Chapter Four

Stoichiometry of Chemical Reaction

1
 CHAPTER FOUR
Introduction
This chapter will describe:
• How to symbolize chemical reactions using
chemical equations,
• How to classify some common chemical
reactions by identifying patterns of reactivity,
• How to determine the quantitative relations
between the amounts of substances involved in
chemical reactions-that is, the reaction
stoichiometry
2
4.1. Writing and Balancing Chemical Equations
4.1.1. Writing Chemical Equations
The relative quantities of substances undergoing a
chemical (or physical) change involve writing and
balancing a chemical equation.
• Consider the reaction between CH4 ( ONE methane
molecules) and O2 (two diatomic oxygen molecules)
• The chemical equation representing this :process:
Reactant Product
64 74 8 64 748
}
Reactant }
Coefficient }
Product } t
Coefficien

CH 4 + 2 O 2 → CO 2 + 2 H2O

3
• It is common practice to use the smallest possible
whole-number coefficients in a chemical equation
• Coefficients represent the relative numbers of
reactants and products
• Methane and oxygen react to yield carbon dioxide and
water in a 1:2:1:2 ratio
• One methane molecule and two oxygen molecules react
to yield one carbon dioxide molecule and two water
molecules.
4.1.2. Balancing Chemical Equations
Balanced chemical equation: Equal numbers of atoms for
each element involved in the reaction are
represented on the reactant and product sides.
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• For example, both product species in the example reaction, CO2
and H2O, contain the element oxygen, and so the number of
oxygen atoms on the product side of the equation is
  2 Oxygen atoms   1 O atom 
 (1CO 2 Molecule ) x   + ( 2H 2 O Molecules ) x    = 4 O atoms
  CO 2 Molecules  H
 2 O Molecules 

5
Additional Information in Chemical Equations
The physical states of reactants and products in chemical equations
very often are indicated with a parenthetical abbreviation following
the formulas.
• S= solids; l = liquids; g = gases; aq= for substances dissolved in
water (aqueous solutions)

Example: 2Na(s) + 2H2O(l) ⟶ 2NaOH(aq) + H2(g)

•Special conditions necessary for a reaction are sometimes designated

by writing a word or symbol above or below the equation’s arrow.
For example, a reaction carried out by heating may be indicated by
the uppercase Greek letter delta (Δ) over the arrow.

CaCO3 ( s ) 
∆
→ CaO ( s ) + CO2 ( g )
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4.1.3. Equations for Ionic Reactions
When ionic compounds dissolve in water, they may
dissociate into their constituent ions, which are
subsequently dispersed homogenously throughout the
resulting solution.
Example: When aqueous solutions of CaCl2 and AgNO3 are
mixed, a reaction takes place producing aqueous Ca(NO3)2
and solid AgCl:
CaCl (aq) + 2AgNO (aq) ⟶ Ca(NO ) (aq) + 2AgCl(s)
2 3 3 2

Ionic compounds dissolved in water are, therefore, more

realistically represented as dissociated ions, in this case:
CaCl2 ( aq ) → Ca 2+ (aq ) + 2Cl− ( aq )
2AgNO3 ( aq ) → 2Ag + ( aq ) + 2NO3− (aq)
Ca ( NO3 ) 2 ( aq ) → Ca 2+ ( aq) + 2NO3− ( aq ) 7
Complete ionic equation:
Ca 2+ ( aq ) + 2Cl− ( aq ) + 2Ag + ( aq ) + 2NO3− ( aq ) → Ca 2+ ( aq ) + 2NO3− ( aq ) + 2AgCl ( s )

Examining this equation shows that two chemical species are present in
identical form on both sides of the arrow, Ca2+(aq) and NO3-(aq).
These spectator ions—ions whose presence is required to maintain
charge neutrality—are neither chemically nor physically changed by
the process, and so they may be eliminated from the equation to yield a
more concise representation called a net ionic equation:
Ca2+(aq) + 2Cl-(aq) + 2Ag+(aq) + 2NO3-(aq) ⟶ Ca2+(aq) + 2NO3-(aq)
+ 2AgCl(s)
2Cl-(aq) + 2Ag+(aq) ⟶ 2AgCl(s)

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 Following the convention of using the smallest possible integers
as coefficients, this equation is then written:
Cl─ (aq) + Ag+ (aq) ⟶ AgCl(s)
This net ionic equation indicates that solid silver chloride may be
produced from dissolved chloride and silver (I) ions, regardless of
the source of these ions.

