Chapter – 4

Reactions in Aqueous Solution

Ours is a world based on water. Approximately 71% of the Earth’s surface is covered by water,
and another 3% is covered by ice; 66% of the mass of an adult human body is water, and water
is needed to sustain all living organisms. So, a large amount of important chemistry takes place
in water—that is, in aqueous solution. In this chapter, we’ll continue our study of chemical
reactions by seeing how different reactions can be classified and by learning some of the
general ways reactions take place.

4. 1. Some ways that chemical reaction occurs

A large number of important and interesting chemical reactions take place in aqueous solution.
Three general categories of solution reactions can be distinguished according to the type of
driving force behind them.

 In precipitation reactions, soluble ionic reactants yield an insoluble solid product. Many
precipitation reactions involve the double displacement of a pair of ionic compounds.
The driving force of a precipitation reaction is the production of the solid product.

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

 In acid-base neutralization reactions, an acid reacts with a base to produce water and
an ionic compound called a salt. The driving force of a neutralization reaction is the
formation of water molecules.

HCl (aq) + NaOH (aq)  H2O (l) + NaCl (aq)

 In oxidation-reduction reactions (redox reactions), electrons are transferred between

reaction partners (atoms, molecules or ions). As a result, the charges on atoms in the
various reactants change

Mg 0 (s) + 2H+1Cl (aq)  Mg+2Cl2 (aq) + H20 (g)

Problem. 4.1 Classify each of the following processes as a precipitation, acid–base

neutralization, or redox reaction:

(a) AgNO3(aq) + KCl(aq)  AgCl(s) + KNO3(aq)

(b) Cl2(g) + 2 NaBr(aq)  Br2(aq) + 2 NaCl(aq)

(c) Ca(OH)2(aq) + 2 HNO3(aq)  2 H2O(l)+ Ca(NO3)2(aq)

4.2. Electrolytes in aqueous solution

Although both sucrose and sodium chloride dissolve in water, the solutions these substances
form have very different properties. When molecular substances such as sucrose (C12H22O11)
dissolve in water, the resulting solution contain neutral sucrose molecule surrounded by water.
However, when ionic substances such as NaCl dissolve in water, the resulting solution contains
separate Na+ and Cl- ions surrounded by water molecules. Because of the presence of charged
ions, NaCl solution conducts an electric current, but sucrose solution does not.

C12H22O11(s) + H2O  C12H22O11(aq)

NaCl(s) + H2O  Na+(aq) + Cl-(aq)

Electrolytes and nonelectrolytes

NaCl and KBr which dissolve in water to produce conducting solution or ions are electrolytes.
Most electrolytes are ionic compounds, but some are molecular. Hydrogen chloride is a
molecular compound when pure, but dissociates into ions when it dissolves in water.

NaCl(s) + H2O  Na+(aq) + Cl-(aq)

HCl(g) + H2O  H+(aq) + Cl-(aq)

In contrast, substances that dissolve in water without forming ions are termed non-
electrolytes.

C12H22O11(s) + H2O   C12H22O11(aq)

Electrical conductivity can be used to distinguish between solutions of electrolytes and non-
electrolytes.

Strong and weak electrolytes

Compounds that dissociate to a large extent (70 to 100%) into ions when dissolved in water are
classified as strong electrolytes. For example, KCl and other ionic compounds. Compounds that
dissociate to a small extent are termed weak electrolytes. For example, CH3COOH.

NOTE : Pure water is a non-electrolyte because it doesn’t dissociate appreciably into H + and OH-
ions.
The classification of some common substances according to their electrolyte properties is
shown in Table 4.1

Calculation of Concentration of ions in a solution

Problem.4.2 What is the total molar concentration of ions in a 0.350 M solution of the strong
electrolyte Na2SO4, assuming complete dissociation?

Problem.4.3 What is the molar concentration of ions in a 0.225 M aqueous solution of FeBr 3,
assuming complete dissociation?

4.3. Aqueous reactions and net ionic equations

The equations written up to this point have been molecular equations. All substances have
been written using their full chemical formulas as if they were molecules.

