General Chemistry I

CHEMY 101, Chapter 4

Dr. Wael Amer

Associate Professor
College of Science, University of Bahrain
2022 – 2023, Semester I
 Chapter 4

General Properties of Aqueous Solutions

2
4.1. General Properties of Aqueous Solutions
A solution is a homogeneous mixture of two or more substances. The solute is the substance
present in a smaller amount, whereas the solvent is the substance present in a larger amount. A
solution may be gaseous (such as air), solid (such as an alloy), or liquid (seawater, for example).

Electrolytic properties
An electrolyte is a substance that, when dissolved in water, results in a solution that can
conduct electricity. A nonelectrolyte does not conduct electricity when dissolved in water.

Test: A pair of inert (copper or platinum) electrodes is immersed in a beaker of water. To light the
bulb, electric current must flow from one electrode to the other, thus completing the circuit.

Pure water is a very poor conductor of electricity. However, if we add a small amount of NaCl, the
bulb will glow as soon as the salt dissolves in the water. Solid NaCl, an ionic compound, breaks
up into Na+ and Cl- ions when it dissolves in water.

3
The Na+ ions are attracted to the negative electrode and the Cl- ions to the positive electrode. This
movement sets up an electrical current that is equivalent to the flow of electrons along a metal wire.
Therefore, NaCl is an electrolyte. Pure water contains very few ions, so it cannot conduct electricity.

A characteristic of strong electrolytes is that the solute is assumed to be 100 percent dissociated into
ions in solution. (By dissociation we mean the breaking up of the compound into cations and anions.)

(a) A nonelectrolyte solution does not

contain ions, and the lightbulb is not lit.

(b) A weak electrolyte solution contains a

small number of ions, and the lightbulb is
dimly lit.

(c) A strong electrolyte solution contains a

large number of ions, and the lightbulb is
brightly lit.

The molar amounts of the dissolved4 solutes

are equal in all three cases.
Acetic acid is a weak electrolyte because its ionization in water is incomplete.
CH3COOH CH3COO- (aq) + H+ (aq)
A reversible reaction.
The reaction can occur in both directions.

Nonelectrolyte does not conduct electricity?

No cations (+) and anions (-) in solution
H2O
Sugar C H O
6 12 6 (s) C6H12O6 (aq)

5
Water is a very effective solvent for ionic compounds. It has a positive region (the H atoms) and
a negative region (the O atom), or positive and negative “poles”; for this reason, it is
a polar solvent.

When an ionic compound such as sodium chloride dissolves in water, the three-dimensional
lattice of ions in the solid is broken apart. The Na+ and Cl− ions are separated from each other
and undergo hydration, the process in which an ion is surrounded by water molecules.

+ -
Na Cl
6
Acids and bases are also electrolytes. Some acids, including hydrochloric acid (HCl) and nitric acid
(HNO3), are strong electrolytes. These acids ionize completely in water.

On the other hand, certain acids, such as acetic acid (CH3COOH), which is found in vinegar, ionize to a
much lesser extent (partially ionized).

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4.2 Precipitation Reactions
They result in the formation of an insoluble product, known as a precipitate. A precipitate is an insoluble
solid that separates from the solution.

Precipitation reactions usually involve ionic compounds. For example, when an aqueous solution of lead(II)
nitrate [Pb(NO3)2] is added to an aqueous solution of potassium iodide (KI), a yellow precipitate of lead(II)
iodide (PbI2) is formed:

This is an example of a metathesis

reaction (also a double-displacement
reaction), a reaction that involves the
exchange of parts between the two
compounds.

(In this case, the cations in the two

compounds exchange anions, so
Pb2+ ends up with I− as PbI2 and K+ ends
up with NO3− as KNO3.) 8
Solubility
How can we predict whether a precipitate will form when a compound is added to a solution or when two
solutions are mixed? It depends on the solubility of the solute, which is defined as the maximum amount
of solute that will dissolve in a given quantity of solvent at a specific temperature.

