Chemistry Unit 1 D.

Hines

Atomic Structure

Dalton’s atomic theory

John Dalton developed the first useful atomic theory of matter, even some of his theories are now
known to be incorrect.

He suggested that;

 Matter consists of small particles called atoms

 Atoms are indestructible or indivisible
 Atoms of the same element are identical in mass and properties
 Atoms combine to form more complex structures (compounds)
 Atoms can combine in more than on simple whole number ratio

Later changes to Dalton’s theory

 Atoms could be sub divided into subatomic particles and can also be destroyed by nuclear
reactions
 Atoms of the same element can have different masses as seen in isotopes

Discovery of subatomic particles

J.J Thompson

Thompson discovered the electron. He suggested electrons are embedded in a sea of positive charge.

Earnest Rutherford

Rutherford suggested that most of the mass of the atom was in a tiny positively-charged nucleus in the
middle of the atom. This led to the planetary model with electrons surrounding the nucleus.

Niels Bohr

He suggested that electrons could only orbit the nucleus at certain distances depending on their energy.

James Chadwick

Chadwick discovered the presence of the neutron in the nucleus.

Atomic Structure

The word atom comes from the greek word ‘atomos’ which means something that cannot be split into
pieces. Atoms are considered the basic building block of chemistry.

Atoms are made up of three fundamental particles: protons, neutrons and electrons.

Protons and neutrons are found in the nucleus and are collectively called nucleons, they are held
together in the nucleus by powerful nuclear forces. Electrons orbit the nucleus in a similar way to that in
which planets orbit a sun. In between the electrons and nucleus there is nothing (empty space).

The mass of the subatomic particles is measured relative to one twelfth the mass of a carbon-12
isotope, while the charge of the particle is compared to the charge of a proton and an electron.

The proton has a mass of 1.67 x 10-27 kg and a charge of +1.6 x 10-19 C.

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The basic properties of these three particles can be summarized in the following table:

Particle Charge Mass Location

Proton +1 1 In the nucleus

Neutron 0 1 In the nucleus

Electron -1 Approx 1/1840 units (very small) Orbiting the nucleus

Subatomic particles and the electric field

If the particles have the same speeds

If beams of the three sorts of particles, all with the same speed, are passed between two
electrically charged plates:

 Protons are deflected on a curved path towards the negative plate.

 Electrons are deflected on a curved path towards the positive plate.
 If the electrons and protons are travelling with the same speed, then the lighter electrons
are deflected far more strongly than the heavier protons.
 Neutrons continue in a straight line.

b) Atomic numbers, mass numbers and isotopes

An atom is named after the number of protons in its nucleus. If the nucleus of an atom has 1 proton, it is
hydrogen; if it has two protons, it is helium; if it has 3, it is lithium etc. The number of protons in the
nucleus of an atom is called the atomic number. It has the symbol Z.

The atomic number (Z) is the number of protons in the nucleus of an atom. It is also equal to the
number of electrons in a neutral atom and it is also the position of the element in the periodic table.

Mass number (A)

Mass number (A) is the number of protons plus neutrons in the nucleus of an atom.

So the number of neutrons in an atom is A- Z (mass number – atomic number). Since the protons and
neutrons are found in the nucleus of the atom, the atomic mass is also referred to as the nucleon
number.

Isotopes

Isotopes are atoms of the same element with the same atomic number but different mass number. The
number of protons is the same but the number of neutrons differs. Since the number of protons is equal
to the number of electrons, isotopes have identical chemical properties however their physical
properties are different because they have different masses.

Most elements exist as more than isotope, for example chlorine-35 and chlorine-37. The proportion of a
given element is called the relative abundance. The relative abundance is the ratio or percentages in

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which they exist in the world. The mass of an element depends on the relative abundance of the
isotopes present in the element.

Relative atomic mass

The relative atomic mass is the mass of an atom compared to one twelfth the mass of a carbon-12
isotope. The relative is not usually a whole number because the average weight and relative abundance
of the isotopes of elements in naturally occurring samples are measured.

Relative isotopic mass

This is the mass of a single isotope compared to one twelfth the mass of a carbon – 12 -isotope.

Mass spectrometer

The mass spectrometer is an instrument used for measuring the masses of atoms and molecules. It can
also be used to measure the relative abundance of different isotopes and to predict the structure of
more complex molecules.

1. How the mass spectrometer works

The workings of the mass spectrometer can be summarized in five stages:

1- Gaseous material released into ionization chamber

2- The element passes into the ionization chamber where the atoms are particles bombarded with
electrons and ionized, mostly to +1 ions (IONISATION)
A metal wire is heated until it starts emitting high energy electrons. These electrons hit the particles,
knocking more electrons off. Most of the particles are ionized to +1 ions

3- Ions accelerated to uniform speed by electric field (ACCELERATION)

The positive ions are attracted to the negative plate and accelerate towards it. The positive ions
move into the accelerating chamber where an electric field accelerates positive ions towards the
magnetic field.

4- Ions deflected by magnetic field; deflection depends on m/e ratio (DEFLECTION). The ions are
deflected according to their mass/charge ratio.The heavier the particle, the less the deflection. The
lighter the particle, the more the deflection.

5- Electric current measured as ions land on plate (DETECTION)

The ions are detected by an instrument which is attached to an amplifier and a recorder. The greater
the abundance of the isotope, the larger the current. To allow ions with different mass/charge ratio

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 to be detected, the electric and magnetic field is varied. The relative heights of the peaks produced
by the recorder give a measure of the relative abundance of the different isotopes present. When the
electric and magnetic field are kept constant only ions of a specific mass to charge ratio can be
detected. By varying the electric field and magnetic field, this allows higher or lower mass to charge
ratios to be detected.