These molecular and complete ionic equations provide

additional information, namely, the ionic compounds used as
sources of Cl- and Ag+.

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4.2. Classification of chemical reactions
The most prevalent types of chemical reactions:
• acid-base, precipitation, and oxidation-reduction
4.2.1. Acid-base reactions
An acid-base reaction is one in which a hydrogen ion, H+, is
transferred from one chemical species to another.
• Acid: a substance that will dissolve in water to yield hydronium
ions, H3O+.
Strong acids: Acids that completely react with water
• HCl is classified as strong HCl ( aq ) + H O ( aq ) → Cl ( aq ) + H O ( aq )
− +
2 3

(Acid) (Water)

Weak acids: Acids that only partially react with water, leaving a
large majority of dissolved molecules in their original form and
generating a relatively small amount of hydronium ions
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 A familiar example of a weak acid is acetic acid
CH3COOH( aq) + H2O( l)  CH3COO− ( aq) + H3O+ ( aq)
When dissolved in water under typical conditions, only about 1% of
acetic acid molecules are present in the ionized form, CH3COO-.
Base: a substance that will dissolve in water to yield hydroxide ions,
OH-.
these compounds do not react chemically with water; instead they
dissolve and dissociate, releasing hydroxide ions directly into the
solution
Strong bases: These bases completely dissociate in water
NaOH(s) ⟶ Na+(aq) + OH−(aq)

Weak bases: compounds react only partially

NH3 ( aq ) + H 2 O ( l )  NH 4 + ( aq ) + OH − ( aq )
• A neutralization reaction: a type of acid-base reaction in which
the reactants are an acid and a base (but not water), and the
products are often a salt and water

Acid + base → salt + water

Mg ( OH ) 2 ( s ) + 2HCl ( aq ) → MgCl2 ( aq ) + 2H 2 O ( l )
(Milkof magnesia) (Excess stomach acid)

Example 4.3: Writing Equations for Acid-Base Reactions

Write balanced chemical equations for the acid-base reactions
described here:
(a) The weak acid hydrogen hypochlorite reacts with water
(b) A solution of barium hydroxide is neutralized with a solution
of nitric acid

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Solution:
(a) The weak acid hydrogen HOCl reacts with H2O:
The transfer of H+ from HOCl to H2O to generate hydronium
ions, H3O+ and hypochlorite ions, OCl-.
HOCl ( aq ) + H 2 O ( l )  OCl− ( aq ) + H3 O+ ( aq )

4.2.2. Precipitation reactions and solubility rules

Precipitation reaction: a reaction in which dissolved substances
react to form one (or more) solid products.
Double displacement, double replacement, or metathesis
reactions: reactions involving the exchange of ions
between ionic compounds in aqueous solution

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The extent to which a substance may be dissolved in water, or any
solvent, is quantitatively expressed as its solubility
• Substances with relatively low solubility are said to be insoluble
• A bright example of precipitation is observed when solutions of
potassium iodide and lead nitrate are mixed, resulting in the
formation of solid lead iodide:
2KI ( aq ) + Pb( NO3 ) 2 ( aq ) → PbI 2 ( s ) + 2KNO3 ( aq )
(potassium iodide) (lead nitrate) (lead iodide)

• The net ionic equation representing this reaction is:

Pb2+ ( aq ) + 2I− ( aq ) → PbI2 ( s )
The solubility guidelines (in Table 4.2 )may be used to predict
whether a precipitation reaction will occur when solutions of
soluble ionic compounds are mixed together.