Chemists refer to substances as soluble, slightly soluble, or insoluble in a qualitative sense. A substance is
said to be soluble if a fair amount of it visibly dissolves when added to water. If not, the substance is
described as slightly soluble or insoluble. All ionic compounds are strong electrolytes, but they are not
equally soluble.

9
Molecular Equations, Ionic Equations, and Net Ionic Equations
The earlier equation describing the precipitation of lead(II) iodide is called a molecular
equation, because the formulas of the compounds are written as though all species existed as molecules
or whole units.

A molecular equation is useful because it identifies the reagents [that is, lead(II) nitrate and potassium
iodide]. If we wanted to bring about this reaction in the laboratory, we would use the molecular equation.
However, a molecular equation does not describe in detail what actually is happening in solution. 10
When ionic compounds dissolve in water, they break apart into their component cations and anions. To be
more realistic, the equations should show the dissociation of dissolved ionic compounds into ions.
Therefore, returning to the reaction between potassium iodide and lead(II) nitrate, we would write

Pb2+(aq)+2NO3−(aq)+2K+(aq)+2I−(aq) → PbI2(s)+2K+(aq)+2NO3−(aq)

The preceding equation is an example of an ionic equation, which shows dissolved species as free,
hydrated ions.

Referring to Table 4.2, we see that PbI2 is an insoluble compound and KNO3 is soluble. Therefore, the
dissolved KNO3 remains in solution as separate K+ and NO3− ions, which are called spectator
ions, or ions that are not involved in the overall reaction.

Because spectator ions appear on both sides of an equation, they can be eliminated from the ionic
equation:

Finally, we end up with the net ionic equation, which shows only the species that actually take part in the
reaction:
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Another example,
when an aqueous solution of barium chloride (BaCl2) is added to an aqueous solution of sodium sulfate
(Na2SO4), a white precipitate is formed.

Treating this as a metathesis reaction, the products are BaSO4 and NaCl. From Table 4.2 we see that only
BaSO4 is insoluble. Therefore, we write the molecular equation as

The ionic equation for the reaction is

Canceling the spectator ions (Na+ and Cl−) on both sides of the equation gives us the net ionic equation

12
The following four steps summarize the procedure for writing ionic and net ionic equations

1. Write a balanced molecular equation for the reaction, using the correct formulas for the reactant and
product ionic compounds. Refer to Table 4.2 to decide which of the products is insoluble and therefore will
appear as a precipitate.

2. Write the ionic equation for the reaction. The compound that does not appear as the precipitate should
be shown as free ions.

3. Identify and cancel the spectator ions on both sides of the equation. Write the net ionic equation for the
reaction.

4.Check that the charges and number of atoms balance in the net ionic equation.

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 Precipitation of Silver Iodide
•Molecular equation:
AgNO3(aq) +NaI(aq) → AgI(s) + NaNO3(aq)

•Complete ionic equation:

Ag+(aq) + NO3−(aq) + Na+(aq) + I −(aq) → AgI(s) + Na+(aq) + NO3−(aq)

spectator ions
•Net ionic equation:
Ag+(aq) + I −(aq) → AgI(s)

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15
16
➢ Write the net ionic equation for the reaction of silver nitrate with sodium chloride

AgNO3 (aq) + NaCl (aq) AgCl (s) + NaNO3 (aq)

Ag+ + NO3- + Na+ + Cl- AgCl (s) + Na+ + NO3-

Ag+ + Cl- AgCl (s)

Predicting Precipitation Reactions

Exercise:
Predict whether a precipitate will form when dilute solutions of the following ionic compounds are
mixed. If so, write a net ionic equation for the reaction.

a) CaCl2 and Na2CO3

b) FeCl3 and AgNO3
c) Cu(NO3)2 and (NH4)2CO3
d) (NH4)3PO4 and K2CO3 17
4.3 Acid-Base Reactions

General Properties of Acids and Bases

Arrhenius’s definition
Acids are substances that ionize in water to produce H+ ions and
bases as substances that ionize in water to produce OH− ions.

