Chapter 2 Atomic Structure

CHAPTER 2

ATOMIC STRUCTURE

Learning Outcomes
Introduction
Concept Map

2.1 Dalton Atomic Theory

2.2 The Discovery of Electron

2.3 Canal Rays and Protons

2.4 Rutherford and The Nuclear Atom

2.5 Neutrons

2.6 Atomic Number

2.7 Isotopes and Mass Number

2.8 Isoelectronic

2.9 Atomic Mass Units (amu)

2.10 Mass Spectrometry and Isotopic Abundances

Summary
Questions
Chapter 2 Atomic Structure

Learning Outcomes

i. Describe early milestones in the development of modern atomic theory.

ii. State the premises of Daltons atomic theory.
iii. Describe J.J. Thomson's experimental evidence for the existence of electrons.
iv. Describe Rutherford's scattering experiments and show how the results of the
experiments imply the existence of atomic nuclei.
v. List the three most important particles that all atoms are composed of, and describe their
charges and relative masses.
vi. Understand the concept of atomic mass unit.
vii. Define isotope and give the mass number and number of neutrons for a specific isotope.
viii. Describe how isotopic masses and isotopic abundances are measured experimentally
using mass spectrometry.
ix. Use a mass spectrum to compute an average atomic mass.

Introduction

The development of modern atomic theory has been contributed by the works of John
Dalton, J.J. Thomson, Robert Millikan, Ernest Rutherford and James Chadwick. In the years
of 1803 1808, John Dalton firstly proposed an atomic theory. In late 1800 a series of
experiments had been done by several scientists to establish a model of an atom that count
the basis of modern atomic theory. The incredible effort and great amount of time these
scientists put in to discover more about atoms and their potential is what led us to the
knowledge we have today. All of their studies combined resulted in the birth of the modern
atomic theory. Eventually, the atoms we know today to consist of three primary sub-
particles; electrons, protons and neutrons, which make up the atoms of all matter.
Chapter 2 Atomic Structure

Concept Map

Atomic Structure

Dalton Atomic Sub-atomic Atomic Atomic Mass

Theory Particles Number Unit

The Discovery of Isotop and

Electrons Mass
Mass Spectrometry
Number and Isotopic
Abundance
Canal Rays and
Proton
Isoelectronics
Rutherford and
the Nuclear
Atom

Neutrons

2.1 Dalton Atomic Theory

The concept of the atom was known by Greek philosophers as early as 500 B.C. In fact, the
word atom comes from the Greek atomos meaning indivisible. In the years of 1803 1808,
Daltons atomic theory was proposed and expressed by the following postulates.

a) All matter is made of atoms.

b) Atoms are indivisible and indestructible.
c) All atoms of a given element are identical in mass and properties.
d) Each element has different atoms.
e) Atoms of different elements combine in constant ratios to form compounds.
f) Atoms are rearranged in chemical reactions.

His ideas account for the law of conservation of mass (atoms are neither created nor
destroyed) and the law of constant composition (elements combine in fixed ratios). Since the
Daltons atomic postulate saying that atoms are indivisible and indestructible are no longer
valid. The atom can be divided and consists of three primary sub-particles namely electrons,
protons and neutrons, which make up the atoms of all matter.
Chapter 2 Atomic Structure

2.2 The Discovery of Electron

In 1899 Marie Curie suggested when atoms are subjected to radioactivity, the atoms
disintegrate, they contradict the Dalton's idea that atoms are indivisible. There must then be
something smaller than the atom (subatomic particles) of which atoms were composed.
The experiment carried out by Humphrey Davy in 1807, passed electricity through molten
salts (a process called electrolysis). He obtained sodium and then potassium, soft metals
which burned violently. He concluded that compounds are held together by electrical forces.

Michael Faraday in 1832-1833 realised that the amount of reaction that occurs during
electrolysis is proportional to the electrical current passed through the compounds.

Cathode ray tubes experiments performed in the late 1800s and early 1900s. J.J. Thomson
modified the cathode ray tube experiments in 1897 by adding two adjustable voltage
electrodes. Figure 2.1 shows the cathode ray tube experiment.