Because we now know that here Pb(NO 3)2, KI and KNO3 are strong electrolytes dissociate in
water to their component ions, it is more accurate to write an ionic equation in which all of the
ionic species are shown.

Note that the NO3– and K+ ions are unchanged on the reactant side and the product side in this
equation. Ions that are unchanged are termed spectator ions. The essential part of this
chemical reaction—the formation of the lead iodide precipitate—can be shown by eliminating
the spectator ions and writing the net ionic equation.
Worked Example : Write a net ionic equation for

2HCl (aq) + Zn (s)  H2 (g) + ZnCl2 (aq)

An ionic equation is

2H+(aq) + 2Cl-(aq) + Zn(s)  H2(g) + Zn2+ (aq) + 2Cl- (aq)

A net ionic equation is

2H+(aq) + Zn(s)  H2(g) + Zn2+(aq)

Problem.4.4 Write net ionic equation for the following reactions

a. 2AgNO3(aq) + Na2CrO4(aq)  Ag2CrO4(s) + 2NaNO3(aq)

b. H2SO4(aq) + MgCO3(s)  H2O(l) + CO2(g) + MgSO4(aq)
c. Hg(NO3)2(aq) + 2NH4I(aq)  HgI2(s) + 2NH4NO3(aq)

4.4. Precipitation reactions and solubility rules

To predict whether a precipitation reaction will occur upon mixing solutions, we must know the
solubility of each of the potential products. A substance that has a low solubility in water will
likely form a precipitate in aqueous solution. A substance with high solubility in water will not
precipitate in solution.

The solubility guidelines are:

1. A compound containing one of the following cations is probably soluble

a. Group 1A cation : Li+, Na+, K+, Rb+, Cs+
b. Ammonium ions : NH4+
2. A compound containing one of the following anions is soluble
a. Halide : Cl-, Br-, I- (except Ag+, Hg22+, Pb2+ compounds
b. Nitrate(NO3-), Perchlorate(ClO4-), Acetate(CH3CO2-), Sulfate (SO42-) except
Sr2+, Ba2+, Hg22+, Pb2+ sulfates

Apart from these, the other ions are probably not soluble. Thus Carbonate, Sulfides,
phosphates and hydroxides are generally not soluble unless they contain an alkali metal or
ammonium cation. The main exceptions are the sulfides and hydroxides of Ca +2, Ba+2 and Sr+2.
 It has been observed that the compounds containing single charged ions are generally more
soluble than the compound containing multiple charged ions. Because, in the compound
containing multiple charged ions the strength of the ionic bonds are greater and it is difficult to
break these bonds apart during dissolution process.

The solubility guidelines helps us to predict (a) whether a precipitate is formed when solution of
two ionic compounds are mixed (b) A specific precipitate can also be formed by mixing
solutions of two ionic compounds. For example, if we have to prepare a sample of Ag 2CO3(s),
we have to mix a solution of AgNO3 with a solution of Na2CO3.

2AgNO3(aq) + Na2CO3(aq)  Ag2CO3(s) + 2 NaNO3(aq)

Both the starting compounds and NaNO3 are soluble in water. Ag2CO3 is the only insoluble
combination of ions and will therefore precipitate from the solution.

Precipitation Reaction

When aq. solutions of two ionic compounds are mixed, a precipitate is formed. Let us take
some examples.

(NO3- / Cl- / CO3-2 / PO4-3) + (Ca+2 / Ag+ / K+ / Cd+2)  Precipitate

Here, only the single charged cations will react with singly charged anions, doubly charged
cations will react with doubly charged anions and so on.

Possible combinations of singly charged ions: AgNO 3, KNO3, AgCl, KCl

Possible combinations of doubly charged ions: CaCO3, CdCO3

Of the possible combinations, AgCl, CaCO3, and CdCO3 are insoluble, so the anion might be Cl- or
CO3-2 and the cation might be Ag+, Ca+2 or Cd+2.

Worked Examples

Will a precipitate reaction occur when aq. Solution of CdCl 2 and (NH4)2S are mixed? If so, write
the net ionic equation.

