Atomic Models (Postulates, limitations)

Postulates of Dalton's Atomic Theory:

1. All matter consists of indivisible particles called atoms.

2. Atoms of the same element are similar in shape and mass, but differ from the
atoms of other elements.
3. Atoms cannot be created or destroyed.
4. Atoms of different elements may combine with each other in a fixed, simple,
whole number ratios to form compound atoms.
5. Atoms of same element can combine in more than one ratio to form two or more
compounds.
6. The atom is the smallest unit of matter that can take part in a chemical reaction.

Drawbacks of Dalton's Atomic Theory

● The indivisibility of an atom was proved wrong: an atom can be further
subdivided into protons, neutrons and electrons. However an atom is the
smallest particle that takes part in chemical reactions.
● According to Dalton, the atoms of same element are similar in all respects.
However, atoms of some elements vary in their masses and densities. These
atoms of different masses are called isotopes. For example, chlorine has two
isotopes with mass numbers 35 and 37.
● Dalton also claimed that atoms of different elements are different in all respects.
This has been proven wrong in certain cases: argon and calcium atoms each
have an atomic mass of 40 amu. These atoms are known as isobars.
● According to Dalton, atoms of different elements combine in simple whole
number ratios to form compounds. This is not observed in complex organic
compounds like sugar (C12H22O11).
● The theory fails to explain the existence of allotropes; it does not account for
differences in properties of charcoal, graphite, diamond.
●
Merits of Dalton's Atomic Theory
● The atomic theory explains the laws of chemical combination (the Law of
Constant Composition and the Law of Multiple Proportions).
● Dalton was the first person to recognize a workable distinction between the
fundamental particle of an element (atom) and that of a compound (molecule).
The Gold Foil Experiment
In 1911, Rutherford and coworkers Hans Geiger and Ernest Marsden initiated a series of
groundbreaking experiments that would completely change the accepted model of the
atom. They bombarded very thin sheets of gold foil with fast moving alpha particles.
Alpha particles, a type of natural radioactive particle, are positively charged particles
with a mass about four times that of a hydrogen atom.

Figure  4.13.14.13.1: (A) The experimental setup for Rutherford's gold foil experiment:
A radioactive element that emitted alpha particles was directed toward a thin sheet of
gold foil that was surrounded by a screen which would allow detection of the deflected
particles. (B) According to the plum pudding model (top) all of the alpha particles
should have passed through the gold foil with little or no deflection. Rutherford found
that a small percentage of alpha particles were deflected at large angles, which could
be explained by an atom with a very small, dense, positively-charged nucleus at its
center (bottom).

Observations of Rutherford Model Experiment

On the basis of the observations made during the experiment, Rutherford
concluded that

● Major space in an atom is empty – A large fraction of α-particles passed

through the gold sheet without getting deflected. Therefore, the major part of
an atom must be empty.
● The positive charge in an atom is not distributed uniformly and it is
concentrated in a very small volume – Few α-particles when bombarded were
deflected by the gold sheet. They were deflected minutely and at very small
angles. Therefore he made the above conclusion.
● Very few α-particles had deflected at large angles or deflected back.
Moreover, very few particles had deflected at 180 o. Therefore, he concluded
that the positively charged particles covered a small volume of an atom in
comparison to the total volume of an atom.

Postulates of Rutherford atomic model based on observations and

conclusions

● An atom is composed of positively charged particles. Majority of the mass of

an atom was concentrated in a very small region. This region of the atom was
called as the nucleus of an atom. It was found out later that the very small
and dense nucleus of an atom is composed of neutrons and protons.
● Atoms nucleus is surrounded by negatively charged particles called electrons.
The electrons revolve around the nucleus in a fixed circular path at very high
speed. These fixed circular paths were termed as “orbits.”
● An atom has no net charge or they are electrically neutral because electrons
are negatively charged and the densely concentrated nucleus is positively
charged. A strong electrostatic force of attractions holds together the nucleus
and electrons.
● The size of the nucleus of an atom is very small in comparison to the total size
of an atom.