Figure 2.1 : Cathode ray tube

When a voltage is applied to the cathodes a glow discharge is emitted. These rays are
emitted from the cathode (- end) and travel to an anode (+ end). Cathode rays must be
negatively charged! Thomson named the cathode rays as electrons and considered to be
the discoverer of electrons. Thomson then used his modification to measure the charge to
mass ratio of electrons.

8 -
Charge to mass ratio, e/m = 1.75881 x 10 coulomb/g of e

In 1909 Robert A. Millikan determined the charge of the electron. Millikan won the first
American Nobel Prize in 1923 for his famous oil-drop experiment.

-19
The charge on a single electron = 1.60218 x 10 coulomb.
Chapter 2 Atomic Structure

-28
Using Thomsons charge to mass ratio we get that the mass of one electron is 9.11 x 10 g.

8
e/m = 1.75881 x 10 coulomb
-19
e = 1.60218 x 10 coulomb
-28
Thus, m = 9.10940 x 10

Figure 2.2 shows Millikans oil drops experiment. Below is the outline of Millikans
experiment.

(a) Tiny droplets of oil are sprayed into a chamber from an atomiser. Some of these tiny
droplets fell through a hole in the upper plate.
(b) The air molecules are ionised by a beam of x-rays and the electrons are transferred to
the oil droplets.
(c) By adjusting the voltage of the plates, the force of gravity is exactly counterbalanced by
the attraction of negative oil drop to the upper, positively charged plate.
(d) The drop suspended in mid-air. When a drop is suspended, its weight mg is exactly
equal to the electric force applied q E
.

Figure 2.2 : Millikans Oil Drops Experiment

2.3 Canal Rays and Protons

Eugene Goldstein noted streams of positively charged particles in cathode rays in 1886.
These particles move in the opposite direction of cathode rays. These particles were named
as Canal rays because they passed through holes (channels or canals) drilled on the
negative electrode. Canal rays must be positive. Goldstein then postulated the existence of
a positive fundamental particle called the proton. Figure 2.3 shows the canal rays tube.
Chapter 2 Atomic Structure

Figure 2.3 : Canal rays tube

2.4 Rutherford and The Nuclear Atom

Ernest Rutherford directed Hans Geiger and Ernst Marsdens experiment in 1910. Figure 2.4
shows the -particle scattering experiment. -particles (obtained from the disintegration of
polonium) were passed through a thin Au foil. The -particle velocity ~ 1.4 x 10 m/s (~5%
7

speed of light).

Figure 2.4 : -particle scattering experiment

They observed that most of the particles went straight through the foil, with a few were
slightly deflected or scattered. One in a million were greatly deflected. This observation gave
us the basic picture of the atoms structure.

Figure 2.5 : Schematic of -particle scattering

Chapter 2 Atomic Structure

Rutherford proposed that the mass of an atom is concentrated in a very small, dense,
positively charged nucleus. As shown in Figure 2.5, -particles that move straight toward a
nucleus, or come very close to the nucleus are deflected by electrostatic repulsion between
the positively charged -particles and the positively charged nucleus.

The much lighter electrons around the nucleus are relatively far from each other and from
the nucleus. -particles are not deflected by electrons. Figure 2.6 shows the atomic
structure proposed by Rutherford.

Rutherfords major conclusions from the -particle scattering experiment include:

(a) The atom is mostly empty space.

(b) It contains a very small, dense center called the nucleus.
(c) Nearly all of the atoms mass is in the nucleus.
(d) The nuclear diameter is 1/10,000 to 1/100,000 times less than the atoms radius.
(e) Because the atoms mass is contained in such a small volume: The nuclear density is
15
10 g/mL.

Figure 2.6: Atomic structure proposed by Rutherford

2.5 Neutrons

James Chadwick in 1932 analysed the results of -particles scattering on thin Be films.
Figure 2.7 shows the neutron ionisation detection chamber used by Chadwick to discover
the neutron.
Chapter 2 Atomic Structure

Figure 2.7: Neutron ionisation detection chamber

The discovery of neutrons has enabled us to understand the structure of the nucleus. It
consists of protons and neutrons.

In the chamber a polonium alpha emitter source is placed behind a sample of beryllium.
When beryllium is hit by the alpha particles, neutrons are emitted. The neutrons then hit a
piece of paraffin. The neutrons stop and protons (hydrogen nuclei) are ejected from paraffin.
The ejected protons hit the ionisation chamber. By observing the speed of these protons,
Chadwick was able to calculate the mass of the neutron to be roughly the same as the
proton.

