Chapter-4

Reaction Stoichiometry

• Stoichiometry is the study of the quantitative relationships

between amounts of reactants used and amounts of products
formed by a chemical reaction.

— Chemical equations
— The mole and molar mass
— Chemical formulas
— Mass relationships in equations
— Limiting reactant

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 4.1. Interpreting Stoichiometric Coefficients

4Fe(s) + 3O2(g) → 2Fe2O3(s)

Iron +oxygen → Iron (III) oxide
4 atoms of Fe + 3 molecules of O2 → 2 formula units of Fe2O3
4 mol of Fe + 3 mol of O2 → 2 mol Fe2O3
223.4 g of Fe + 96 g of O2 → 319.4 g of Fe2O3
319.4 g reactants → 319.4 g products
• The chemical equation does not directly tell you anything about the
masses of reactants and products. However, by converting the
known mole quantities to mass.
▪ Moles are converted to mass by multiplying their molar mass
55.85 g Fe
4 mol Fe × = 223.4 g Fe
1 mol Fe

32.0 g O2
3 mol O2 × = 96.0 g O2
1 mol 𝑂2
159.7 g Fe2O3
2 mol Fe2O3 × = 319.4 g Fe2O3 2
1 mol Fe2O3
 4.1.1. Mole Calculations
➢ The identity of a substance is defined not only by the types of atoms or ions it
contains, but by the quantity of each type of atom or ion.

For example

❖ water (H2O), and hydrogen peroxide (H2O2) are alike in that their respective
molecules are composed of hydrogen and oxygen atoms.

However,

❖ The number of hydrogen and oxygen atoms in both molecules are different
and hence exhibit very different properties.

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 Cont’d
Mole
➢ It is an amount of unit similar to familiar units like pair, dozen, gross,
thus refers to a particular number of things

➢ It provides a specific measure of the number of atoms or molecules

in a sample of matter.

➢ The mole provides a link between

✓ an easily measured macroscopic property,

✓ bulk mass, and

✓ number of atoms, molecules, ions and so forth.

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 Cont’d

➢ A mole of substance contains;

6.02214076 X 1023 discrete entities (atoms or molecules).

Avogadro’s number (NA)

➢ This constant is properly reported with an explicit unit of “per mole,” a

conveniently rounded version being 6.022 X 1023/mol.

➢ One mole of any element contains the same number of atoms as one mole of
any other element.

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 Cont’d
➢ One mole of every;
• Element:
• Molecule
• Atom or particle 6.022 x 1023 units
• Ionic or
• Molecular compound

Example1: One mole of ionic substance (NaCI) contain

▪ 6.02 x 1023 NaCI particles

▪ 6.02 x 1023 Na+ ions
▪ 6.02 x 1023 CI- ions
▪ 2 x 6.02 x 1023 CI- and Na+ ions

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 Cont’d

Example2: One mole of CO2 molecule contain

▪ 6.02 x 1023 C atoms

▪ 2 x 6.02 x 1023 O atoms

Activity: Calculate the number of atoms, molecules and ions for each of the
following compounds

▪ Na2CO3

▪ H2SO4

▪ Fe2O3

▪ MgCl2

▪ CH3CO2H 7
 Converting Mass-to-Mole

➢ Use the molar mass of a substance as a conversion factor, and set up an

equation so that the unwanted unit cancels.

Mass of Substance (g)

Divided by molar mass(g/mol)

Mole of Substance (mol)

Example: How many moles of sucrose are in a tablespoon of sugar containing 2.85

g? (The molar mass of sucrose, C12H22O11 =342.0 g/mol )

Solution
2.85 g sucrose x 1 mol sucrose
= 0.00833 mol Sucrose
342.0 g sucrose
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 Converting Mole –to-Mass

➢ Use the mole of a substance as a conversion factor, and set up an equation so

that the unwanted unit cancels.

Mole of Substance (mol)

Multiply by molar mass (g/mol)

Mass of Substance (g)

Example: How many grams are in 0.0626 mol of NaHCO3, the main ingredient in

Alka-Seltzer tablets? ( Formula Mass NaHCO3=84.0 g/mol)

Solution
0.0626 mol NaHCO3 x 84.0 g NaHCO3 = 5.26 g NaHCO3
1 mol NaHCO3

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 Converting Mass –to- Number of Atoms and Molecules

➢ Use the molar mass of a substance as a conversion factor, and set up an

equation so that the unwanted unit cancels.