Acids
•Acids have a sour taste; for example, vinegar owes its sourness to acetic acid, and lemons and other
citrus fruits contain citric acid.
•Acids cause color changes in plant dyes; for example, they change the color of litmus from blue to red.
•Acids react with certain metals, such as zinc, magnesium, and iron, to produce hydrogen gas.
2HCl(aq)+Mg(s)→MgCl2(aq)+H2(g)

•Acids react with carbonates and bicarbonates, such as Na2CO3, CaCO3, and NaHCO3, to produce carbon
dioxide gas.
2HCl(aq)+CaCO3(s)→CaCl2(aq)+H2O(l)+CO2(g)
HCl(aq)+NaHCO3(s)→NaCl(aq)+H2O(l)+CO2(g)
•Aqueous acid solutions conduct electricity.
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Bases
•Bases have a bitter taste.
•Bases feel slippery; for example, soaps, which contain bases, exhibit this property.
•Bases cause color changes in plant dyes; for example, they change the color of litmus from red to blue.
•Aqueous base solutions conduct electricity.

Brønsted definitions
Brønsted acid is a proton donor, and a Brønsted base is a proton acceptor. Note that Brønsted’s
definitions do not require acids and bases to be in aqueous solution.

Hydrochloric acid is a Brønsted acid because it donates a proton, symbolized by H+(aq), in water:

The size of a proton is about 10−15 m, compared to a diameter of 10−10 m for an average atom or ion.

Such an exceedingly small charged particle cannot exist as a separate entity in aqueous solution owing to
its strong attraction for the negative pole (the O atom) in H2O. Consequently, the proton exists in the
hydrated form

hydronium ion 19
Monoprotic acids; that is, each unit of the acid yields one hydrogen ion upon ionization.

Because the ionization of acetic acid is incomplete (note the double arrows), it is a weak electrolyte. For
this reason, it is called a weak acid.

On the other hand, HCl and HNO3 are strong acids because they are strong electrolytes, so they are
completely ionized in solution.

Sulfuric acid (H2SO4) is a diprotic acid, because each unit of the acid gives up two H+ ions, in two
separate steps:

H2SO4 is a strong electrolyte or strong acid, but HSO4− is a weak acid or weak electrolyte.

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Triprotic acids, which yield three H+ ions, are relatively few in number. The best known triprotic acid is
phosphoric acid, whose ionizations are:

All three species (H3PO4, H2PO4−, and HPO42−) in this case are weak acids.

21
Sodium hydroxide (NaOH) and barium hydroxide [Ba(OH)2] are strong electrolytes. This means that
they are completely ionized in solution:

The OH− ion can accept a proton as follows:

Thus, OH− is a Brønsted base.

Common strong bases: LiOH, NaOH, KOH, Ca(OH)2, Sr(OH)2, Ba(OH)2

Ammonia (NH3) is classified as a Brønsted base because it can accept a H+ ion

Ammonia is a weak electrolyte (and therefore a weak base)

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23
Acid-Base Neutralization
A neutralization reaction is a reaction between an acid and a base. Generally, aqueous acid-base
reactions produce water and a salt, which is an ionic compound made up of a cation from the base and an
anion from the acid:

The substance we know as table salt, NaCl, is a product of the acid-base reaction

However, because both the acid and the base are strong electrolytes, they are completely ionized in
solution. The ionic equation is

Therefore, the reaction can be represented by the net ionic equation

Both Na+ and Cl− are spectator ions.

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A reaction between a weak acid such as hydrocyanic acid (HCN) and a strong base is

Because HCN is a weak acid, it does not ionize appreciably in solution. Thus, the ionic equation is written
as

and the net ionic equation is

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26
27
Strong acid ― Weak bases

Note: Weak base NH3(aq) = NH3/H2O = NH4OH

HNO3 (aq) + NH3(aq) NH4NO3 (aq)

H+ + NO3- + NH3 NH4+ + NO3-

Net ionic equation

H+ + NH3 NH4+

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Strong acid ― Weak bases

Note: Weak base NH3(aq) = NH3/H2O = NH4OH

HNO3 (aq) + NH4OH(aq) H2O (l) + NH4NO3(aq)

H+ + NO3- + NH4OH H2O (l) + NH4+ + NO3-

Net ionic equation

H+ + NH4OH H2O + NH4+

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Example
Write a net ionic equation for each of the following reactions in
aqueous solutions.
(a) Hypochlorous acid (HClO) and calcium hydroxide.
(b) Ammonia with perchloric acid (HClO4).
(c) Hydriodic acid (HI) with sodium hydroxide.