Solution : First we have to predict the probable equation and solubility of each of the products.
In this case, the probable equation is

CdCl2(aq) + (NH4)2S(aq)  CdS + 2 NH4Cl

According to solubility guidelines CdS, a sulfide is insoluble and NH 4Cl, an ammonium
compound and halide is soluble. Thus, a precipitation reaction will occur

Cd+2 (aq) + S-2(aq)  CdS(s)

Problem.4.5 Predict whether each of the following compounds is likely to be

soluble in water:
(a) CdCO3 (b) MgO (c) Na2S

(d) PbSO4 (e) (NH4)3PO4 (f) HgCl2

Problem.4.6 Predict whether a precipitation reaction will occur in each of the following
situations. Write a net ionic equation for each reaction that occurs.
(a) NiCl2(aq) + (NH4)2S(aq)  ?
(b) AgClO4(aq) + CaBr2(aq)  ?
(c) Na2CrO4 (aq) + Pb(NO3)2 (aq)  ?
(d) ZnCl2 (aq) + K2CO3 (aq)  ?

Problem.4.7 How might you use a precipitation reaction to prepare a sample of Ca 3(PO4)2?
Write the net ionic equation.

4.5. Acids, bases and neutralization reactions

The Arrhenius system classifies acids as substances that dissociate in water to produce
hydrogen ions (H+), and bases as substances that dissociate in water to yield hydroxide ions
(OH–). The general formula HA is commonly used to represent an acid, and MOH to represent a
metal hydroxide.

The hydrogen ion H+(aq) does not exist as such in aqueous solutions. Hydrogen ions combine
with water molecules to give a more stable species, the hydronium ion H3O+, as demonstrated
in the following equation:

HCl(aq) + H2O(l)   H3O+(aq) + Cl-(aq)

Acids dissociate to different extents in aqueous solution. Acids that dissociate to a large extent
are strong electrolytes and strong acids. In contrast, acids that dissociate only to a small extent
are weak acids and weak electrolytes.

Acids can contain different numbers of acidic hydrogens, and can yield different numbers of
H3O+ ions in solution.

In a similar manner, bases can be strong or weak depending on the extent to which they
dissociate and produce OH – ions in solution. Most metal hydroxides are strong electrolytes
and strong bases. Ammonia, NH3, is a weak electrolyte and weak base.

Table 4.2 summarizes the names, formulas, and classifications of some common acids and
bases.

Naming of Acids:

Most acids are oxoacids. That means they contain both oxygen as well as hydrogen. When
dissolved in water, an oxoacid yields one or more H+ ions and an oxoanion.
For eg., HNO2(aq) + H2O(l)  H+ + NO2-
Nitrous acid Oxoanion i.e., nitrite ion
+ -
HNO3(aq) + H2O(l)  H + NO3
Nitric acid Oxoanion i.e., nitrate ion

The names of oxoacids are related to the names of corresponding oxoanions with the –ite or,
-ate ending of the anion name replaced by –ous acid or –ic acid respectively. The acid with
fewer oxygen has an –ous ending and the acid with more oxygen has an –ic ending.

Similarly, H2SO3 (aq) + H2O(l)  H3O+ (aq) + SO3-2

Sulfurous acid Sulfite ion

H2SO4 (aq) + H2O(l)  H3O+ (aq) + SO4-2

Sulfuric acid Sulfate ion

In addition to oxoacids, there are a small number of other common acids such as HCl, that
donot contain oxygen. For such compounds the prefix hydro and the suffix –ic acid are used for
the aqueous solution.

Hydrogen chloride gives hydrochloric acid

HCl(g)+ H2O(l) : H3O+(aq)+ Cl-(aq)

Worked example

Naming acids

Name the following acids: (a) HBrO(aq) (b) H2S(aq)

Solution :

To name an acid, look at the formula and decide whether the compound is an oxoacid. If so, the
name must reflect the number of oxygen atoms. If the compound is not an oxoacid, it is named
using the prefix hydro- and the suffix -ic acid.

(a) This compound is an oxoacid that yields hypobromite ion ( BrO-)) when dissolved
in water. Its name is hypobromous acid.