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15
For example, mixing solutions of silver nitrate and sodium fluoride
will yield a solution containing Ag+, NO3−, Na+, and F−
ions.
Mixing solutions of silver nitrate (AgNO3) and sodium fluoride
(NaF), forming nitrate salts (NaNO3, soluble) and AgF
A precipitation reaction, therefore, is predicted to occur, using
solubility guidelines

NaF ( aq ) + AgNO3 ( aq ) → AgF ( s ) + NaNO3 ( aq ) ( molecular )

Ag + ( aq ) + F− ( aq ) → AgF ( s ) ( net ionic )

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4.2.3. Oxidation-Reduction Reactions
Oxidation-reduction (Redox) reactions are those in which one or
more elements involved undergo a change in oxidation
number.
• For redox reactions, the loss and gain of electrons define the
corresponding processes that occur:
• Oxidation = loss of electrons; increase in oxidation number;
• Reduction = gain of electrons, decrease in oxidation number
• reducing agent = species that is oxidized;
• oxidizing agent = species that is reduced
Half-reaction: the process with regard to each individual reactants
2Na ( s ) + Cl2 ( g ) → 2NaCl ( s ) ⇐ Redox − reaction

Cl2 ( g ) + 2e− → 2Cl− ( s ) ⇐ half − reaction

2Na ( s ) → 2Na + ( s ) + 2e− ⇐ half − reaction ,sodium isoxidized

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 These equations show that Na atoms lose electrons while Cl
atoms (in the Cl2 molecule) gain electrons
2Na ( s ) + Cl2 ( g ) → 2NaCl ( s ) ⇐ Redox − reaction
sodium is oxidized (its oxidation number increases from 0 in Na
to +1 in NaCl)
chlorine is reduced (its oxidation number decreases from 0 in
Cl2 to -1 in NaCl)
sodium functions as a reducing agent (reductant)
chlorine functions as an oxidizing agent (oxidant)
Some redox processes, however, do not involve the transfer of
electrons.
• For example: a reaction similar to the one yielding NaCl
redox processes not involving
H 2 ( g ) + Cl 2 ( g ) → 2HCl ( g ) ⇐
electron transfer

The product of this reaction is a covalent compound, so transfer of

electrons in the explicit sense is not involved.
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 In the reaction between molecular hydrogen and chlorine, hydrogen
is oxidized (its oxidation number increases from 0 in H2 to +1 in
HCl) and chlorine is reduced (its oxidation number decreases from
0 in Cl2 to −1 in HCl).
The oxidation number (or oxidation state) of an element in a
compound: the charge its atoms would possess if the compound was
ionic
The following guidelines are used to assign oxidation numbers to each
element in a molecule or ion.
1.The oxidation number of an atom in an elemental substance is zero.
2. The oxidation number of a monatomic ion is equal to the ion’s
charge.
3. Oxidation numbers for common nonmetals are usually assigned as
follows:
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Hydrogen: +1 when combined with nonmetals, -1 when combined
with metals
Oxygen: -2 in most compounds, sometimes -1 (so-called peroxides,
O22-), very rarely -1/2 (so-called superoxides, O21- ),
positive values when combined with F (values vary)
Halogens: -1 for F always, -1 for other halogens except when
combined with oxygen or other halogens (positive
oxidation numbers in these cases, varying values)
4. The sum of oxidation numbers for all atoms in a molecule or
polyatomic ion equals the charge on the molecule or ion.

Note: The proper convention for reporting charge is to write the

number first, followed by the sign (e.g., 2+), while oxidation
number is written with the reversed sequence, sign followed
by number (e.g., +2). This convention aims to emphasize the
distinction between these two related properties.
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Example 4.5: Follow the guidelines in this section of the text to
assign oxidation numbers to all the elements in the
following species:

Solution: (a) H2S:

• the oxidation number for H is +1 , ( guideline 1)
• calculating the oxidation number for sulfur (S) (guideline 4)
Charge on H 2 S = 0 = ( 2 × +1) + 1× x)
Oxidation number for sulfur = x = 0 − ( 2 × +1) = − 2
Solution: (b) SO32- :
• the oxidation number for oxygen is -2, , ( guideline 3)
• calculating the oxidation number for sulfur (S) (guideline 4),
Using this oxidation number and the ion’s formula (guideline 4)
 oxidation number for sulfur : charge on SO3 2− = −2 = ( 3 × −2 ) + (1 × x ) x 
 
 = −2 − ( 3 × −2 ) = +4 
 ⇒ oxidation number for sulfur = x = + 4 
 
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Single-displacement (replacement) reactions: Redox reactions
in which an ion in solution is displaced (or replaced) via
the oxidation of a metallic element.
Example: the acid oxidation of certain metals:
Zn ( s ) + 2HCl ( aq ) → ZnCl2 ( aq ) + H 2 ( g )
(Metal) (Acid)