(a)

Net ionic equation

(b)

Net ionic equation

(c)

Net ionic equation

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Acid-Base Reactions Leading to Gas Formation
Certain salts like carbonates (containing the CO32− ion), bicarbonates (containing the HCO3− ion),
sulfites (containing the SO32− ion), and sulfides (containing the S2− ion) react with acids to form gaseous
products. For example, the molecular equation for the reaction between sodium carbonate (Na2CO3) and
HCl(aq) is

Carbonic acid is unstable and if present in solution in sufficient concentrations

decomposes as follows:

Similar reactions involving other mentioned salts are

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4.5 Concentration of Solutions
The concentration of a solution is the amount of solute present in a given amount of solvent, or a given
amount of solution. The concentration of a solution can be expressed in many different ways. Molarity
(M), or molar concentration, is the number of moles of solute per liter of solution.

Molarity is defined as

where n denotes the number of moles of solute and V is the volume of the solution in liters.

A 1.46 molar glucose (C6H12O6) solution, written as 1.46 M C6H12O6, contains 1.46 moles of the solute
(C6H12O6) in 1 L of the solution. Of course, we do not always work with solution volumes of 1 L. Thus, a
500-mL solution containing 0.730 mole of C6H12O6 also has a concentration of 1.46 M:

Note that concentration, like density, is an intensive property, so its value does not depend on how much
of the solution is present.
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Consider what happens when a sample of potassium chloride (KCl) is dissolved in enough water to make a
1 M solution:

Because KCl is a strong electrolyte, it undergoes complete dissociation in solution. Thus, a 1 M KCl
solution contains 1 mole of K+ ions and 1 mole of Cl− ions, and no KCl units are present. The
concentrations of the ions can be expressed as [K+] = 1 M and [Cl−] = 1 M, where the square brackets [ ]
indicate that the concentration is expressed in molarity.

Similarly, in a 1 M barium nitrate [Ba(NO3)2] solution

we have [Ba2+] = 1 M and [NO3-] = 2 M and no Ba(NO3)2 units at all.

The procedure for preparing a solution of known molarity

1) First, the solute is accurately weighed and transferred to a volumetric flask through a funnel.
2) Next, water is added to the flask, which is carefully swirled to dissolve the solid.
3) After all the solid has dissolved, more water is added slowly to bring the level of solution exactly to the
volume mark. 33
4) Knowing the volume of the solution in the flask and the quantity of compound (the number of moles)
dissolved, we can calculate the molarity of the solution

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• Ex., for 0.1 M MgCl2 solution
H2O
MgCl2 (s) Mg2+ (aq) + 2 Cl- (aq)
➢ Total number of moles of ions per mole of MgCl2 is 3.

[Mg2+] = 0.1 M [Cl-] = 2 x 0.1 = 0.2 M

• Ex., for 0.2 M Cr2(SO4)3 solution

H2O
Cr2(SO4)3 (s) 2Cr3+ (aq) + 3SO42- (aq)
➢ Total number of moles of ions per mole of Cr2(SO4)3 is 5

[Cr3+] = 2 x 0.2 = 0.4 M [SO42-] = 3 x 0.2 = 0.6 M

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 n = M x VL

mass = moles x molar mass

36
n = mass / molar mass

37
Potassium dichromate, K2Cr2O7, is used in the tanning of leather. A flask containing 125 mL of
solution is labeled 0.145 M K2Cr2O7.
a) What is the molarity of each ion in solution?
b) A sample containing 0.200 moles of K+ is added to the solution. Assuming no volume
change, what is the molarity of the new solution