(b) This compound is not an oxoacid but yields sulfide ion when dissolved in water. As a
pure gas, H2S is named hydrogen sulfide. In water solution, it is called hydrosulfuric acid.
Problem.4.8 Name the following acids:

(a) HIO4 (b) HBrO2 (c) H2CrO4

Problem.4.9 Give likely chemical formulas corresponding to the following names:

(a) Phosphorous acid (b) Hydroselenic acid

Neutralization Reaction

When an acid and a base are mixed in stoichiometric proportions, their acidic and basic
properties disappear as the result of a neutralization reaction.

Because the salts that form in neutralization reaction are generally strong electrolytes, we can
write the neutralization reaction as an ionic equation.

When the spectator ions are removed, the net ionic equation is revealed.

This net ionic equation is the same for the neutralization reaction of any strong acid and strong
base.

For the reaction of a weak acid with a strong base, a similar neutralization occurs. Consider the
neutralization of HF with KOH.

HF(aq) + KOH(aq)   KF(aq) + H2O(l) molecular equation

HF(aq) +  (aq) + OH-(aq)    (aq) + F-(aq) + H2O(l) ionic equation

HF(aq) + OH-(aq)   F-(aq) + H2O(l) net ionic equation

The weak acid HF is written as a molecular formula because its dissociation is incomplete.

Worked example

Writing ionic and net ionic equations for an acid–base reaction

Write both an ionic equation and a net ionic equation for the neutralization reaction of aqueous
HBr and aqueous Ba(OH)2.

Solution

Hydrogen bromide is a strong acid whose aqueous solution contains H + ions and Br- ions.
Barium hydroxide is a strong base whose aqueous solution contains Ba 2+ and OH- ions. Thus, we
have a mixture of four different ions on the reactant side. Write the neutralization reaction as
an ionic equation, and then cancel spectator ions to give the net ionic equation.

Ionic equation : 2H+(aq) + 2Br-(aq) + Ba+2(aq) + 2OH-(aq)  2H2O(l) + 2Br-(aq) + Ba+2(aq)

Net ionic equation : 2H+(aq) + 2OH-(aq)  2H2O(l)

Or, H+(aq) + OH-(aq)  H2O (l)

The reaction of HBr with Ba(OH) 2 involves the combination of a proton (H + ) from the acid with
OH- from the base to yield water and an aqueous salt (BaBr 2).

Problem.4.10 Write a balanced ionic equation and net ionic equation for each of the following
acid–base reactions:

(a) 2CsOH(aq) + H2SO4 (aq) 

(b) Ca(OH)2(aq) + 2CH3COOH(aq) 

4.6 Oxidation-Reduction (Redox) Reactions

In addition to precipitation and neutralization reactions, aqueous ions can participate

in oxidation-reduction reactions or redox reactions.
Examples of Redox reactions in use

a. Rusting of Fe i.e., an oxidation of Fe4Fe(s) + 3O2 (g)  2 Fe2O3 (s)

b. Manufacture of Fe i.e., reduction of Fe2O3 2Fe2O3 (s) + 3 C(s)  4Fe(s) + 3CO2(g)

Oxidation is defined as the loss of electrons, whereas reduction is defined as the gain of

electrons. Thus, redox reactions can be considered electron transfer reactions.

Oxidation numbers are a useful tool for determining whether a substance has been oxidized or
reduced. An element that undergoes a change in oxidation number in the course of a reaction
has been oxidized or reduced. Let's learn how to assign oxidation numbers.

Assigning Oxidation Number

1. An atom in its elemental state has an oxidation number of 0.

Na,  H2, Cl2, S, Xe

Each atom in these elements has an oxidation number of 0.

2. An atom in a monoatomic ion has an oxidation number identical to its charge.

Na+ Ba2+ Al3+ Br– S2–

+1 +2 +3 -1 -2

The oxidation number is equal to the charge on the monoatomic ion.