Metallic elements may also be oxidized by solutions of other metal

salts; for example:

Cu ( s ) + 2AgNO3 ( aq ) → Cu ( NO3 ) 2 ( aq ) + 2Ag ( s )

(Metal) (metal salts)

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Balancing Redox Reactions via the Half-Reaction Method

Half-Reaction Method: one of useful approach to balance

redox reactions
It involves the following steps:
1. Write the two half-reactions representing the redox process.
2. Balance all elements except oxygen (O) and hydrogen (H).
3. Balance oxygen (O) atoms by adding H2O molecules.
4. Balance hydrogen (H) atoms by adding H+ ions.
5. Balance charge by adding electrons ( e-).
6. If necessary, multiply each half-reaction’s coefficients by the
smallest possible integers to yield equal numbers of electrons in
each.
7. Add the balanced half-reactions together and simplify by
removing species that appear on both sides of the equation.

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8. For reactions occurring in basic media (excess hydroxide ions, ),
carry out these additional steps:
a. Add OH- ions to both sides of the equation in numbers equal
to the number of H+ ions.
b. On the side of the equation containing both H+ and OH- ions,
combine these ions to yield water molecules.
c. Simplify the equation by removing any redundant water
molecules.
9. Finally, check to see that both the number of atoms and the total
charges1 are balanced.

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Example 4.7: Balancing Redox Reactions in Acidic Solution:
Example 4.7: Write a balanced equation for the
reaction between dichromate ion and iron (II) to yield
iron (III) and chromium (III) in acidic solution.
Cr2 O 7 2− + Fe 2+ → Cr 3+ + Fe3+
Solution:
Step 1: Write the two half-reactions.
 → Fe3+ (half − reaction for Oxidation) 
+
Fe 2 
Oxidation

 2− 3+

Cr2 O7  → Cr (half − reaction for reduction) 
Re duction

Step 2: Balance all elements except oxygen and hydrogen.

The Cr half − reaction shows two Cr atoms on
 → Fe3+ 
+
Fe 2 
Oxidation
the left & one Cr atom on the right. Changing
 2− 3+

Cr2 O 7  → 2Cr  the coefficient on the right side of the equation
Re duction

to 2 achieves balance with regard to Cr atoms.

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Step 3: Balance oxygen atoms by adding H2O molecules.
The iron half-reaction(at step-2) does not contain O atoms.
The Cr half − reaction shows seven O atoms
 
+
Fe 2 → Fe3+
 2− 3+
 on the left and none on the right, so 7 water
 2 7
Cr O → 2Cr + 7H O
2   molecules are added to the right side.
Step 4: Balance hydrogen atoms by adding H+ ions.
• The iron half-reaction (at step-3) does not contain H atoms.
The Cr half − reaction shows 14 H atoms
 
+
Fe2 → Fe3+
 2− + 3+
 on the right and none on the left, so 14
Cr2 O7 + 14H → 2Cr + 7H 2 O  hydrogen ions are added to the left side.

Step 5: Balance charge by adding electrons.

• The iron half-reaction (at step-4) shows a total charge of 2+ on

the left side (1 Fe2+ ion) and 3+ on the right side (1 Fe3+ ion).
The chromium half-reaction (at step-4) shows a total charge of (1
× 2-) + (14 × 1+) = 12+ on the left side (1 Cr2O72- ion and 14 H+
ions). The total charge on the right side is (2 × 3+) = 6 + (2 Cr3+
ions). 26
 Adding one electron to the right
side brings that side’s total charge
to ( 3 + ) + (1 − ) = 2 + , and charge
 
+
Fe 2 → Fe 3 + + e − balance is achieved.
 2− + − 3+

 2 7
Cr O + 14H + 6e → 2Cr + 7H 2 O  Adding six electrons to the left side
will bring thatside’s total charge to
( (12 + ) + (6 − ) ) = 6 + , &charge
balance is achieved.