Limitations of Rutherford Atomic Model

Rutherford’s experiment was unable to explain certain things. They are:

● Rutherford’s model was unable to explain the stability of an atom. According

to Rutherford’s postulate, electrons revolve at a very high speed around a
nucleus of an atom in a fixed orbit. However, Maxwell explained accelerated
charged particles release electromagnetic radiations. Therefore, electrons
revolving around the nucleus will release electromagnetic radiation.
● The electromagnetic radiation will have energy from the electronic motion as
a result of which the orbits will gradually shrink. Finally, the orbits will shrink
and collapse in the nucleus of an atom. According to the calculations, if
 Maxwell’s explanation is followed Rutherford’s model will collapse with 10-8
seconds. Therefore, Rutherford atomic model was not following Maxwell’s
theory and it was unable to explain an atom’s stability.
● Rutherford’s theory was incomplete because it did not mention anything
about the arrangement of electrons in the orbit. This was one of the major
drawbacks of Rutherford atomic model.

Conclusion
Even though the early atomic models were inaccurate and could not explain the
structure of atom and experimental results properly. But it formed the basis of
the quantum mechanics and helped the future development of quantum mechanics.

J.J. Thomson and the discovery of the electron

In the late 19th century, physicist J.J. Thomson began experimenting with cathode
ray tubes. Cathode ray tubes are sealed glass tubes from which most of the air has
been evacuated. A high voltage is applied across two electrodes at one end of the
tube, which causes a beam of particles to flow from the cathode (the negatively-
charged electrode) to the anode (the positively-charged electrode). The tubes are
called cathode ray tubes because the particle beam or "cathode ray" originates at
the cathode. The ray can be detected by painting a material know
as phosphors onto the far end of the tube beyond the anode. The phosphors spark,
or emit light, when impacted by the cathode ray.

A diagram of a cathode ray tube.

 A diagram of J.J. Thomson's cathode ray tube. The ray originates at the cathode
and passes through a slit in the anode. The cathode ray is deflected away from the
negatively-charged electric plate, and towards the positively-charged electric
plate. The amount by which the ray was deflected by a magnetic field helped
Thomson determine the mass-to-charge ratio of the particles. Image from
Openstax, CC BY 4.0.
To test the properties of the particles, Thomson placed two oppositely-charged
electric plates around the cathode ray. The cathode ray was deflected away from
the negatively-charged electric plate and towards the positively-charged plate. This
indicated that the cathode ray was composed of negatively-charged particles.
Thomson also placed two magnets on either side of the tube, and observed that this
magnetic field also deflected the cathode ray. The results of these experiments
helped Thomson determine the mass-to-charge ratio of the cathode ray particles,
which led to a fascinating discovery- the mass of each particle was much, much
smaller than that of any known atom. Thomson repeated his experiments using
different metals as electrode materials, and found that the properties of the cathode
ray remained constant no matter what cathode material they originated from. From
this evidence, Thomson made the following conclusions:
● The cathode ray is composed of negatively-charged particles.
● The particles must exist as part of the atom, since the mass of each particle is only
1/2000 end fraction the mass of a hydrogen atom.
● These subatomic particles can be found within atoms of all elements.
While controversial at first, Thomson's discoveries were gradually accepted by
scientists. Eventually, his cathode ray particles were given a more familiar
name: electrons. The discovery of the electron disproved the part of Dalton's
atomic theory that assumed atoms were indivisible. In order to account for the
existence of the electrons, an entirely new atomic model was needed.

The plum pudding model

Thomson knew that atoms had an overall neutral charge. Therefore, he reasoned
that there must be a source of positive charge within the atom to counterbalance
the negative charge on the electrons. This led Thomson to propose that atoms
could be described as negative particles floating within a soup of diffuse positive
charge. This model is often called the plum pudding model of the atom, due to the
fact that its description is very similar to plum pudding, a popular English dessert
(see image below).