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 Solution
K2Cr2O7(s) → 2 K+ (aq) + Cr2O72- (aq)
a) M 2M M
Molarity of K+ , [K+ ]= 2 X 0.145 = 0.290 mol/L = 0.290 M
Molarity of Cr2O72- , [Cr2O72- ]= = 0.145 mol/L = 0.145 M

b)
n = M x VL

[Cr2O72- ]= ½ [K+ ] = 1.89/2 = 0.945 M

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A bottle containing 75.0 mL of nitric acid (HNO3) solution is labeled 6.0 M HNO3.
a) How many moles of HNO3 are in the bottle?
b) A reaction needs 5.00 g of HNO3. How many mL of solution are required? [MM
(HNO3)= 63.02 g/mol)]
c) 10 mL of water are added to the solution. What is the molarity of the resulting
solution?

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 Solution
a) M = 6, V = 75 mL = 0.075 L, n=?
M = n/VL 6 = n / 0.075 n = 0.45 mol

b) M = 6 m = 5 g, MM = 63.02 V=?L
m (g) 5 (g)
M= MM X V(L) 6=
63.02 X V(L)
V = .013 L = 13 mL
c) Now total volume is V = 75 + 10 = 85 mL = 0.085 L,
n = 0.45 mol, M = ?
M = n/VL M = 0.45 / 0.085 = 5.3 mol/L = 5.3 M
N.B. The molarity of a solution decreases when water is added to the solution, but the moles of
solute in solution remain the same.
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Dilution of Solutions
Concentrated solutions are often stored in the laboratory stockroom for use as needed. Frequently we
dilute these “stock” solutions before working with them. Dilution is the procedure for preparing a less
concentrated solution from a more concentrated one.

Dilution
Add Solvent
Two KMnO4 solutions of different
concentrations.

Moles of solute before dilution (i)

= Moles of solute after dilution (f)

MiVi = MfVf
42
where Mi and Mf are the initial and final concentrations of the solution in molarity and Vi and Vf are the
initial and final volumes of the solution, respectively.

Of course, the units of Vi and Vf must be the same (mL or L) for the calculation to work.

To check the reasonableness of your results, be sure that Mi > Mf and Vf > Vi.

Adding more solvent to a given amount of the stock solution changes (decreases) the concentration of the
solution without changing the number of moles of solute present in the solution.

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44
 How would you prepare 60.0 mL of 0.2 M HNO3 from a stock
solution of 4.00 M HNO3?

MiVi = MfVf

Mi = 4.00 Mf = 0.200 Vf = 0.06 L Vi = ? L

MfVf 0.200 x 0.06

Vi = = = 0.003 L = 3 mL
Mi 4.00

Dilute 3.00 mL of acid with water to a total volume of 60.0 mL.

3 mL of acid + 57 mL of water = 60 mL of solution

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Example:
A stock solution of CuSO4 is prepared by adding 40 g of CuSO4 to enough water to
make 500 mL of solution
a) Find the molarity of the CuSO4 stock solution
b) How would you prepare 1.5 L of 0.1 M solution from the stock solution. [MM =
159.6]
Mass (g) 40 x 1000 = 0.5 M
a) M= =
159.6 x 500
MM X V(L)

b) Mi = 0.5 Mf = 0.1 Vf = 1.5 L Vi = ? L

MiVi = MfVf MfVf 0.10 x 1.5

Vi = = = 0.3 L = 300 mL
Mi 0.50
300 mL of stok + 1200 mL of water = 1500 mL of solution
(1.5 L) 46
47
4.7 Acid-Base Titrations
In titration, a solution of accurately known concentration, called a 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.

Sodium hydroxide, it is difficult to obtain solid sodium hydroxide in a pure form because 1) it has a
tendency to absorb water from air, and 2) its solution reacts with carbon dioxide.

For these reasons, a solution of sodium hydroxide must be standardized by titrating it against an acid
solution of accurately known concentration.