Step 6: Multiply the two half-reactions so the number of electrons

in one reaction equals the number of electrons in the other
reaction.
  the Fe half − reaction’s coefficient
+
(Fe 2 → Fe3+ + e − ) x6
 2− + − 3+

 2 7
Cr O + 14H + 6e → 2Cr + 7H O
2   must be multiplied by 6.

 
+
6Fe2 → 6Fe3+ + 6e −
 2− + − 3+

Cr2 O7 + 14H + 6e → 2Cr + 7H 2 O 
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Step 7: Add the balanced half-reactions and cancel species that
appear on both sides of the equation.
 6Fe 2+ → 6Fe3+ + 6e− 
 
 Cr2 O7 2− + 14H + + 6e− → 2Cr 3+ + 7H 2 O 
 
 _____________________________________________________ 
Cr O 2− + 6e− + 14H + +6Fe2+ → 2Cr 3+ + 6Fe3+ + 6e − + 7H O 
 2 7 2 
• only the six electrons are redundant species. Removing them from
each side of the equation yields the simplified, balanced equation
here:
Cr2 O 7 2 − + 14H + +6Fe 2 + → 2Cr 3+ + 6Fe3+ − + 7H 2 O
• A final check of atom and charge balance confirms the equation
is balanced Reactants Products

Fe 6 6

Cr 2 2

O 7 7

H 14 14

Charge 24+24+

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4.3. Reaction stoichiometry
Chemical formulas provide the identities of the reactants and
products involved in the chemical change, allowing classification
of the reaction.
Coefficients provide the relative numbers of these chemical
species
quantitative assessment of the relationships between the
amounts of substances consumed and produced by the reaction
Stoichiometry: reaction’s quantitative relationships
The coefficients in the balanced equation are used to derive
stoichiometric factors that permit computation of the desired
quantity.

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Consider the production of ammonia by reaction of hydrogen and
nitrogen:
N 2 ( g ) + 3H 2 ( g ) → 2NH 3 ( g )
Stoichiometric factors may be derived using any amount (number)
unit:
(2NH3 molecule) (2 doz NH3 molecule) (2 mole NH3 molecules)
Or Or
(3H2 molecule ) (3 doz H2 molecule ) (3 mole H2 molecules )

These stoichiometric factors can be used to compute the number of

ammonia molecules produced from a given number of hydrogen
molecule or the number of hydrogen molecules required to produce
a given number of ammonia molecules.

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Example 4.8: Moles of Reactant Required in a Reaction:
Example 4.8: How many moles of I2 are required to react with
0.429 mol of Al according to the following
equation?2Al+ 3I2→2AlI3
Solution: 2Al+ 3I2→2AlI3
 3mol I 2 
stoichiometric factor relating the two substances of interest is  2mol Al 
 

The molar amount of iodine is derived by multiplying the provided

molar amount of aluminum by this factor:
⇒ Moles of Al Moles of Al 
Stoichiometric Factor
→ Moles of I 2

  3mol I2 
  
⇒ 0.429 Moles of Al 
 2mol Al 
→ 0.644 Moles of I2 
 
 
⇒ mol I2 = 0.429mol Al ×  3mol I 

2
 = 0.644 mol I2 mo l 
  2mol Al  
 
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Number of Product Molecules Generated by a Reaction
Example 4.9: How many carbon dioxide (CO2) molecules are
produced when 0.75 mol of propane (C3H8 ) is
combusted according to this equation?
C3H8 + 5O2→ 3 CO2 + 4H2O
Solution:
The balanced equation shows that is produced from (C3H8) in a 3:1
ratio:  3mol CO 
2
 
 1mol C3 H8 

Using this stoichiometric factor, the provided molar amount of

propane, and Avogadro’s number
Moles of Moles of Molecules of
⇒ 
Stoichiometric
→ →
Avogadro’s
C3 H 8 factorr CO 2 Numberr CO 2

 3mol CO 2   6.022 × 1023 CO 2 Molecules 

Moles of CO 2 = 0.75mol C3 H8 ×  x 
⇒  1mol C3 H 8   mol CO 2 
= 1.4 × 1024 CO 2 molecules
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Example 4.10: Relating Masses of Reactants and Products
Example 4.10: What mass of sodium hydroxide, NaOH,
would be required to produce 16 g of the antacid
milk of magnesia [magnesium hydroxide,
Mg(OH)2] by the following reaction?
MgCl2(aq) + 2NaOH(aq) →Mg(OH)2(aq) + 2NaCl (aq)
Solution:
Deriving stoichiometric factor from the balanced chemical equation
to relate the amounts of the two substances of interest

