2.

1 RELATIVE MASSES OF ATOMS AND MOLECULES

OBJECTIVES
By the end of the subtopic the learner should be able to:
• Explain the terms relative atomic, isotopic, molecular and formula masses.
• Analyse mass spectra in terms of isotopic abundances and molecular fragments.
• Relate a mole to Avogadro constant.
• Determine empirical and molecular formulae using combustion data or composition by
mass.
• Construct balanced equations.
• Perform calculations including the use of mole concept involving reacting masses,
volumes of gases.

INTRODUCTION
• All the elements on the periodic table have a mass termed the relative atomic mass.
• The word relative means all the elements are being compared to one common element
which is carbon-12.

THE CARBON-12 SCALE

• Carbon has two isotopes, carbon-12 and carbon-13.
• An isotope is an element with the same proton number but different neutron number.
• The carbon-12 isotope has been chosen as the standard element against which all other
elements are compared because:
• It is the most abundant isotope of carbon constituting approximately 99% of the
carbon isotopes.
• At standard conditions of temperature and pressure, carbon-12 is a solid and stable
element making it easy to handle.
• The carbon 12 element is assigned an exact mass of 12 atomic mass unit (a.m.u) (the
carbon-12 scale).

THE ATOMIC MASS UNIT (a.m.u)

• It is defined as of the mass of one carbon-12 element.

• Consider the arrangement of a carbon atom from the periodic table:

 • From the periodic table, the atom of carbon has symbol C, 6 protons, 6 neutrons and 6
electrons in its natural state.
• On the carbon-12 scale:
• Proton mass = 1.0074 a.m.u.
• Neutron mass = 1.0089 a.m.u.
• Electron mass = 0.0005 a.m.u.
Therefore the total mass of carbon-12 atom is:

• Note that the carbon-12 scale says that carbon weighs 12 a.m.u which is different from
the 12.1008 calculated, why?
• In the calculation, uncombined electrons, protons and neutrons are added.
• When these sub atomic particles fuse together to form an atom, some of the mass is
converted into energy according to Einstein’s equation,
• The converted mass is called the mass defect and the equivalent amount of energy is
called the binding energy.
Now:

Therefore, the mass of a carbon-12 atom is:

• Although the S.I unit for mass is the kilogram, in Stoichiometry and laboratory chemistry
the standard unit is the gram.

THE RELATIVE ISOTOPIC MASS

• It is the mass of a specific isotope of an element compared to the mass of the carbon-12
isotope.
Mathematically,

OR:
The relative atomic mass, Ar

• It is the average weight of all the isotopes of an element relative to the carbon-12
isotope.
Mathematically,

OR:

• It is important to note that of the mass of one carbon-12 atom is equal to 1 a.m.u
Hence the formula reduces to:

Method of determining relative atomic mass, Ar

• Determine the isotopes present in the sample using mass spectrometry.

• Determine relative abundances of each isotope in the sample from the mass spectrum.
• Multiply the atomic mass of each isotope by its proportion in the sample.
• Add the results.
Example 2.1.1
A mass spectrometer used to analyse a sample of naturally occurring copper gave these
readings, 69.2% copper-63 and 30.8% copper-65. What is the relative atomic mass of the
element copper?
Solution
 Example 2.1.2

The relative atomic mass of chlorine is 35.45. It has two isotopes with mass numbers 35
and 37.Calculate the relative abundances of each isotope.

Solution

• Let x be the % abundance of first isotope, the second isotope is (100-x)%

• Recall the formula for relative atomic mass and substitute

Therefore Chlorine-35 has 77.5% and chlorine-37 has 22.5%

THE RELATIVE MOLECULAR MASS, Mr

• It is the weighted average mass of all molecules involved in a molecular formula relative
to the carbon-12 isotope.
• Mathematically,

• Only applicable to substances which exist as molecules.

Method:

• Determine the molecular formula of the molecule.

• Determine the number of atoms of each element in the molecule.
• Assign each element its relative atomic mass using the periodic table.
• Multiply the number of atoms of each element with its respective atomic mass.
• Add the values as summarised below:

The relative formula mass, Mr

 • It is the weighted average mass of all the units in the formula relative to the carbon-12
isotope.
• Mathematically,

OR simply

• It works for both ionic and covalent compounds.