There is a clear difference between protons and neutrons. Neutrons are uncharged for that
they have high penetration power on traveling through a certain medium. This is not the
case of protons.

Three fundamental particles make up the atoms. Table 2.1 listed these particles together
with their masses and their charges.

Table 2.8 : Three fundamental particles make up the atoms

Particle Mass (g) Charge Charge (units)
(Coulombs)

- -28 -19
Electron (e ) 9.1 x 10 - 1.6 x 10 -1
+ -24 -19
Proton (p ) 1.67 x 10 + 1.6 x 10 +1
-24
Neutron (n) 1.67 x 10 0 0
Chapter 2 Atomic Structure

2.6 Atomic Number

In 1913 H. G. J. Moseley realised that the atomic number determines the element. Each
element has a unique number, atomic number that identifies how many protons are in one
atom of that element.

In other words, the number of protons in the nucleus of an atom determines an element's
atomic number. The elements differ from each other by the number of protons in the
nucleus. All carbon atoms, and only carbon atoms, contain six protons and have an atomic
number of 6. Then the number of electrons in a neutral atom is also equal to the atomic
number.

Sometimes the atomic number is assigned by the symbol Z. On the periodic chart, Z is the
uppermost number in each elements box. Figure 2.8 shows an example of a Periodic Chart
for Cd element.

Figure 2.8: Periodic Chart of Cd

Isotopes and Mass Number

Isotopes are defined as for the atoms of the same element but with different neutron
numbers or having different masses. A particular isotope of an element is identified by
specifying its atomic number, given the symbol Z, and its mass number A. The mass
number is the sum of the number of protons and neutrons.

Z = proton number
N = neutron number
A=Z+N
A
A common symbolism used to show mass and proton numbers is ZE

For example;
14 48
6
N and 20Ca

and can be shortened to this symbolism.

14 48
N and Ca
Chapter 2 Atomic Structure

1
One example of an isotopic series is the hydrogen isotopes. H or protium is the most
2
common hydrogen isotope which having one proton and no neutron. H or deuterium is the
3
second most abundant hydrogen isotope which having one proton and one neutron. H or
tritium is a radioactive hydrogen isotope which having one proton and two neutrons.

16
The stable oxygen isotopes provides another example. O is the most abundant stable O
18
isotope having 8 protons and 8 neutrons. O the second most abundant stable O isotope
contains 8 protons and 10 neutrons

2.8 Isoelectronic

When two elements have the same number of electrons, it is said that they are
"isoelectronic" with one another.

EXAMPLE 2.1
Which of the following have the same number of electrons (isoelectronic)?

19 20
1. 9F 10Ne
20 24
2. Ne 12
Mg
10
20 27 3+
19
3. 9F 10
Ne 13Al

14 20 27 3+
3-
4. 7N 10
Ne 13Al

SOLUTION
14 20 27 3+
3-
Number 4. 7N 10
Ne 13 Al

2.9 Atomic Mass Units (amu)

Mass of atoms and their sub-particles are expressed in atomic mass units. An atomic mass
unit (amu) is exactly 1/12 of the mass of a carbon atom that has six protons and six neutrons
in its nucleus.

12
If we define the mass of C as exactly 12 atomic mass units (amu), then it is possible to
establish a relative weight scale for atoms.

12
By definition, 1 amu = (1/12) mass of C

-24
or 1 amu = 1.66056 x 10 g

The weighted average mass of all the isotopes of an element is known as atomic mass or
atomic weight of the element. The atomic weights of all elements are relative to the mass of
Chapter 2 Atomic Structure

a carbon-12 atom. The amount of matter that contains as many atoms, ions or molecules as
the number of atoms in exactly 12 grams of carbon-12 isotope is called mole.

12 23
The number of atoms in 12 g of C is 6.0221 x 10 (Avogadro number). The mass of 1
mole of naturally occurring carbon is 12.011 g. The atomic weight of an element is the
weighted average of the masses of its stable isotopes.