48
The acid is a monoprotic, weak acid called potassium hydrogen phthalate (KHP), KHC8H4O4 (molar
mass = 204.2 g). KHP is a white, soluble solid that is commercially available in highly pure form.
The reaction is

NaOH solution is carefully added to the KHP

solution from a buret until we reach the NaOH
equivalence point, that is,

the point at which the acid has completely Reddish-pink color

reacted with or been neutralized by the base. appears at the
equivalence point
The equivalence point is usually signaled by KHP
a sharp change in the color of an indicator
in the acid solution.
49
In acid-base titrations, indicators are substances that have distinctly different colors in acidic and basic
media.

One commonly used indicator is phenolphthalein, which is colorless in acidic and neutral solutions but
reddish pink in basic solutions.

At the equivalence point, all the KHP present has been neutralized by the added NaOH and the solution is
still colorless. However, if we add just one more drop of NaOH solution from the buret, the solution will
immediately turn pink because the solution is now basic.

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The neutralization reaction between NaOH and a diprotic acid such as H2SO4:

Because 2 mol NaOH ≏ 1 mol H2SO4, we need twice as much NaOH to react completely with a H2SO4
solution of the same molar concentration and volume as a monoprotic acid like HCl.
51
On the other hand, we would need twice the amount of HCl to neutralize a Ba(OH)2 solution

In calculations involving acid-base titrations, regardless of the acid or base that takes place in the reaction,
keep in mind that the total number of moles of H+ ions that have reacted at the equivalence point
must be equal to the total number of moles of OH- ions that have reacted.

52
53
 a acid + b base salt + water
❖ At the Equivalence point: Molar ratio = (a/b)
Millimoles acid = Millimoles base X Molar ratio
(M X VmL) acid = (M X VmL) base X (a/b)

Example
What volume of a 1.42 M NaOH solution is required to neutralize 25 mL of a 4.50 M
H2SO4 solution?

H2SO4 + 2 NaOH 2H2O + Na2SO4

(4.5 X 25 mL) acid = (1.42 X VmL) base X (1/2)
V = 158 mL 54
Example: A 20 mL sample of HCl is titrated with 25 mL of 0.2 M Ba(OH)2. What is
the molarity of the acid?
2 HCl + Ba(OH)2 2H2O + BaCl2
(M X 20 mL) acid = (0.2 X 25 mL) base X (2/1)

M = 0.5 mol/L
Example: pure Na2CO3 sample is reacted with 32.7 mL of 0.2 M HCl solution.
Calculate the mass of Na2CO3 (MM = 106)?
2 HCl + Na2CO3 H2O + 2NaCl + CO2
(0.2 X 32.7 mL) acid = (Millimoles) base X (2/1)
Millimoles (Na2CO3)= 3.27 Millimoles = 3.27 x 10-3 moles
mass (g)= Moles X MM = 3.27 x 10-3 X106 = 0.347 g
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Example:
A 35 mL of 0.35 M Ca(OH)2 is reacted with 40 mL H3PO4. Find is the molarity of the
acidic solution and the mass of H3PO4?

2 H3PO4 + 3 Ca(OH)2 6H2O + Ca3(PO4)2

(M X 40 mL) acid = (0.35 X 35 mL) base X (2/3)

M = 0.2 mol/L

M =
Mass (g)
MM X VL

Mass = M X VL X MM = 0.2 X 0.04 L X 98 = 0.784 g

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4.4 Oxidation-Reduction Reactions
The class of reactions called oxidation-reduction, or redox, reactions are considered electron-transfer
reactions.
Oxidation-reduction reactions are very much a part of the world around us. They range from the burning of
fossil fuels to the action of household bleach.

Consider the formation of magnesium oxide (MgO) from magnesium and oxygen

Magnesium oxide (MgO) is an ionic

compound made up of Mg2+ and O2- ions.
Two Mg atoms give up or transfer four
electrons to two O atoms (in O2).

We can think of this process as two

separate steps,
1) one involving the loss of four electrons by
the two Mg atoms Each of these
2) the gain of four electrons by an O2 steps is called a
molecule: half-reaction
57
The sum of the half-reactions gives the overall reaction:

or, if we cancel the electrons that appear on both sides of the equation,

Finally, the Mg2+ and O2− ions combine to form MgO:

The term oxidation reaction refers to the half-reaction that involves loss of electrons. Chemists originally
used “oxidation” to denote the combination of elements with oxygen.

