Lesson 2: Atomic structure

Dalton´s Atomic theory

Postulates of Dalton’s Atomic Theory

 All matter is made up of tiny, indivisible particles called atoms.

 All atoms of a specific element are identical in mass, size, and
other properties. However, atoms of different element exhibit
different properties and vary in mass and size.
 Atoms can neither be created nor destroyed. Furthermore,
atoms cannot be divided into smaller particles.
 Atoms of different elements can combine with each other in
fixed whole-number ratios in order to form compounds.
 Atoms can be rearranged, combined, or separated in chemical
reactions.

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Limitations of Dalton’s Atomic Theory
 It does not account for subatomic particles: Dalton’s atomic theory stated that atoms were
indivisible. However, the discovery of subatomic particles (such as protons, electrons, and
neutrons) disproved this postulate.
 It does not account for isotopes: As per Dalton’s atomic theory, all atoms of an element
have identical masses and densities. However, different isotopes of elements have different
atomic masses (Example: hydrogen, deuterium, and tritium).
 It does not account for isobars: This theory states that the masses of the atoms of two
different elements must differ. However, it is possible for two different elements to share
the same mass number. Such atoms are called isobars (Example: 40Ar and 40Ca).
 Elements need not combine in simple, whole-number ratios to form compounds: Certain
complex organic compounds do not feature simple ratios of constituent atoms. Example:
sugar/sucrose (C11H22O11).
 The theory does not account for allotropes: The differences in the properties of diamond
and graphite, both of which contain only carbon.
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Thomson experiment of discharge tube: evidence of electron
Cathode Ray Tube
In a cathode ray tube, electrons are accelerated
from one end of the tube to the other using an
electric field. When the electrons hit the far
end of the tube they give up all the energy they
carry due to their speed and this is changed to
other forms such as heat.

J. J. Thomson designed a glass tube that was partly evacuated, i.e. all the air had been drained
out of the building. He then applied a high electric voltage at either end of the tube between
two electrodes. He observed a particle stream (ray) coming out of the negatively charged
electrode (cathode) to the positively charged electrode (anode). This ray is called a cathode
ray and is called a cathode ray tube for the entire construction.
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Results of Thomson experiment demonstrated that:

(i) The cathode rays cause the florescent screen to glow with green light when the rays fall on
it.

(ii) The rays are bent towards the positive electrode when an electric field is placed on their
path.

(iii) A magnetic field has a similar effect on the rays as the electric field.

(iv) An object placed behind the perforated anode casts a shadow on the screen.

(v) The rays penetrated sheets of metal as 1mm thick aluminium without casting a shadow.

(vi) The rays can impart mechanical motion on a tiny paddle wheel.
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Explanation of the Results of Thomson experiments:
(i) The bending of the rays by both electric and magnetic fields suggest that cathode rays
are negatively charged particles.

(ii) The casting of the shadow of an object in their path on the screen shows that the rays
travel in straight line.

(iii) That the cathode rays can pass through aluminium foil indicates that they are smaller
particles than atoms.

(iv) They are able to rotate a paddle wheel because they are particles, which possess some
mass (though negligible).

(v) The constant mass and charge of the particles irrespective of the nature of the cathode
or the residual gas proves that they are basic constituents of matter. These particles are
called electrons.
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Measurement of e/m for electrons
Magnetic field applied to deflect electrons in a circular path away from straight path
Electrostatic field applied to return electron to its straight path position
Relationship between magnetic force and centrifugal force
Bev = mv2/r
Where
B = magnetic field strength
v = velocity of electrons
e = charge on the electron
m = mass of the electron
r = radius of the circular path

e/m = v/(Br)

Counterbalancing magnetic and electric field

Bev = Ee
Thus, v = E/B
e/m = E/(B2r) = -1.76 108 Coulomb/g

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 Millikan oil drop experiment
 Oil is passed through the atomizer from where it came in the form of tiny droplets. They pass the droplets through the
holes present in the upper plate of the apparatus.
 The downward motions of droplets are observed through a microscope and the mass of oil droplets, then measure their
terminal velocity.
 The air inside the chamber is ionized by passing a beam of X-rays through it. The electrical charge on these oil droplets is
acquired by collisions with gaseous ions produced by ionization of air.
 The electric field is set up between the two plates and so the motion of charged oil droplets can be affected by the
electric field.
 Gravity attracts the oil in a downward direction and the electric field pushes the charge upward. The strength of the
electric field is regulated so that the oil droplet reaches an equilibrium position with gravity.
 The charge over the droplet is calculated at equilibrium, which is dependent on the strength of the electric field and mass
of droplet.