Thomson Model of an atom

The description of Thomson’s atomic model is one of the many scientific models
of the atom. It was proposed by J.J Thomson in the year 1904 just after the
discovery of electrons. However, at that time the atomic nucleus was yet to be
discovered. So, he proposed a model on the basis of known properties available at
that time. The known properties are:

● Atoms are neutrally charged

● Negatively charged particles called electrons are present in an atom.

Thomson’s Atomic Model- Postulates

● According to the postulates of Thomson’s atomic model, an atom resembles a

sphere of positive charge with electrons (negatively charged particles) present
inside the sphere.
● The positive and negative charge is equal in magnitude and therefore an atom
has no charge as a whole and is electrically neutral.
● Thomson’s atomic model resembles a spherical plum pudding as well as a
watermelon. It resembles a plum pudding because the electrons in the model
look like the dry fruits embedded in a sphere of positive charge just like a
 spherical plum pudding. The model has also been compared to a watermelon
because the red edible part of a watermelon was compared to the sphere
having a positive charge and the black seeds filling the watermelon looked
similar to the electrons inside the sphere.

Limitations of Thomson’s Atomic Model

● Thomson’s atomic model failed to explain how the positive charge holds on
the electrons inside the atom. It also failed to explain an atom’s stability.
● The theory did not mention anything about the nucleus of an atom.
● It was unable to explain the scattering experiment of Rutherford.
 

Conclusion
Even though Thomson’s atomic model was inaccurate and had a few drawbacks, it
provided the base for several other atomic structure models afterward. It is one of
the foundation models that led to significant and revolutionary inventions later.

Bohr's Model of the Atom

The Rutherford model had a major drawback, it could not explain why
electrons do not fall into the nucleus by taking a spiral path. 
It was in concurrence with the electromagnetic theory that states "if a
charged particle undergoes accelerated motion, then it must radiate
energy (lose) continuously".
The objections of Rutherford atomic model was contested by Niels Bohr
atomic model in 1913. Niels Bohr proposed the quantum theory of an atom.
The theory was based on the quantum theory of radiation. Bohr retained
the main postulates of Rutherford planetary model and did some
medication on the basis of quantum physics. Hence, Bohr atomic model is
also known as Rutherford-Bohr atomic model.
He depicts the atom as a tiny, spherical body which consists nucleus at
center and negatively charged particles (electrons) revolving around
nucleus in a certain path known as orbit. He proposed some new postulate
with same basis concepts of Rutherford theory. 
Bohr's Atomic Model
In order to explain the stability of an atom, Neils Bohr gave a new
arrangement of electrons in the atom in 1913. According to Neils Bohr, the
electrons could revolve around the nucleus in only 'certain orbits' (energy
levels), each orbit having a different radius. 
When an electron is revolving in a particular orbit or particular energy level
around the nucleus, the electron does not radiate energy (lose energy)
even though it has accelerated motion around the nucleus.

Niels Bohr Atomic Theory

● An atom is made up of three particles, electrons, protons and

neutrons. Electrons have a negative charge and protons have a
positive charge whereas neutrons have no charge. They are neutral.
Due to the presence of equal number of negative electrons and
positive protons, the atom as a whole is electrically neutral.
● The protons and neutrons are located in a small nucleus at the center
of the atom. Due to the presence of protons, the nucleus is positively
charged.
● The electrons revolve rapidly around the nucleus in fixed circular
paths called energy levels or shells. The 'energy levels' or 'shells' or
'orbits' are represented in two ways: either by the numbers 1, 2, 3, 4,
5 and 6 or by letters K, L, M, N, O and P. The energy levels are
counted from center outwards.
● Each energy level is associated with a fixed amount of energy. The
shell nearest to the nucleus has minimum energy and the shell
farthest from the nucleus has maximum energy.
● There is no change in the energy of electrons as long as they keep
revolving with the same energy level. But, when an electron jumps
from a lower energy level to a higher one, some energy is absorbed
while some energy is emitted.
● When an electron jumps from a higher energy level to a lower one,
the amount of energy absorbed or emitted is given by the difference
of energies associated with the two levels. Thus, if an electron jumps
from orbit 1 (energy E1) to orbit 2 (energy E2), the change in energy is
given by E2 - E1. 
 ● The energy change is accompanied by absorption of radiation
energy of E = E2 E1 = hν where, h is a constant called 'Planck's
constant' and is the frequency of radiation absorbed or emitted. The
value of h is 6.626 x 10-34 J-s. The absorption and emission of light
due to electron jumps are measured by use of spectrometers.