Example 2.1.3

Use the periodic table to answer the following question

What is the relative molecular or formula mass of the following?

• Ammonia,
• Phenylamine,
• Hexa-aqua cobalt pink,
• Sodium sulphate,
Solution

a. Relative molecular mass,

b. Relative molecular mass,

c. Relative formula mass,

d. Relative formula mass, (

\
Summary

• Relative isotopic mass, relative atomic mass, relative molecular mass and relative
formula mass are all measured against the carbon-12 scale.
• The carbon-12 scale has been assigned the mass of carbon-12 isotope which is 12 a.m.u.

MASS SPECTROMETRY
• Mass spectrometry is a method chemists use to determine the masses of atoms or
molecules in a given sample.
• The method is used to find relative isotopic abundance, atomic mass, molecular mass
and the structure of a compound.
• Consider the mass spectrometer and simplified block flow below:

Figure 2.1.2: Simplified diagram and block flow diagram for mass spectrometry.

Vaporization chamber

• A known sample is placed in the chamber and very high temperatures are applied so
that all atoms are converted into gaseous atoms.

Ionization chamber
• The purpose of ionisation is to turn the gaseous atoms into positive gaseous ions.

Acceleration chamber

• The gaseous ions are then accelerated by an electric field created by introducing a very
high voltage between plate X and Y so that the electrons all move with same velocity.

Magnetic field region

• A magnetic field is turned on and the positive ions are deflected according to:
• The mass of the ion (The lighter the ion the more deflected they are).
 • The charge on the ion (Ions with 2 (or more) positive ions are deflected more).

Ion detection

• The deflected ions are detected by the ion detector and the data is fed onto a computer
where the data is printed on a mass spectrum.

The mass spectra of an element

• The mass spectrum is a simple graph used to analyse masses of both, the relative mass
per charge) against relative abundance as shown below:

Figure 2.1.4: General mass spectrometry of an element.

• From the mass spectrometry, the following information is provided:

• Isotopes present and their relative isotopic masses.
• Relative abundance of the present isotopes.
• With this information, the relative atomic mass of the element can be calculated using
the formula:

Mass spectra of Molecules

• The mass spectra of molecules contains two types of lines:

• The line due to the whole molecule.
• Lines due to molecular fragments.
• The line with the highest abundance is called the base peak.
• The line with the highest m/e value is called the molecular ion.
• Consider the following mass spectrum of carbon dioxide:

Figure 2.1.5: Mass spectrometry of molecules.

• Carbon dioxide, has the highest mass, (m/e = 120) and represents the whole molecule,
hence the relative molecular mass of element X = 120.
 Example 2.1.4

Below is the mass spectrum of methyl bromide. List down all the peaks of the spectrum
using carbon-12 and the two isotopes of bromine 79Br and 81Br.

Fig 2.1.6: Mass spectrum of methyl bromide CH3Br.

Solution

• [CH3]+
• [79Br]+
• [81Br]+
• [C79Br]+
• [CH79Br]+
• [C81Br]+ And [CH279Br] +
• [CH81Br]+ And [CH3Br] +
• [CH281Br]+
• [CH381Br]+

THE MOLE CONCEPT

The Mole
 • A mole is defined as the amount of any substance that contains the same number of
elementary entities (particles) as there are in 12 grams of the carbon-12 isotope.
• The number of moles of any substance can be calculated as shown below:

Where:

• Mass represents the weight of the sample.

• Molar mass is the relative atomic mass (from periodic table) of the substance in.
Example 2.1.5

• How many moles are contained i n a sample of 2g of calcium, ?

• Use the periodic table to predict the element that weighs 2.875g and contains
0.125moles?
Solution

The element isbecause its molar mass =

 Example 2.1.6

A pilot plant produced 184g of ethanol, :

• How many moles of ethanol are present?

• How many moles of hydrogen atoms are present in the ethanol produced?
Solution

The molar mass of ethanol is 46.

• Each molecule of ethanol contains 6 hydrogen atoms.