3. An atom in a polyatomic ion or a molecular compound usually has the same oxidation
number it would have if it were in a monoatomic ion.
a) Elements to the left on the periodic table are "cation like" and have positive oxidation
numbers.
b) Elements to the right on the periodic table are "anion like" and have negative oxidation
numbers. Consider NH3. N has an oxidation number of –3; each H has an oxidation
number of +1.
c) Hydrogen has a +1 oxidation number when bonded to nonmetals, and has a –1
oxidation number when bonded to a metal. NaH (H : –1 oxidation number) H 2O (H : +1
oxidation number)
d) Oxygen often has a –2 oxidation number, but can have a –1 oxidation number in the
peroxide ion, O22–. H2O (O : –2 oxidation number) HOOH (O : –1 oxidation number)
 e) Halogens usually have an oxidation number of –1, unless bonded to oxygen, when they
have a positive oxidation number. HCl (Cl : –1 oxidation number) HOCl (Cl : +1 oxidation
number)

4. The sum of the oxidation numbers is 0 for a neutral compound and is equal to the net
charge for a polyatomic ion. Worked example

Assigning oxidation numbers

Assign oxidation numbers to each atom in the following substances

(a) CdS (b) AlH3 (c) S2O3-2(d) Na2Cr2O7

Solution : (a)+2, -2, (b) +3, -1 (c) +2, -2 (d) +1,+6,-2

Problem 4.11 Assign an oxidation number to each atom in the following compounds:

(a) SnCl4 (b) CrO3 (c) VOCl3

(d) V2O3 (e) HNO3 (f) FeSO4

4.7. Identifying Redox Reactions

Let us consider the example of a redox reaction (Rusting of iron).

4Fe(s) + 3 O2 (g)  2Fe2O3(s)

Here, both Fe and O in the reactant side have O.N. 0 . But, in Fe 2O3, Fe is having O.N +3
whereas, O is having O.N -2. So, here Fe is oxidized where as O is reduced. So, here oxidation
and reduction are taking place simultaneously. Note that in a redox reaction, the total number
of electrons given up by the atoms being oxidized is equal to the total number of electrons
gained by the atoms being reduced. For eg., in the oxidation of Fe, the total no of e - being
oxidized = 4 Fe X 3 e- = 12 e-. Similarly, total no. of e- being reduced = 6 O X 2 e- = 12 e-.

For different metals in Gr. IA (Li, Na etc), O.N. is +1. For different metals in Gr.IIA (Be, Mg etc.)
O.N. is +2. Similarly, transition metals in the middle of the periodic table can give up a variable
no. of e- to yield variable +ve oxidation states. Ti can react with Cl 2 to yield either TiCl 3 or TiCl4.
So, Ti is having either +3 or +4 O.S. because, Cl is having -1 O.S.
Oxidation and reduction always occur together. Whenever one atom loses electrons (is
oxidized), another atom must gain those electrons (be reduced). The reactants can be classified
as either a reducing agent or an oxidizing agent.

Reducing agent

 causes reduction
 loses one or more electrons
 is oxidized
 oxidation number of atom increases

Oxidizing agent

 causes oxidation
 gains one or more electrons
 is reduced
 oxidation number of atom decreases

Worked example

Identifying oxidizing and reducing agents

Assign oxidation numbers to all atoms, tell in each case which substance is undergoing
oxidation and which reduction, and identify the oxidizing and reducing agents.

(a) Ca(s) + 2H+(aq)  Ca+2(aq) + H2(g)

(b) 2Fe+2(aq) + Cl2(aq)  2Fe+3(aq) + 2Cl-(aq)

Solution

(a) O.N. of Ca = 0, H+ = +1, Ca+2 = +2 and H2 = 0. Ca is undergoing oxidn,( O.N.

increases from 0 to +2) and H+ is undergoing redn (O.N. decreases from +1 to
0).
So, Ca is reducing agent whereas H+ is oxidising agent.
(b) O.N. of Fe+2 = +2, Cl = 0, Fe +3 = +3 and Cl- = -1. Fe+2 is undergoing oxidn,( O.N.
increases from +2 to +3) and Cl2 is undergoing redn (O.N. decreases from 0 to -1).
So, Fe+2 is reducing agent whereas Cl2 is oxidising agent.
Problem.4.12 Aqueous copper(II) ion reacts with aqueous iodide ion to yield solid copper(I)
iodide and aqueous iodine. Write the balanced net ionic equation, assign oxidation numbers to
all species present, and identify the oxidizing and reducing agents.