This model of the atom was able to explain the stability of the atom. It also
explained the phenomenon of atomic spectra and ionization of gases.

Postulates of Niels Bohr Atomic Theory

The important postulates in his theory are,

1. Electrons revolve round the nucleus with definite velocities in

concentric circular orbits situated at definite distances from the
nucleus. The energy of an electron in a certain orbit remains
constant. As long as it remains in that orbit, it neither emits nor
absorbs energy. These are termed stationary states or main energy
states.
2. Bohr proposed that the angular momentum of an electron is
quantized. Thus, the motion of an electron is restricted to those orbits
where its angular momentum is an integral multiple of h/2π, where h is
Planck’s constant.
3. Thus we have the relationship mvr = n(h/2π), where m is mass of
electron, v is velocity of electron of said orbit, r is radius of that orbit,
n is a simple integer.
4. The stationary states or allowed energy levels are only those where n
= 1, 2, 3, this is called Bohr quantum condition.
5. The energy of an electron changes only when it moves from one orbit
to another. An electronic transition from an inner orbit to outer orbit
involves absorption of energy. Similarly, when an electron jumps from
an outer orbit to inner orbit it releases energy, which is equal to the
difference between the two energy levels.
6. The energy thus released in the form of a radiation of a certain
frequency appears in the form a line in the atomic spectrum. If the
energy of an electron in the outer orbit (n2) is E2 and energy of
electron in the inner orbit (n1) is E1 then E2 - E1 = ΔE = hν.
7. The value of n could be small integers 1, 2, 3 and these correspond
to the first, second, third, and so on. Quantum states are shells for
the electron; n is termed as principal quantum number.
 8. Based on the Bohr theory Bohr calculated the radii of the various
orbits and the energies associated with the electrons present in those
shells. 

Spectral Evidence for Quantization Bohr Theory

1. When electron jumps from lower energy level to higher energy level,
it absorbs relevant amount of energy and this results in the
absorption spectrum.
2. When an electron drops to higher level from lower level, it emits some
amount of energy and emission spectrum is observed.
3. Since there is only one electron in hydrogen atom, there should be
one line in hydrogen spectrum. But in Bohr theory, there are infinite
number of orbits, so more than one line is observed in spectrum.

Limitation of Bohr Model

1. Bohr model could not explain those atoms which have more than one
electron like lithium, helium. This model was applicable only for those
atoms which have one electron.
2. Bohr theory explained only spherical orbits. There was no explanation
for elliptical orbits.
3. This model failed to explain Zeeman Effect and stark effect.
4. Bohr model could not explain the uncertainty principle of Heisenberg.
5. Bohr model was not related with classification and periodicity of
elements.
6. By using Bohr atomic model, one can’t explain the intensity of
spectrum line.

Reference and Contributors

● Binod Shrestha (University of Lorraine)
● CK-12 Foundation by Sharon Bewick, Richard Parsons, Therese Forsythe, Shonna
Robinson, and Jean Dupon.
● https://www.toppr.com/guides/chemistry/structure-of-atom/rutherfords-model-of-an-
atom/
● https://www.khanacademy.org/science/chemistry/electronic-structure-of-atoms/history-
of-atomic-structure/a/discovery-of-the-electron-and-nucleus
● https://chemistry.tutorvista.com/inorganic-chemistry/bohr-s-model-of-the-atom.html
●