The Avogadro number,

• Defined as the number of particles in one mole of any substance.

• The number is a constant and has the value to 3s.f.
• Examples:
• 1 mole of Ne contains
• 1 mole of NH3 contains but
• It is possible to find the number of particles on any given sample according to the
equation:
 Example 2.1.7

Use the data booklet to calculate number of particles in 7g of Nitrogen sample.

Solution

Recall:

Therefore,

Moles of Gases
• All gases occupy equal volume at same conditions of temperature and pressure
(Avogadro’s law).
• For example: 22.4 dm3 of ammonia, oxygen, methane and ammonia all contain 1 mol of
gas at 1 atm and 0.
• Always check out for the following terms:
• Standard temperature and pressure (s.t.p) which is 0 (273K) and 101.325kPa (1atm)
respectively.
• Room temperature and pressure (r.t.p) which is 25 (298K) and 101.325kPa (1atm)
respectively.
• At s.t.p, 1 mole of any gas occupies 22.4dm3 (22400cm3) or 24 litres.
• At r.t.p, 1 mole of any gas occupies 24 dm3 (24000cm3) or 22.4 litres.
 Example 2.1.8

Use the data booklet to calculate the volume of molecules of hydrogen at:

• Standard temperature and pressure.

• Room temperature and pressure.
Solution

Recall:

Let the number of moles of hydrogen be x

• At s.t.p,

• At r.t.p,

• At standard temperature and pressure, gases occupy less volume compared to room
temperature and pressure.
• This is because as temperature is increased the intermolecular forces holding the gases
together become less significant until the gas reach ideality.
• When the gas reaches ideal state, the intermolecular forces become negligible.

DETERMINATION OF EMPIRICAL AND MOLECULAR FORMULA

• Empirical formula is the simplest ratio of elements in a given compound.

 • Molecular formula is a chemical formula that gives the total number of atoms of each
element in each molecule of a substance.
• There are mainly two methods of determining the empirical and molecular formula of a
compound:
• Composition by mass.
• Combustion data.

1. Composition by mass

• To determine the empirical formula of a compound, follow the procedure below:

• Assume a basis of 100g for the sample e.g. a compound containing 57.5%C, 3.5%H
and 39%F is assumed to have 57.5gC, 3.5gH and 39gF respectively.
• Write down the relative atomic mass of each element in the compound.
• Convert the individual elemental masses into moles using the formula:

• Determine the element with the least number of moles and divide all the other mole
values with this number to determine the mole ratios.
• Check if the mole ratios are whole numbers, if they are not multiply by the smallest
possible factor that produces whole number mole ratios e.g. 1:0.33 may be
multiplied by 3 to have 3:1 mole ratio.
• To write the empirical formulas of the compound attach these whole number mole
ratios to the respective elements as subscripts.
• The molecular formula can then be deduced from the empirical formula using:

Example 2.2.7

• An organic compound was analysed and /found to contain 40.0% carbon, 6.7%
hydrogen, and 53.3% oxygen, what is its empirical formula.
• The relative molecular mass of the sample was found to be 180g/mol, calculate
the molecular formula of the compound. What is the name of the compound?
Solution

a. The empirical formula of the compound is calculated as follows:

 Carbon, C Hydrogen, H Oxygen, O

Step 1 Assume a basis of 100g

Write down Ar of all elements
Convert into elemental moles
Divide by the smallest mole
ratio
mole ratios as integers
 Attach numbers to elements

The empirical formula of the compound is

 b. The molecular formula is calculated as follows:

Also

2. Combustion data analysis

• Combustion data analysis is the most common way of determining elemental

composition of organic compounds.
• The technique assumes complete combustion at room temperature and pressure and
has the general combustion formula written as:

• Note that at room temperature all the other reactants or products are in gaseous state
except the water produced hence the volume of water is negligible i.e. .
Example 2.2.7

A chemist measured of a hydrocarbon that required oxygen gas for complete

combustion. Upon complete combustion, of carbon dioxide was produced. Calculate the
molecular formula of the hydrocarbon.

Solution

Recall:

If of is burnt in oxygen, of carbon dioxide would be produced i.e.

Substituting for x,

The molecular formula of the compound is