Problem.4.13 In each of the following reactions, tell which substance is undergoing an

oxidation and which a reduction, and identify the oxidizing and reducing agents.

a. SnO2(s) + 2C(s)  Sn(s) + 2CO(g)

b. Sn+2(aq) + 2Fe+3(aq)  Sn+4(aq) + 2Fe+2(aq)
c. 4NH3(g) + 5O2 (g)  4NO(g) + + 6 H2O(l)

4.8 The Activity Series of the Elements

The knowledge of the reaction of an aqueous cation, usually a metal ion, with a free
element to give a different cation and a different element is obtained from activity series.
For eg., whether reaction occurs between a given ion i.e., Ag + and a given element i.e., Cu,
will be known from activity series. It depends on the relative ease with which the various
species gain or lose electrons (are reduced or oxidised). An activity series ranks the
elements in order of their reducing ability in aqueous solution.
The elements at the top of the table readily give up electrons and are stronger reducing agents.
The elements at the bottom give up electrons less readily and are weaker reducing agents. Any
element higher in the activity series will react with the ion of any element lower in the activity
series.

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 gives electrons to
Ag+ ions.

Cu(s) + 2 Ag+(aq)  Cu+2(aq) + 2Ag(s)

Conversely, because gold is below silver in the activity series, gold metal does not
give electrons to Ag+ ions.

Au(s) + 3 Ag+(aq)  Au+3 (aq) + 3 Ag(s) (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 series
—the 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.

For eg., 2Na(s) + 2H2O(l)  2Na+(aq) + 2OH-(aq) + H2(g)

In 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(s) + 2 H+ (aq)  Fe+2 (aq) + H2(g)

Ag (s) + H+(aq)  No reaction

Note that the most reactive metals at the top of the activity series are on the left of the periodic
table, while the least reactive metals are on the right side of the periodic table.

Worked example

Predicting the products of redox reactions

Predict whether the following redox reactions will occur:

 a. Hg+2(aq) + Zn(s)  Hg(l) + Zn+2(aq)
b. 2H+(aq) + Cu(s)  H2(g) + Cu+2(aq)

Solution

(a) Zinc is above mercury in the activity series, so this reaction will occur
(b) Copper is below hydrogen in the activity series, so this reaction will not occur

Problem 4.14 Predict whether the following reactions will occur:

a. 2H+(aq) + Pt(s)  H2(g) + Pt+2(aq)

b. Ca+2(aq) + Mg(s)  Ca(s) + Mg+2(aq)

Problem.4.15 Element B will reduce the cation of element A (A +) but will not reduce the cation
of element C (C+). Will element C reduce the cation of element A? Explain.

4.9 Balancing Redox Reactions: The Half-Reaction Method

The half-reaction method is another way to balance redox reactions. In this method, the overall
reaction is separated into two half-reactions. Each redox reaction can be broken down into an
oxidation half-reaction and a reduction half-reaction. Each half-reaction is balanced separately
for mass and charge, and then the two half-reactions are added to obtain the final balanced
equation.
As an example, let’s look at the reaction of aqueous potassium dichromate (K 2Cr2O7) with
Aqueous NaCl. The reaction occurs in acidic solution according to the unbalanced net ionic
Equation

Cr2O72-(aq)+ Cl-(aq)  Cr3+(aq)+ Cl2(aq) (Unbalanced)

The first step is to decide which atoms have been oxidized and which have been reduced. In the
present case, the chloride ion is oxidized from -1 to 0, and the chromium atom is reduced from
+6 to +3. Thus, we can write two unbalanced half reactions that show the separate parts:
Oxidn half reaction : Cl-(aq)  Cl2(aq)

Redn. half reaction : Cr2O7-2 (aq)  Cr+3 (aq)

With the two half-reactions identified, each is balanced separately. Begin by balancing for all
atoms other than H and O. The oxidation half-reaction needs a coefficient of 2 before the Cl -,
and the reduction half-reaction needs a coefficient of 2 before the Cr +3. Then oxidn. and redn.
half reactions become

Oxidn half reaction : 2Cl-(aq)  Cl2(aq)

Redn. half reaction : Cr2O7-2 (aq)  2Cr+3 (aq)