A reduction reaction is a half-reaction that involves gain of electrons.

In the formation of magnesium oxide, magnesium is oxidized. It is said to act as a reducing agent,
because it donates electrons to oxygen and causes oxygen to be reduced.

Oxygen is reduced and acts as an oxidizing agent, because it accepts electrons from magnesium,
causing magnesium to be oxidized.

The extent of oxidation must be equal to the extent of reduction; that is, the number of electrons lost by
a reducing agent must be equal to the number of electrons gained by an oxidizing agent. 58
When metallic zinc is added to a solution containing copper(II) sulfate (CuSO4), zinc reduces Cu2+ by
donating two electrons to it:

In the process, the solution loses the blue color that characterizes the presence of hydrated Cu2+ ions:

The oxidation and reduction half-reactions are:

Similarly, metallic copper reduces silver ions

in a solution of silver nitrate (AgNO3):

or:

59
Oxidation Number
An atom’s oxidation number, also called oxidation state, signifies the number of charges the atom would
have in a molecule (or an ionic compound) if electrons were transferred completely.

In both reactions shown, there is no charge on the atoms in the reactant molecules. Thus, their
oxidation number is zero.

Oxidation numbers enable us to identify elements that are oxidized and reduced at a glance. The
elements that show an increase in oxidation number—hydrogen and sulfur in the preceding examples—are
oxidized. Chlorine and oxygen are reduced, so their oxidation numbers show a decrease from their initial
values.

Note that the sum of the oxidation numbers of H and Cl in HCl (+1 and -1) is zero. Likewise, if we add the
charges on S (+4) and two atoms of O [2  (-2)], the total is zero. 60
Rules to assign oxidation numbers:
1. In free elements (that is, in the uncombined state), each atom has an oxidation number of zero.
Thus, each atom in H2, Br2, Na, Be, K, O2, and P4 has the same oxidation number: zero.

2. For ions composed of only one atom (that is, monatomic ions), the oxidation number is equal to the
charge on the ion. Thus, Li+1 ion has an oxidation number of +1; Ba2+ ion, 2+; Fe3+ ion, 3+; I- ion, -1; O2-
ion, -2; and so on.
All alkali metals have an oxidation number of +1 and all alkaline earth metals have an oxidation number of
+2 in their compounds. Aluminum has an oxidation number of +3 in all its compounds.

3. The oxidation number of oxygen in most compounds (for example, MgO and H2O) is -2, but in hydrogen
peroxide (H2O2) and peroxide ion (O22-), it is -1.

4. The oxidation number of hydrogen is +1, except when it is bonded to metals in binary compounds. In
these cases (for example, LiH, NaH, CaH2), its oxidation number is -1. 61
5. Fluorine has an oxidation number of -1 in all its compounds. Other halogens (Cl, Br, and I) have
negative oxidation numbers when they occur as halide ions in their compounds. When combined with
oxygen—for example in oxoacids and oxoanions—they have positive oxidation numbers.

6. In a neutral molecule, the sum of the oxidation numbers of all the atoms must be zero. In a polyatomic
ion, the sum of oxidation numbers of all the elements in the ion must be equal to the net charge of the ion.

For example, in the ammonium ion, NH4+, the oxidation number of N is -3 and that of H is +1. Thus, the
sum of the oxidation numbers is -3 + 4(+1) = +1, which is equal to the net charge of the ion.

7. Oxidation numbers do not have to be integers. For example, the oxidation number of O in the
superoxide ion, O2-, is -1/2.

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The known oxidation numbers of the
familiar elements, arranged according
to their positions in the periodic table.

• Metallic elements have only

positive oxidation numbers,
whereas nonmetallic elements may
have either positive or negative
oxidation numbers.

• The highest oxidation number an

element in Groups 1A–7A can
have is its group number. For
example, the halogens are in
Group 7A, so their highest possible
oxidation number is +7.