The calculations required are outlined in this flowchart:

 Mass of Moles of Moles of Mass of 
 
Molar
→ 
Stoichiometric
→ 
Molar
→ 
 Mg(OH) 2 mass Mg(OH) 2 factorr NaOH mass NaOH 2 
 1mol Mg ( OH)2   2mol NaOH   40.0 g NaOH 
Mass of NaOH = (16g Mg(OH)2 )x   x   x  
 58.3g Mg ( OH)
⇒  2   1mol Mg ( OH)2   mol NaOH 
= 22 g NaOH
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Example 4.11: Relating Masses of Reactants
Example 4.11: What mass of oxygen gas, O2, from the air is
consumed in the combustion of 702 g of octane, C8H18, one
of the principal components of gasoline?
2C8H18+ 5O2→ 16CO2 + 18H2O2
Solution:
 Mass of Moles of Moles of Mass of 
 
Molar
→ 
Stoichiometric
→ 
Molar
→ 
 C8 H18 mass C8 H18 factorr O 2 mass O2 

 1mol C8 H18   25mol O2   32.00 g O2 

Mass of O2 = (702g C8 H18 )x  x x 
⇒  114.23g C H
8 18   2mol C H
8 18   mol O 2 
= 2.46 × 103 g O2

Regardless of the details, all these calculations share a common

essential component: the use of stoichiometric factors derived from
balanced chemical equations.
Figure 4.9 provides a general outline of the various computational
steps associated with many reaction stoichiometry calculations.
34
Figure 4.9: The flowchart depicts the various computational steps
involved in most reaction stoichiometry calculations
35
4.4. Reaction Yield
Stoichiometric amounts: The relative amounts of reactants and
products represented in a balanced
chemical equation
4.4.1. Limiting Reactant
Limiting reactant: the reactants that are entirely consumed, thus
limiting the amount of product that may be
generate
Limiting reactant: The reactant yielding the lesser amount of
product
Consider this concept now with regard to a chemical process, the
reaction of hydrogen with chlorine to yield hydrogen chloride:
H2(g) + Cl2(g) → 2HCl(g)
For example, imagine combining 3 moles of H2and 2 moles of
Cl2.
stoichiometric ratio of 1:1 for Hydrogen to chlorine :
Hydrogen is present in excess
36
 chlorine (2 mol) will consume 2 mol of the 3 mol of hydrogen
provided, leaving 1 mol of hydrogen unreacted
Hydrogen is present in excess.
H 2 ( g ) + Cl2 ( g ) → 2HCl ( g )  chlorine is the limiting reactant.
 
⇒ 3 moles ∗ 2 moles 4 moles  chlorine ( 2 mol ) will consume
(excess ) (limiting reactant)  2 mol of 3 mol of H 2 provided,
 
leaving 1 mol of H 2 unreacted

An alternative approach to identifying the limiting reactant involves

comparing the amount of product expected for the complete reaction
of each reactant.
The reactant yielding the lesser amount of product is the limiting
reactant.
 2mol HCl 
Moles of HCl produced = 3 mol H 2 ×  
⇒  1mol H 2 
= 6 mol HCl

37
Complete reaction of the provided chlorine would produce
 2mol HCl 
Moles of HCl produced = 2 mol Cl2 ×  
⇒  1mol Cl 2 
= 4 mol HCl
The chlorine will be completely consumed once 4 moles of HCl
have been produced
H 2 ( g ) + Cl2 ( g ) → 2HCl ( g ) 
 
⇒ 3 moles ∗ 2 moles 4 moles 
(excess ) (limiting reactant) 
 

Example 4.12: Identifying the Limiting Reactant:

Example 4.12: Silicon nitride is a very hard, high-temperature-
resistant ceramic used as a component of turbine
blades in jet engines. It is prepared according to the
following equation: 3Si (s) + 2N2(g) → Si3N4 (s)
Which is the limiting reactant when 2.00 g of Si and 1.50
g of N2 react?
38
Solution:
To identify the limiting reactant: molar amounts of reactants
compare these amounts to the
balanced equation  1mol Si 
Moles of Si = 2.00g Si ×  
 28.09g Si 
= 0.0712 mol Si
⇒
 1mol N 2 
Moles of N 2 = 1.50g N 2 ×  
 28.09g N 2 

= 0.0535 mol N 2

The provided Si: N2 molar ratio is:

 0.0712 mol Si  1.33 mol Si
⇒ =
 .535 mol N 2  1 mol N2
The stoichiometric Si:N2 ratio is:
 3 mol Si  1.5 mol Si
⇒ =
 2 mol N 2  1mol N2
Si is limiting reactant (Si is in a less-than-stoichiometric amount
39
4.4.2. Percent Yield
Theoretical yield: The amount of product that may be produced by
a reaction under specified conditions, as
calculated per the stoichiometry of an
appropriate balanced chemical equation
Actual yield: the amount of product obtained in practice
• it is often less than the theoretical yield for a number of reasons:
by side reactions .etc.
• The extent to which a reaction’s theoretical yield is achieved is
commonly expressed as its percent yield:
 Actual yield 
⇒ Percent yield =   x100%
 Theoretical yield 

40
Example 4.13: Upon reaction of 1.274 g of copper sulfate with
excess zinc metal, 0.392 g copper metal was
obtained according to the equation:
CuSO4(aq) + Zn(s) → Cu(s) + ZnSO4(aq)
What is the percent (%) yield?
Solution:
copper sulfate (CuSO4)is the limiting reactant
Theoretical yield found:
 1 mol CuSO 4   1 mol Cu   63.55g Cu 
Mass of Cu = (1.274g CuSO4 )x  x x 
⇒  159.62g CuSO 4   1 mol CuSO 4   1 mol Cu 
= 0.5072 g Cu

The percent yield is calculated as :

 Actual yield 
Percent yield of Cu =   x100%
 Theoretical yield 
 0.392 g Cu 
⇒ Percent yield of Cu ==   x100% = 77.3%
 0.5072 g Cu 
 0.392 g Cu 
∴ Percent yield ==   x100% = 77.3%
 0.5072 g Cu 
41
4.5. Quantitative Chemical Analysis
The amount of a substance present in a sample is determined by
measuring the amount of product that results

Analyte: in sample solution, the substance whose concentration is

to be measured
Titrant: Solution containing a known concentration of some
substance
Equivalence point of the titration: the volume of titrant solution
required for complete reaction with the analyte
• Precipitation, acid-base, and redox titrations are the most
common types of titration analysis

42
Example 4.14: Titration Analysis
Example 4.14: The end point in a titration of a 50.00 mL sample of
aqueous HCl was reached by addition of 35.23 mL
of 0.250 M NaOH titrant. The titration reaction is:
HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)
What is the molarity of the HCl?
Solution:
• The calculation will follow the following outlined steps:
 Volume of Moles of Moles of Concentration of 
 
Molar
→ 
Stoichiometric
→ 
Solution
→ 
 NaOH Concentration NaOH factorr HCl Volume HCl 

The molar amount of HCl is calculated to be:

  1L   0.250mol NaOH   1 mol HCl  
 Molar amount of HCl = (35.23 mL NaOH)x  x x 
  1000 mL   1L   1mol NaOH  
 = 8.81 × 10−3 mol HCl 
 

The HCl concentration, in molarity (M):

43
  mol HCl 
 Molarity = M = 
L solution
 
  8.81 × 10 −3 mol HCl   1L 
⇒ = x
  
  50.00mL   1000 mL 
 = 0.176M HCl 
 
 
Note: solution molarity(M) is also equal to the number of milli-
moles of solute per milli-liter of solution
   103 mmol  
   
  mol solute    mol  
⇒ Molarity = M =  x
 L Solution   103 mL  
    
  
   L  
Using this version of the molarity unit will shorten the calculation
by eliminating two conversion factors
   0.250 mmol NaOH   1 mmol HCl   
  (35.23mL NaOH)x  x  
   mL NaOH   1 mmol NaOH   
⇒ Molarityof HCl = M = 
 50.00mL Solution 
 = 0.176M HCl 