Next, balance both half-reactions for oxygen by adding H 2O to the side with less O, and then
balance for hydrogen by adding H+ to the side with less H. The oxidation half-reaction has no O
or H, but the reduction half-reaction needs 7 H 2O on the product side to balance for O, and
then 14 H+ on the reactant side to balance for H. So, the reduction half reaction will be

Cr2O7-2 (aq) + 14 H+(aq)  2 Cr3+(aq) + 7 H2O(l)

Now, balance both half-reactions for charge by adding electrons (e -) to the side with the greater
positive charge. The oxidation half-reaction has 2 minus charges on the reactant side ( 2Cl -) and
2e- must therefore have added to the product side. The reduction half-reaction has a net of 12
positive charges on the reactant side and 6 positive charges on the product side and so 6e - must
have added to the reactant side: So, oxidation and reduction half reactions will be

Oxidn half reaction : 2Cl-(aq)  Cl2(aq) + 2e-

Redn. half reaction : Cr2O7-2 (aq) + 14 H+(aq) + 6e-  2 Cr3+(aq) + 7 H2O(l)

With both half-reactions now balanced, we need to multiply the equations by suitable
coefficients so that the number of electrons is the same in both. So,
Oxidn half reaction : [ 2Cl-(aq)  Cl2(aq) + 2e- ] X 3

Redn. half reaction : Cr2O7-2 (aq) + 14 H+(aq) + 6e- 2 Cr3+(aq) + 7 H2O(l)

Adding the two half-reactions together and canceling the species that occur on both sides (only
the electrons in this example) then gives the final balanced equation.
Check the answer to make sure it is balanced both for atoms and for charge.

6Cl-(aq)  3Cl2(aq) + 6e-

Cr2O72−(aq) + 14 H+(aq) + 6e-  2 Cr3+(aq) + 7 H2O(l)

Cr2O72−(aq) + 14 H+(aq) + 6Cl-(aq)  3Cl2(aq) + 2 Cr3+(aq) + 7 H2O(l)

Problem.4.16 Write unbalanced half-reactions for the following net ionic equations:

a.MnO4 - (aq)+ IO3 - (aq)  MnO2(s)+ IO4-(aq)

b.NO3-(aq)+ SO2(aq)  SO4-2(aq)+ NO2(g)

Problem.4.17 Balance the following net ionic equation by the half-reaction method.

The reaction takes place in acidic solution.

NO3-(aq)+ Cu(s) NO(g)+ Cu2+(aq) (Unbalanced)

4.10 Redox Stoichiometry

Previously, you have already learnt how the concentration of an acid or base solution can be
determined by titration. A similar procedure can be used to determine the concentration of
oxidizing or reducing agents. In a redox titration, a redox reaction is performed under
stoichiometric conditions and a color change is observed that signals the completion of the
reaction. For example, consider the following reaction of aqueous potassium permanganate
and oxalic acid:

The characteristic purple color of the permanganate ion is useful as an indicator for this
reaction.

The flow diagram below outlines the steps for using a redox titration to determine a
concentration.

To calculate the molarity of the KMnO4 solution, we need to find the number of moles of
KMnO4 present in the 22.35 ml of solution used for titration. We do this by first calculating the
number of moles of oxalic acid that react with the permanganate ion, using a gram-to-mole
conversion with the molar mass of H2C2O4 as the conversion factor:

Moles of H2C2O4 = g of H2C2O4 / Mol. Mass of H2C2O4

= 0.2585 / 90.04 = 2.871 X 10-3 mol

According to the balanced equation, 5 mol of oxalic acid react with 2 mol of permanganate ion.
Thus, we can calculate the number of moles of KMnO 4 that react with 2.871 X 10-3 mol of
H2C2O4.

Moles of KMnO4 = 2.871 X 10-3 mol H2C2O4 X (2mol KMnO4/5 mol H2C2O4.)