Mass of Mole of
Substance (g) Divided by Substance (mol)
molar mass(g/mol)
Multiply by Avogadro's no (mol-1)

Number of Atoms/Molecules
Example1. How many molecules are there in a 3.46-g sample of hydrogen
chloride, HCl?
Solution 23 HCl
3.46 g HCl x 1 mol HCl 6.02 x10
x = 5.71x1022 HCl molecules
36.5 g HCl 1mol HCl

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 Cont’d

Example2: How many hydrogen atoms are present in 43.8 g of urea [(NH2)2CO],
which is used as a fertilizer? (Molar mass of urea is 60.06 g /mol)
Solution
Step1. calculate moles of Urea Step3. calculate number of hydrogen
atoms from urea
Given mass of Urea
Moles of Urea =
Molar mass of Urea
6.02 x10 23 H
43.8 g Atoms of H = 2.917 mol H x
Moles of Urea = 1 mol H
60.06 g/mol
Moles of Urea = 0.729 mol No. of H atoms = 1.76 x1024 H atoms

Step2. calculate moles of hydrogen

from urea
Moles of H = 0.729 mol Urea x 4 mol H
1 mol urea

Moles of H = 2.917mol 11
 Cont’d

Activity:

▪ Which of the following 100.0 g samples contains the greatest number of

atoms?( Mg, Zn and Ag)

▪ Rank the following according to number of atoms (greatest to least): (107.9 g

Ag , 70.0 g Zn and 21.0 g Mg)

▪ How many carbon atoms are in 72.5 g of isopropanol ( C3H8O)

▪ Consider separate 100.0 gram samples of each of the following: Rank them
from greatest to least number of oxygen atoms.(H2O, N2O, C3H6O2, CO2)

▪ Calculate the number of molecules in 14.9 g N2O5

▪ Calculate number of Ca2+ ions in 4.71 g Ca3(PO4)2

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 4.1.2. Determining empirical and molecular formulas
Percent Composition
➢ The percent composition is the percent by mass of each element in a
compound.

➢ Percent composition is obtained by dividing the mass of each element in 1 mole

of the compound by the molar mass of the compound and multiplying by 100
percent.
Mass of element
Percent composition of element = x100%
Molar mass of compond

Example: Analysis of a 12.04-g sample of a liquid compound composed of carbon,

hydrogen, and nitrogen showed it to contain 7.34 g C, 1.85 g H, and 2.85
g N. What is the percent composition of this compound?
Solution 1.85
%H = x100%= 15.4%
12.04
7.34
%C = x100% = 61%
12.04
2.85
%N = x100 = 23.7% 13
12.04
 cont’d

Determining Percent Composition from Formula Mass

Example: Aspirin is a compound with the molecular formula C9H8O4. What is its
percent composition? (Mass of asprin 180.159 g/mol)

n x Mass of element
Percent composition of element = x100%
Molar mass of compond

9 mol x 12.01 g/mol

%C = x100% = 60%
180.15 g/mol

8 mol x 1.008 g/mol

%H = x100% = 4.47%
180.15 g/mol

4mol x 16.0 g/mol

%O = x100% = 35.52%
180.15 g/mol

Activity: What is the percent composition of each elements in citric acid, an organic
acid, commonly found in citrus fruits?(C₆H₈O₇)
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 Determination of Empirical Formulas

➢ Empirical formula is the simplest whole number ratio of atoms of each

elements in the compound

➢ Steps to determine an empirical formula are as follows

Step 1:- Write mass or % of each element
Step 2: - Calculate the number of moles of each element (divide with molar mass)
Step 3: - Divide each by smallest number, to obtain simplest ratio
Example: Ascorbic acid (vitamin C) cures scurvy. It is composed of 40.92 %
carbon (C), 4.58 % hydrogen (H), and 54.50 % oxygen (O) by mass.
Determine its empirical formula.
Solution
Step 1. convert the mass of each element to moles.
1 mol C
n C = 40.92g x = 3.407 mol
12.01 g/mol
1 mol H
n H = 4.58 g x = 4.54 mol 15
1.008 g/mol
 Cont’d
1 mol O
n O = 54.50 g x = 3.406 mol
16.00 g/mol

Step 2. convert to whole numbers by dividing all the subscripts by the smallest
subscript
3.407 4.54 3.4O6
C= =1 H= = 1.33 O= =1
3.406 3.406 3.406
Step 3: multiply all the above results by 3
C = 1x3 = 3
H = 1.33 x 3 = 3.99  4
O =1 x 3 = 3
Therefore: C3H4O3 is the empirical formula for ascorbic acid.
Activity: a) Determine the empirical formula of a compound having the following
percent composition by mass: K: 24.75 %; Mn: 34.77 %; O: 40.51%
b) Determine the empirical formula for benzopyrene having C20H12
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chemical formula?
 Determination of Molecular Formulas

▪ The molecular formula of a compound is a multiple of its empirical formula.