44
4.5.2. Gravimetric Analysis
A gravimetric analysis is one in which a sample is subjected to
some treatment that causes a change in the physical state of the
analyte that permits its separation from the other components
of the sample.
Gravimetric methods were the first techniques used for
quantitative chemical analysis
Gravimetric analysis may be achieved by various physical
and chemical processes.
The moisture (water) content of a sample is routinely
determined by measuring the mass of a sample before and
after it is subjected to a controlled heating process that
evaporates the water.
Precipitation reaction: common gravimetric techniques
• The precipitate is typically isolated from the reaction mixture by
filtration, carefully dried, and then weighed
• The mass of the precipitate may be used to calculate analyte 45
concentration
 Example 4.15: Gravimetric Analysis
Example 4.15: A 0.4550-g solid mixture containing MgSO4 is
dissolved in water and treated with an excess of
Ba(NO3)2, resulting in the precipitation of 0.6168 g
of BaSO4.
MgSO4(aq) +Ba(NO3)2(aq) → BaSO4(s) + MgSO4(aq)
What is the concentration (mass %) of MgSO4 in the mixture?
Solution:
The connection between the moles of BaSO4 and MgSO4 through
their stoichiometric factor The sample mixture to calculate the
requested percentage concentration
 Mass of Moles of Moles of Mass of Percent 
 
Molar
→ 
Stoichiometric
→ 
Molar
→ →
Sample 
 BaSO4 mass BaSO4 factorr BaSO4 mass O2 mass BaSO4 

The concentration of MgSO4 in the sample mixture is then

calculated to be

46
The concentration of MgSO4 in the sample mixture is then
calculated to be  Mass MgSO4 
Percent MgSO 4 =   x100%
 Mass sample 
⇒
 0.3181g 
=  x100% = 69.91%
 0.4550g 

The elemental composition of hydrocarbons and related compounds

may be determined via a gravimetric method known as combustion
analysis
In a combustion analysis, a weighed sample of the compound is
heated to a high temperature under a stream of oxygen gas,
resulting in its complete combustion to yield gaseous products of
known identities

47
Example 4.16: Combustion Analysis:
Example 4.16: Polyethylene is a hydrocarbon polymer used to
produce food-storage bags and many other flexible
plastic items. A combustion analysis of a 0.00126-g
sample of polyethylene yields 0.00394 g of CO2
and 0.00161 g of H2O.
What is the empirical formula of polyethylene?

Solution:
Carbon in the sample combusted is converted to carbon dioxide,
and all the hydrogen in the sample is converted to water
y
Cx H y ( s ) + excess O2 ( g ) → xCO2 ( g ) + H2 O ( g )
2
To derive the empirical formula of the compound, only the
subscripts x and y are needed
Calculate the molar amounts of carbon and hydrogen in the sample:
An outline of this approach is given in the following flow chart:
48
49
   mol CO 2   1 mol C  −5

 Molesof C = (0.00394g CO 2 )x   
x  = 8.95 × 10 mol C 
  44.01 g   1 mol CO 2  
⇒ 
Moles of H = (0.00161g H O)x  1 mol H O   2 mol H  −4 
 2 
2
 x   = 1.79 × 10 mol H 
  18.02g   1 mol H 2 O  

The empirical formula for the compound is then derived by

identifying the smallest whole number multiples for these molar
amounts.
  mol H   .79 ×10 mol H  2 mol H 
−4
⇒ The H − to − C molar ratio = = −5 = 
  mol C   8.95 ×10 mol C  1mol C 
The empirical formula for polyethylene is CH2.
Cx H y ( s ) + excess O2 ( g ) → xCO2 ( g ) + y2H 2 O ( g )
 y 
C H
 x y ( s ) + excess O 2 ( g ) → xCO 2 ( g ) + H 2 O ( g ) 
2
  2 mol H
 2  H − to − C molar ratio =
⇒ C1 H 2 ( s ) + excess O 2 ( g ) → 1CO2 ( g ) + H 2 O ( g )  1 mol C
 2  x = 1 and y = 2
C1 H 2 ( s ) + xcess O 2 ( g ) → CO2 ( g ) + H 2 O ( g ) 
 
 
50