EXAMPLE 2.2
50
Naturally occurring Vanadium consists of 2 isotopes. It is 0.25% V with a mass of 49.95
50
amu, and 99.75% V, which has a mass of 50.94 amu. Calculate the atomic mass of Cu to
one decimal place.
SOLUTION

50 51
Atomic weight = V isotope + V isotope

Atomic weight = (0.0025)(49.95) + (0.9975)(50.94)

= 50.94 amu for vanadium

2.10 Mass Spectrometry and Isotopic Abundances

The masses of atoms and molecules can be determined by using a mass spectrometer
(Figure 2.9). Francis Aston (1919) devised the first mass spectrometer.

Figure 2.9 : Schematic diagram of a mass spectrometer

Below is the outline of the experiment carried out using a mass spectrometer.

(a) Gaseous substance is injected into an evacuated chamber.

(b) Atoms or molecules are ionised in ionisation chamber.
(c) Ions are accelerated through an electric field and pass through two slits to produce a
narrow beam.
(d) The beam is deflected in the magnetic field toward collector plate.
Chapter 2 Atomic Structure

The deflection of ions depends on the masses and charges. The greater the positive charge
and the smaller the mass of an ion, the more it is deflected. By varying the strength of the
magnetic field, ions of different mass can be focused progressively on a detector. The
detector identifies the mass of each ion from its path. Data is recorded as a mass spectrum.
+
Example of a mass spectrum of Ne ions is shown in Figure 2.10.

+
Figure 2.10 : Mass spectrum of Ne ions

20 21 22
The atomic mass of Ne = mass of ( Ne isotope + Ne isotope + Ne isotope )
= (0.9048 x 20) + (0.0027 x 21) + (0.0925 + 22)
= 20.1877 amu for neon.
Chapter 2 Atomic Structure

Summary

Development of the modern atomic theory, we have today came from contributions of many
different scientists. Dalton, Thomson, Millikan, Rutherford and Chadwick, all had their
specific contributions to the development of the atomic theory we have come to know today.
Dalton developed an atomic theory that matter is composed of tiny indivisible particles called
atoms. All atoms of the one element are identical, but are different from the atoms of other
elements.

Thomson proposed model of the divisible atom by experiments with cathode ray tubes
showed evidence for the existence of electrons. Millikan determined the charge on electron
by using oil-drop experiment. Millikan was able to calculate the mass of an electron using his
results and the ratio discovered earlier by Thomson.

Rutherford carried out scattering experiments and obtained results which are implied in the
existence of atomic nuclei. Chadwick discovered of neutrons, electrically neutral particles
with a mass similar to that of a proton, has enabled us to understand the structure of the
nucleus consists of protons and neutrons. Since then, the atoms with their charges and
relative masses, we knew today to consist of three primary sub-particles; electrons, protons
and neutrons, which make up the atoms of all matter. An atomic mass unit (amu) is exactly
1/12 of the mass of a carbon atom that has six protons and six neutrons in its nucleus. The
discovery of neutrons explained the existence of isotopes, first observed by F. Aston when
he invented the mass spectrometer. From a mass spectrum, we are to compute an average
atomic mass.
Chapter 2 Atomic Structure

Questions

1. State the basic ideas of Daltons atomic theory. How does that theory differ from
modern theory?

2. Describe J. J. Thomson's experimental evidence for the existence of electrons.

3. Millikan was able to determine the charge on electron using his famous oil-drop
experiment. Describe the experiment and explain how Millikan was able to calculate the
mass of an electron using his results and the ratio discovered earlier by Thomson.

4. Describe Rutherford's scattering experiments and show how the results of the
experiments imply the existence of atomic nuclei.

5. What is the difference between the mass number and the atomic number of an atom?

6. Give the mass number of each of these atoms:

(a) beryllium with 5 neutrons
(b) titanium with 26 neutrons
(c) tungsten with 110 neutrons.

7. Give the complete symbol AZX for each of these atoms:

(a) nitrogen with 8 neutron
(b) zinc with 34 neutron
(c) xenon with 75 neutrons

36 38
8. Argon has three naturally occurring isotopes: 0.337% Ar, 0.063% Ar, and 99.60%
40
Ar. Estimate the atomic weight of argon. If the masses of the isotopes are 35.968,
37.963 and 39.962 respectively, what is the atomic mass of natural argon?

9. How can a mass spectrometer be used to measure the masses of individual isotopes of
an element?