• The transition metals (Groups 1B,

3B–8B) usually have several
possible oxidation numbers.
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 HCO3- O = –2 H = +1
What are the oxidation numbers of
all the elements in HCO3- ? 3x(–2) + 1 + ? = –1
C = +4
What are the oxidation numbers of all the elements in each of these compounds?
NaIO3 IF7 K2Cr2O7

NaIO3 Na = +1 O = -2 3x(-2) + 1 + ? = 0 I = +5

IF7 F = -1 7x(-1) + ? = 0 I = +7
Iodine heptafluoride

K2Cr2O7 O = -2 K = +1 7x(-2) + 2x(+1) + 2x(?) = 0

Cr = +6 66
What are the oxidation numbers of S2O32-
all the elements Mn and S in these 3x(-2) + 2x(?) = -2
compounds?
MnO4- S2O32- 2 S = +4
S = +2

MnO4-
4x(-2) + ? = -1
Assign oxidation states: Mn = +7

+3 +2 -2 0 +4 -2
D
Fe2O3(s) + 3 CO(g) → 2 Fe(l) + 3 CO2(g)
Fe3+ is reduced to metallic iron.
CO(g) is oxidized to carbon dioxide.
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 Identify oxidized and reduced

• Mn is reduced from +7 to +2
– Net gain of 5 electrons
• Br is oxidized from -1 to 0
– Net loss of 1 electron

+7 -1 +2 0

− − 2+
MnO (aq) + 2 Br (aq) → Mn (aq) + Br2 (aq)
4

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 Try These!!

+1 = Fe 2+ is oxidized (reducing agent)

5 Fe2+ + MnO4- + 8 H+ → 5 Fe3+ + Mn2+ + 4 H2O

- 5 = Mn 7+ is reduced (oxidizing agent)

+2 = Zn 0 is oxidized (reducing agent)

Zn + 2 HCl → ZnCl2 + H2

- 1 = H 1+ is reduced (oxidizing agent)

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What is oxidized and reduced?
What are the oxidizing and reducing agents?
3Br2 + 2AlI3 2AlBr3 + 3I2

0 +3 -1 +3 -1 0
3Br2 + 2AlI3 2AlBr3 + 3I2

Br2 is reduced and is the oxidizing agent

I-1 is oxidized and is the reducing agent

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What is oxidized and reduced?
What are the oxidizing and reducing agents?
0 +1 +2 0
Sr + 2H2O Sr(OH)2 + H2
+4 0 0 +2
TiCl4 + 2Mg Ti + 2MgCl2
0 -1 -1 0
Cl2 + 2KBr 2KCl + Br2

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Exercise
What is oxidized and reduced?
What are the oxidizing and reducing agents?

Mg + CuSO4 MgSO4 + Cu

2K + Br2 2KBr

Cu + 2AgNO3 Cu(NO3)2 + 2Ag

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Disproportionation Reaction
It is a special type of redox reactions in which an element in one oxidation state is simultaneously oxidized
and reduced.
One reactant in a disproportionation reaction always contains an element that can have at least three
oxidation states. The element itself is in an intermediate oxidation state, that is, both higher and lower
oxidation states exist for that element in the products.

e.g. The decomposition of hydrogen peroxide

The formation of household bleaching agents, for it is the hypochlorite ion (ClO-) that oxidizes the color-
bearing substances in stains, converting them to colorless compounds.

+4 +3 +5

3Cl2 + 6NaOH → 5NaCl + NaClO3 + 3H2O

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18.1 Redox Reactions
Balancing Redox Equations
There are some special techniques for handling redox reactions. Here we will discuss one such procedure,
called the ion-electron method. In this approach, the overall reaction is divided into two half-reactions,
one for oxidation and one for reduction. The equations for the two half-reactions are balanced separately
and then added together to give the overall balanced equation.

Suppose we are asked to balance the equation showing the oxidation of Fe2+ ions to Fe3+ ions by
dichromate ions (Cr2O72−) in an acidic medium. As a result, the Cr2O72− ions are reduced to Cr3+
ions.

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5Fe2++MnO4−+8H+→5Fe3++Mn2++4H2O
Thank You
Dr. Wael Amer