it can be seen that the number of moles HCl is equal to the number of
moles NaHCO3

moles HCl = moles NaHCO3

The number of moles HCl can be expressed in terms of its molarity and the volume
measured at equivalence point while the number of moles of NaHCO 3 can be expressed in terms
of the mass of NaHCO3 and its formula weight such that

moles HCl = (MV)HCl

grams NaHCO 3
moles NaHCO 3=
F W NaHCO 3

Therefore,

grams NaHCO 3
( MV ) HCl=
F W NaHCO
3

Solving for the mass of NaHCO3, we have

grams NaHCO3=¿

gram
¿
(
( 0.100 M ) ( 0.02000 L ) 84.0
mole )
❑
¿ 0.168 grams

Solving for the percent purity of the antacid,

0.168 grams Na HCO 3 ×100

%Na HCO3=
0.5000 grams antacid

¿ 33.6 %

Chapter 8 Exercises

Name:______________________________________________ Time/Day:_________________

Course:_______________ Score:_____________________
 1. Classify the following reactions as acid-base reaction, precipitation reaction, or redox
reaction.

a. Cu(NO3)2(aq) + 2NaOH(aq) Cu(OH)2(s) + 2NaNO3(aq)

b. Fe(s) + Cu(NO3)2(aq) Fe(NO3)2(aq) + Cu(s)

c. Ca(OH)2(aq) + H2SO4(aq) CaSO4(aq) + 2H2O(l)

2. Write the net ionic equation for the following reaction.

a. Zn(s) + H2SO4(aq) ZnSO4(aq) + H2(g)

b. NH4NO3(aq) + KOH(aq) NH3(aq) + KNO3(aq) + H2O(l)

3. In the following redox reaction, determine the reducing agent and oxidizing agent.

a. Cu2+ + I- Cu+ + I2

b. Cl2 + 2Br- 2Cl- + Br2

4. Based on the activity series, determine which reaction will occur.

a. 2Li(s) + Mg2+ 2Li+ + Mg(s)

b. Fe(s) + Zn2+ Fe2+ + Zn(s)

5. Calculate the concentration in molarity of a solution containing 1.06 grams of Na2CO3

(FW=106g/mol) with a total volume of 500.0 mL.

6. How many grams of KOH (FW=56.1g/mol) is required to prepare 0.05M of 250.0mL

solution of KOH?

7. What is the concentration of nitrate ion in 0.10M Cu(NO3)2 solution?

8. How many moles of NaCl (FW=58.44g/mol) are there in 100.0 mL of 0.50M NaCl?

9. What volume of 12.0M HCl stock solution is required to prepare 500.0mL of 0.10M HCl
solution?

10 .What is the volume of 0.10M HCl solution required to neutralize 1.00 grams of CaCO3
(FW=100 g/mol)?