Millikan equation:
Electric field intensity × charge on oil drop = mass of oil drop – upthrust on oil drop
Conclusion: The charge over any oil droplet is always an integral value of e (-1.6 x 10 -19 Coulombs).
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Thomson and Millikan oil drop experiment

The ratio of charge e to the mass m of the cathode rays calculated to give e/m and e as
the mass of an electron as 1/1837 of H-atom, i.e. 0.00055 amu (atomic mass unit).

NB: 1 amu = 1/12 the mass of C-12 or 1.6605 × 10-24 g

According to Thomson, e/m gives -1.76 × 108 Coulombs/g

R. Millikan using the oil drop experiment was able to calculate the charge of an electron
as -1.60 × 10-19 Coulombs

Therefore, the mass of an electron can be calculated based on Thomson and Millikan
experiments to be 9.1 × 10-28 g

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Evidence of proton: Thomson experiment

Thomson used a discharge tube with a cathode at

the centre
Green fluorescence caused by cathode rays
Red glow caused by positive charged particles called
positive rays
Much larger force required to deflect positive rays
Mass of positive rays depend on the nature of gas
used
Number of positive rays equal number of electrons
Positive rays constitute half the mass of the atom
Positive rays are called protons

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Evidence of proton: Thomson experiment
 Alpha particles generated from polonium
 Chadwick bombarded a thin sheet of Beryllium with alpha particles

 When Beryllium is placed, alpha particles are not detected by

Geiger-Muller counter

 When piece of paraffin is placed, charged particles are detected by

the counter

 Explanation: Alpha particles striking Beryllium sheet displaced

uncharged particles called neutrons from the nuclei of Beryllium
atoms. These uncharged particles are not detected.

 However, when paraffin wax is placed, the uncharged particles

displace charged particles from the paraffin wax which are
detected by the counter.

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Electromagnetic radiation
 Energy: ability to do work
 Work is force (f) and distance (d) moved in the direction of force i.e., w = f × d
 Force is measured in Newtons (N) while distance is measured in metres hence w has units N.m
 A wave may be defined as a wave is a disturbance that transfers energy from one point to another without
imparting net motion to the medium through which it travels. Thus, the particles of the medium are not
permanently displaced, but just oscillate back and forth about their equilibrium position.

 Mechanical waves (pulse waves on a rope or a string, sound waves, waves travelling across the surface of water,
seismic waves, etc.); they require a medium for their propagation.

 Electromagnetic waves (visible light, IR radiations, ultraviolet radiation, radio and TV waves, X – rays, gamma rays,
ultrasound,……). Those consist of transverse oscillations of Electrical (E) and magnetic (B) fields. In this case we
have oscillations of fields and not material particles. They do not require a medium for their propagation (they can
carry energy through the vacuum).

 Matter waves which are waves associated to electrons and other micro- particles (protons, neutrons, alpha
particles, atoms, molecules, etc.). Electrons, protons, neutrons, …. are described, in quantum mechanics, by De
Broglie waves – “probability waves” associated to these micro -particles.
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Properties of waves

 Crest: the highest point of the wave

 Trough: the lowest point of the wave

 Wavelength, λ (m): The distance between one

point on a wave and the exact same place on
the next wave.
 Wave number: 1/λ (m-1)

 Frequency, f: How many waves go past a point in one

second; unit of measurement is hertz (Hz or s-1). The
higher the frequency, the more energy in the wave.

 Amplitude: How far the medium moves from rest

position (where it is when not moving).

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Properties of waves

The energy of a wave is proportional to the square of its amplitude. Mathematically speaking . . .