▪ The molecular mass is some multiple of the empirical formula mass, which is
obtained by summing the atomic masses of the atoms in the empirical formula.

▪ For any molecular compound, you can write

Molecular mass = n x empirical formula mass

▪ The molecular formula can be determine by multiplying the subscripts of the

empirical formula by n, which you calculate from the equation
Molecular mass
n=
Empirical formula mass
Example: Nicotine contains 74.02% C, 8.710% H, and 17.27% N. If 40.57 g of
nicotine contains 0.2500 mol nicotine, what is the molecular formula?
Assuming a convenient, a 100-g sample of nicotine yields the
following molar amounts of its elements: 17
 Cont’d
Example: the percentage composition of acetic acid to be 39.9% C, 6.7% H, and
53.4% O. What is its molecular formula? ( MM of acetic acid = 60.0 amu)
Solution
Step 1. convert the mass of each element to moles.
1 mol C
n C = 39.9 g x = 3.32 mol
12.01 g/mol

1 mol H
n H = 6.7g x = 6.65 mol
1.008 g/mol

1 mol O
n O = 53.4 g x = 3.34 mol
16.00 g/mol
Step2. calculate the molar ratios of these elements relative to the least abundant
element, C
3.32 6.65 3.34
C= =1 H= =2 O= =1
3.32 3.32 3.32
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 Cont’d
▪ So the empirical formula is CH2O.

Step3. Calculate the formula units

Molecular mass
n=
Empirical formula mass

60.0 g/mol
n= = 2 formula units
30.0 g/mol
Finally, derive the molecular formula for acetic acid from the empirical formula
by multiplying each subscript by two:
(Empirical formula)n = Molecular formula
(CH 2O )2 = C 2 H 4O 2
Activity: An unknown liquid is composed of 5.57% H, 28.01% Cl, and 66.42% C.
The molecular mass found by mass spectrometry is 126.58 amu. What is
the molecular formula of the compound? 19
 4.2. Limiting Reagents

Reactants are usually not present in exact stoichiometric amounts,

that is, in the proportions indicated by the balanced equation.

• The goal of a reaction is to produce the maximum quantity of a

useful product from the starting materials, frequently a large
excess of one reactant is supplied to ensure that the more
expensive reactant is completely converted to the desired product.

• Consequently, some reactant will be left over at the end of the

reaction (excess reagents). The reactant used up first in a reaction
is called the limiting reagent.

• Excess reagents are the reactants present in quantities greater

than necessary to react with the quantity (Stoichiometric
proportion) of the limiting reagent.
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 Limiting reagents (cont’d…)
• Stoichiometric Proportion – Reactants are present in a ratio
equivalent to the ratio of the stoichiometric coefficients.

A + 2B → 2C

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Cont’d...

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 Percent Yield
The amount of product that is produced by a reaction under specified
conditions, as calculated per the stoichiometry of an appropriate
balanced chemical equation, is called the theoretical yield.

Most reactions do not go to completion

The amount of product made in an experiment is the actual yield
The extent to which a reaction’s theoretical yield is achieved is
commonly expressed as its percent yield.

Actual Yield
Percent Yield = x 100%
Theoretical Yield
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 Cont’d…
Example: Upon reaction of 1.274 g of copper sulfate with excess zinc
metal, 0.392 g copper metal was obtained according to theequation:
What is the percent yield?
CuSO4 (aq) + Zn(s) ⟶ Cu(s) + ZnSO4(aq)

Using this theoretical yield and the provided value for actual yield;

Percent Yield = Actual Yield x 100%

Theoretical Yield

Activity: Determine the Mass of CO2 produced when 48.0 g of O2 reacts

with 56.0 g of CO if 72.0 g of CO2 is actually made, what is the Percentage 24
Yield?
 4.3. 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 most commonly used unit to express concentration in chemistry
is Molarity (M) which is defined as the number of moles of solute
per litre of solution.
Molarity
Mole of solute
𝐌 = Molarity =
Volume (L) of solution

Example: What mass of KI is required to make 500. mL of a 2.80 M KI solution?

volume of KI solution moles KI grams KI
1L 2.80 mol KI 166 g KI
500. mL x x x = 232.4 g KI
1000 mL 1 L soln 1 mol KI

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 Cont’d
Dilution Solutions
▪ Dilution is the procedure for preparing a less concentrated solution from a
more concentrated solution.
▪ By adding solvent to a measured portion of a more concentrated stock solution,
a solution of lesser concentration may be prepared.