The degree of deflection depends on the mass and the charge; the greater the mass, the less the
deflection, and the greater the charge, the greater the deflection. It can be shown that the deflection is
inversely proportional to the m/e ratio.

In most cases, however, the charge is +1, so the deflection depends essentially on the relative mass of
the species in the mass spectrometer. If the spectrometer is calibrated, the masses of all the species can
be directly measured.

The greater the number of particles landing at a single point on the detector, the greater the electric
current and the larger the peak. Thus the relative abundance of different isotopes can be measured.

Since the position at which an ion appears on the detector depends on its mass, different isotopes
appear at different points on the detector. The magnitude of the peak gives the relative abundance of
the isotope.

Thus the relative atomic mass of the element can be calculated from its mass spectrum.

Calculating accurate relative atomic masses

The relative atomic mass can be calculated by the formula:

Σ (perentage abundance of each isotope x mass of each isotope)

100

eg 1. Using the mass spectrum of neon below:

100

80

relative 60
abundance

40

20

18 20 22 24 26

M/Z

ram = (90 x 20 + 10 x 22)/100 = 20.2

All relative atomic masses have been found in this way.

Eg 2. The mass spectrum of chlorine atoms shows the relative shows the relative abundance of chlorine-
35 is 75.8% and chlorine-37 is 24.2%. Calculate the relative atomic mass (Ar) of chlorine.

Radioactivity

Isotopes of some elements have nuclei which break down (decay) spontaneously. The unstable nuclei
are called radioactive isotopes. As the nuclei break down they emit particles or rays followed by
radiation. These are called emissions. The nuclei become stable by spontaneously ejecting alpha
particles, beta particles and gamma radiation. The emission of alpha and beta particles changes the
number of protons in the nucleus so that a different atom is produced.

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The table shows three types of emission;

Name of emission Type of particles/ray emitted Stopped by

Alpha (α) Helium nuclei 42He2+. Thin sheet of paper

Beta (β) Electrons 0-1e 6 mm thick aluminium foil

Gamma (µ) Very high frequency Thick lead sheet

electromagnetic radiation

Alpha particles

The emission of alpha particles leads to a decrease in atomic number by 2 and mass number by 4.

Beta particles

Beta particles are formed when a neutron disintegrates giving a proton and an electron.

The proton remains in the nucleus of the atom, so its atomic number increase by 1. The mass number is
unchanged

Gamma rays

Emission of alpha or beta particles is often accompanied by the emission of gamma rays. When particles
are emitted, the atomic nucleus becomes excited and the excess energy is released as gamma radiation
for the nucleus to return to a more stable energy level.

Band of stability

Repulsion between the positive charges of the protons is minimized by the presence of neutrons in the
nucleus. As the atomic number of an element increases, the neutron to proton ratio must also increase
to keep the nucleus together. In larger atoms, even increasing number of neutrons is not enough to
keep the nucleus together and the nucleus becomes unstable.

A plot of the number of neutrons against the number of protons in stable nuclei shows the stable nuclei
are located in a shaded area of the graph known as the band of stability. The majority of radioactive
nuclei occur outside this band.

Graph showing the band of stability

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The type of radioactive decay that a particular radioisotope undergoes depends to a large extent on its
neutron to proton ratio compared to those of nearby nuclei within the band of stability. Nuclei above
the band of stability can move towards the band of stability by emitting a beta particle and thus
increasing the number of protons in the nucleus.

Heavy nuclei which have atomic number greater than 84 tend to undergo alpha emission (below the
band of stability.

Uses of radioisotopes

 Tracers for searching for faults in pipelines and for studying the working of certain organs in the
body eg iodine-131 is used to study thyroid function.

 In medicine, for radiotherapy in the treatment of cancers.

 Dating the age of objects, eg. Using 14C to date objects which were once living.

 Smoke detectors often use 241Am (Amencium).

 Generating power. Eg. 235U is used in many nuclear reactors as a source of energy.

Exercise

1. State the four main tenets of Dalton’s atomic theory and explain any modifications to his theory
in light of later discoveries concerning the atom.
2. Explain the direction and degree of deflection of protons, electrons and neutrons in an electric
field.
3. What is the rationale for using the relative masses and relative charges of sub-atomic particles
rather than their absolute masses and charges?
4. How many protons, electrons and neutrons are in the following atoms?
(a) 2713Al (b) 3919K (c) 13153I (d) 23994Pu
5. The analysis of a compound in the mass spectrometer involves ionization, acceleration,
deflection and detection. Briefly explain how each of these processes is achieved in the mass
spectrometer.
6. Calculate the relative atomic mass of boron given that its two isotopes 10B and 11B have relative
abundances of 18.7% and 81.3% respectively.
7. What do understand by the following terms;
(a) Mass number
(b) Isotope
(c) Relative atomic mass
8. (a) What are radioisotopes
(b) State the uses of four named radioisotopes
(c)The mass spectrum of element X shows it has two isotopes of masses 63 and 65 with relative
abundance of 75% and 25% respectively. Calculate the relative atomic mass of X.
9. (a) Write equations showing the alpha decay of the following radioisotopes:
(i) 23892U (ii) 22288Ra
(b) Write equations showing the beta decay of the following radioisotopes:
(i) 23390Th (ii) 146C