E = kA2

Where: E = energy (the capacity to do work) k = a constant (depends on the medium) A = amplitude

Speed of a wave: Depends on the medium in which the wave is traveling. It varies in solids,
liquids and gases. A mathematical way to calculate speed: wave speed = wavelength x
frequency

i.e., ν = λ × f
Where ν = speed of wave (m/s)
λ = wavelength (m)
f = frequency (Hz)

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Electromagnetic radiation
Electromagnetic radiation of frequency ν,
wavelength λ, in free space obeys:

c = λυ where
c = speed of light Individual photons
For light c = 3.0 ×108 m/s

The energy of photons is given as:

E = hν
where h = Planck’s constant, 6.626 ×10−27 erg.s

Energies are often given in electron volts,

where: 1 eV = 1.6 ×10−12

erg = 1.6 ×10−19 J

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Electromagnetic radiation

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Electromagnetic spectrum

Visible region is of
interest in chemical
analysis

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Emission Spectrum of atoms

Emission spectrum: each element emits light when it is excited by an electric

current passing through its gas or vapor:
 the atoms first absorb energy, then lose the energy as they emit light

 passing light emission through a prism gives a unique atomic emission spectrum

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Emission Spectrum of atoms
White light gives a continuous spectrum

But:
Atomic emission spectra: relatively few lines. This suggests that
the emission of very specific, exact frequencies of energy/light

And each line corresponds to a specific amount of energy being

emitted!!

The light emitted by an element when its electrons return to a

lower energy state can be viewed as a bright line emission
spectrum.
Emission spectrum: each element emits light when it is excited by an
electric current passing through its gas or vapor:
 the atoms first absorb energy, then lose the energy as they emit light

 passing light emission through a prism gives a unique atomic emission

spectrum
 Photons absorb or emit energy in quantum amounts
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Emission Spectrum of atoms

The emission spectrum of each element is unique to that element

Emission spectra can be used to identify the components of an unknown compound (flame test experiments)

The Quantum Concept

According to classical physics, there is no limit to how small the energy gained or lost by an object can be…so… classical
physics cannot explain emission spectra which only allows SOME amounts of energy, but not others…enter:

Max Planck! (1858-1947) – he wondered, what if light energy consists of little packets of energy called “QUANTA”?

Einstein added the proposal we can describe light as composed of particles, or photons

Each photon of light has a particular amount or packet of energy (a quantum).

The amount of energy (frequency) possessed by a photon depends on the color (wavelength) of the light.

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Photoelectric effect
The photoelectric effect is a phenomenon in which electrons are
ejected from the surface of a metal when light is incident on it.
These ejected electrons are called photoelectrons.

It is important to note that the emission of photoelectrons and

the kinetic energy of the ejected photoelectrons is dependent
on the frequency of the light that is incident on the metal’s
surface.

The process through which photoelectrons are ejected from the

surface of the metal due to the action of light is commonly
referred to as photoemission.

The photoelectric effect occurs because the electrons at the

surface of the metal tend to absorb energy from the incident
light and use it to overcome the attractive forces that bind them
to the metallic nuclei.
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Photoelectric effect
The photoelectric effect cannot be explained by considering light as a wave. However, this phenomenon can
be explained by the particle nature of light, in which light can be visualized as a stream of particles of
electromagnetic energy. These ‘particles’ of light are called photons. The energy held by a photon is related to
the frequency of the light via Planks equation:

E = h𝜈 = hc/λ

Where,
E = the energy of the photon
h = Planck’s constant
𝜈 = the frequency of the light
c = the speed of light (in a vacuum)
λ = the wavelength of the light

Thus, it can be understood that different frequencies of light carry photons of varying energies. For example,
the frequency of blue light is greater than that of red light (the wavelength of blue light is much shorter than
the wavelength of red light). Therefore, the energy held by a photon of blue light will be greater than the
energy held by a photon of red light.
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Photoelectric effect
The energy of photon = energy needed to Guidelines about Photoelectric Effect
remove an electron + kinetic energy of the  For a light of any given frequency; photoelectric current
emitted electron is directly proportional to the intensity of light

i.e., hν = W + E  For any given material, there is a certain minimum

(energy) frequency, called threshold frequency, below
Where, which the emission of photoelectrons stops completely,
no matter how high is the intensity of incident light.
h = Planck’s constant.
ν = the frequency of the incident photon  The maximum kinetic energy of the photoelectrons is
W = work function. found to increase with the increase in the frequency of
E = the maximum kinetic energy of ejected incident light, provided the frequency exceeds the
electrons given as K.E = 1/2 mv² threshold limit. The maximum kinetic energy is
independent of the intensity of light.

Photons – light quanta or “packets of energy”  The photo-emission is an instantaneous process.

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