= 1.148 X 10-3 mol KMnO4

Knowing both the number of moles of KMnO 4 that react (1.148 X 10-3 mol ) and the volume of
the KMnO4 solution (22.35 ml), we can calculate the molarity:

Molarity = (1.148 X 10-3 mol KMnO4/22.35 mol) X ( 1000ml/1L)

= 0.05136 M

The molarity of the KMnO4 solution is 0.05136 M

Worked example

Using a redox reaction to determine a solution’s concentration

The concentration of an aqueous I3- solution can be determined by titration with aqueous
sodium thiosulfate, Na2S2O3, in the presence of a starch indicator, which turns from deep blue
to colourless when all the I3- has reacted. What is the molar concentration of I 3- in an aq.
solution if 24.55 ml of 0.102 M Na2S2O3 is needed for complete reaction with 10ml of the I 3-
solution ? The net equation is

2 S2O3-2(aq)+ I3-(aq)  S4O6-2(aq)+ 3 I-(aq)

Solution

We first need to find the number of moles of thio sulfate ion used for the titration:

(24.55ml /1000ml) X (0.102 mol S2O3-2) = 2.50 X 10-3 mol S2O3-2

According to the balanced equation, 2 mol of S2O3-2 ion react with 1 mol of I3- ion.

Thus, we can find the number of moles of I3- ions :

2.50 X 10-3 mol S2O3-2 X ( 1 mol I3-/ 2 mol S2O3-2) = 1.25 X 10-3 mol I3-
Knowing both the no. of moles of I3- (1.25 X 10-3 mol) and the volume of the I3- solution (10 ml),
let us calculate the molarity :

(1.25 X 10-3 mol I3- / 10 ml) X (103 ml / 1L) = 0.125 M

The molarity of I3- solution is 0.125 M.

Problem 4.18 What is the molar concentration of Fe +2 ion in an aqueous solution if 31.50 mL of
0.105 M KBrO3 is required for complete reaction with 10.00 mL of the Fe +2 solution ? The net
ionic equation is:
6 Fe2+(aq)+ BrO3-(aq)+ 6 H+(aq)  6 Fe3+(aq)+ Br-(aq)+ 3 H2O(l)

4.11. Some Applications of Redox Reactions

Redox reactions take place with almost every element in the periodic table except the noble
gases. A vast number of redox reactions occur in nature, industrial and biological processes. A
few are summarized here.

1. Combustion is the burning of fuel by oxidation with oxygen in air. Fuels include natural gas,
wood, paper, and other organic substances composed of carbon and hydrogen. Some metals
like Ca, Mg also burn in air.

CH4(g) + 2 O2(g)   CO2(g) + 2 H2O(l)

2Mg(s) + 2 O2(g)   2 MgO(s)

2. Bleaching is the use of redox reactions to decolorize or lighten colored materials. Oxidizing
agents used in bleaching include hydrogen peroxide (H 2O2) for hair and sodium hypochlorite
(NaClO) for clothes. In all cases, coloured impurities are destroyed by reaction with a strong
oxidizing agent.

3. Batteries are all based on redox reactions. The inexpensive alkaline battery commonly used
in flashlights and other small household items uses a thin steel can containing zinc powder and
a paste of potassium hydroxide as one reactant, separated by paper from a paste of powdered
carbon and manganese dioxide as the other reactant. A graphite rod with a metal cap sticks
into the MnO2 to provide electrical contact. When the can and the graphite rod are connected
by a wire, zinc sends electrons flowing through the wire toward the MnO 2 in a redox reaction.
The resultant electrical current can be used to light a bulb or power a small electronic device.
The reaction is
Zn(s)+ 2 MnO2(s)  ZnO(s)+ Mn2O3(s)
4. Metallurgy is the science of extracting and purifying metals from their ores making use of
various redox processes. For example, metallic zinc is prepared by reduction of ZnO with coke, a
form of carbon:
ZnO(s)+ C(s)  Zn(s)+ CO(g)

5. Corrosion is the deterioration of a metal by oxidation, such as the rusting of iron

in moist air.
4 Fe(s) + 3 O2(g)  2 Fe2O3.H2O(s) (Rust)

6. Respiration is the process of breathing and using oxygen for many biological redox reactions
that occur in living organisms. For example, the simple sugar glucose (C 6H12O6) reacts with O2 to
give CO2 and H2O according to the following equation:

C6H12O6(s) + 6 O2(g)   6 CO2(g) + 6 H2O(l) + energy

Glucose

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