Dilution
Add Solvent

Moles of solute Moles of solute

before dilution (i)
= after dilution (f)
MiVi = MfVf
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 Cont’d

Example: How would you prepare 60.0 mL of 0.200 M HNO3 from a solution
of 4.00 M HNO3?
MiVi = MfVf

Mi = 4.00 M Mf = 0.200 M Vf = 0.0600 L Vi = ? L

MfVf 0.200 M x 0.0600 L

Vi = = = 0.00300 L = 3.00 mL
Mi 4.00 M
Dilute 3.00 mL of acid with water to a total volume of 60.0 mL.

Activity: a) How would you prepare 2.00 x102 mL of a 0.866 M NaOH solution,
starting with a 5.07 M stock solution?
b) How can you prepare a solution of 50 mL of 0.05 M H2SO4 from its stock
solution (18 M)? Hint: series dilution!
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 Titrations
Titrimetry is an analytical method that is based on determining the
quantity of a reagent of known concentration that is required to
react completely with the analyte.

SOME TERMS USED IN VOLUMETRIC TITRIMETRY

Titration: is a process in which a standard reagent is added to a

solution of an analyte until the reaction between the analyte and
reagent is judged to be complete.

Standard solution: is a reagent of exactly known concentration that

is used in a titrimetric analysis.
Titrant: a solution containing a known concentration of the substance
Analyte: a sample solution containing a substance whose
concentration is to be measured.
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 Cont’d
The equivalence point: in a titration is a theoretical point reached
when the amount of added titrant is chemically equivalent to the
amount of analyte in the sample.
—The equivalence point of a titration may be detected visually
if a distinct change in the appearance of the sample solution
accompanies the completion of the reaction.
End point: the point at which the color change of the indicator is
observed. Here the volume of titrant required is measured.
Determined by:
— Indicator: are special dyes added to the • indicator color change
sample solutions to impart a change in color • dramatic change
at or very near to the equivalence point of the in pH
titration.
— The difference in volume or mass between the
equivalence point and the end point is the
titration error.
Et = V ep - V eq 29
 Cont’d
A primary standard: is an ultra pure compound that serves as the
reference material for a titrimetric method of analysis.
Important requirement
— High purity;
— Atmospheric stability;
— Absence of hydrate water so that the composition of the solid does
not change with variations in humidity.
— Reasonable solubility in the titration medium.
— Reasonably large molar mass so that the relative error associated
with weighing the standard is minimized.
— Examples
Potassium Acid Phthalate (KHP), Sodium carbonate
A secondary standard is a compound whose purity has been
established by chemical analysis and that serves as the reference
material for a titrimetric method of analysis.
Standardization is a process in which the concentration of a secondary
standard is determined to a high level of accuracy by titration with a primary
standard. 30
 Types of titrations
Classified into four types based on type of reactions involved
— Acid-base
— complexometric
— precipitation titrations
A sigmoidal curve: the p-function
— redox
of analyte is plotted as a function
Acid-base titration: in which an acidic of reagent volume.
or basic titrant reacts with an analyte
that is a base or an acid.
Example: H+ + OH- → H2O Solution
Solution
of
of NaOH
NaOH
— In the beginning the pH increases
very slowly. Step by step NaOH is
added, and the pH rises as the
equivalence point is approached.
Solution
— As additional NaOH is added; the of HCl

pH increases and then levels off as 5 mL

NaOH is added beyond the

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equivalence point.
 Cont’d
Complexometric titration is a form of volumetric titration in which the
formation of a coloured complex is used to indicate the end point of a
titration. The complexes are formed by the reaction of a metal (an acceptor,
a central atom or a cation) with an anion, a neutral molecule or very rarely a
positive ion.

Example: EDTA + Ca2+ → (Ca-EDTA)2-

Precipitation titration: is a titration with a precipitating agent which is
useful for determining certain analytes e.g. chloride can be determined
when titrated with AgNO3
Ag+ (aq) + Cl-(aq) → AgCl(ppt)
● Indicator used is Ag2CrO4
Redox titrations: are based on an oxidation-reduction reaction between the
analyte and titrant. Redox titrations are carried out by using a
potentiometer or a redox indicator to determine the end point.
Example: 5H2O2 + 2MnO4- + H+ → 5O2 + 2 Mn2+ + 8H2O
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 Cont’d
Example:

The end point for 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 dilution formula is used here to calculate the molarity

or volume of analyte or titrant.

(C1*V1)HCl = (C2*V2)NaOH

(C1*50 mL = (0.25M*35.23)NaOH
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C1 HCl = 0.176 M
 Activity

a) What volume of 0.1 M NaOH solution is required to neutralise 100

mL of concentrated aqueous H2SO4 which contains 98 %(w/w).
The density of concentrated H2SO4 solution is 1.84 g/mL. (Atomic
mass of H=1, S=32, O=16 and Na=23 amu).

b) What volume of 0.5 M HCl is required to titrate 100 mL of 3.0 M

Ca(OH)2?

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