Kech 102
Kech 102
UNIT 2
STRUCTURE OF ATOM
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28 CHEMISTRY
(iii) In the absence of electrical or magnetic (ii) the mass of the particle — lighter the
field, these rays travel in straight lines particle, greater the deflection.
(Fig. 2.2). (iii) the strength of the electrical or magnetic
(iv) In the presence of electrical or magnetic field — the deflection of electrons from
field, the behaviour of cathode rays are its original path increases with the
similar to that expected from negatively increase in the voltage across the
charged particles, suggesting that the electrodes, or the strength of the
cathode rays consist of negatively magnetic field.
charged particles, called electrons. When only electric field is applied, the
(v) The characteristics of cathode rays electrons deviate from their path and hit the
(electrons) do not depend upon the cathode ray tube at point A. Similarly when
material of electrodes and the nature of only magnetic field is applied, electron strikes
the gas present in the cathode ray tube. the cathode ray tube at point C. By carefully
Thus, we can conclude that electrons are balancing the electrical and magnetic field
basic constituent of all the atoms. strength, it is possible to bring back the
electron to the path followed as in the absence
2.1.2 Charge to Mass Ratio of Electron
of electric or magnetic field and they hit the
In 1897, British physicist J.J. Thomson screen at point B. By carrying out accurate
measured the ratio of electrical charge (e) to measurements on the amount of deflections
the mass of electron (me ) by using cathode observed by the electrons on the electric field
ray tube and applying electrical and magnetic strength or magnetic field strength, Thomson
field perpendicular to each other as well as to
was able to determine the value of e/me as:
the path of electrons (Fig. 2.2). Thomson
argued that the amount of deviation of the e
me = 1.758820 × 10 C kg (2.1)
11 –1
particles from their path in the presence of
electrical or magnetic field depends upon:
Where me is the mass of the electron in kg
(i) the magnitude of the negative charge on
and e is the magnitude of the charge on the
the particle, greater the magnitude of the
charge on the particle, greater is the electron in coulomb (C). Since electrons
interaction with the electric or magnetic are negatively charged, the charge on electron
field and thus greater is the deflection. is –e.
Fig. 2.2 The apparatus to deter mine the charge to the mass ratio of electron
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concluded that α- particles are helium represented in Fig. 2.5. A stream of high
nuclei as when α- particles combined energy α–particles from a radioactive source
with two electrons yielded helium gas. was directed at a thin foil (thickness ∼ 100
β-rays are negatively charged particles nm) of gold metal. The thin gold foil had a
similar to electrons. The γ-rays are high circular fluorescent zinc sulphide screen
energy radiations like X-rays, are neutral around it. Whenever α–particles struck the
in nature and do not consist of particles. screen, a tiny flash of light was produced at
As regards penetrating power, α-particles that point.
are the least, followed by β-rays (100 The results of scattering experiment were
times that of α–particles) and γ-rays quite unexpected. According to Thomson
(1000 times of that α-particles). model of atom, the mass of each gold atom in
the foil should have been spread evenly over
2.2.2 Rutherford’s Nuclear Model of Atom the entire atom, and α– particles had enough
energy to pass directly through such a
Rutherford and his students (Hans Geiger and uniform distribution of mass. It was expected
Ernest Marsden) bombarded very thin gold that the particles would slow down and
foil with α–particles. Rutherford’s famous change directions only by a small angles as
α –particle scattering experiment is
they passed through the foil. It was observed
that :
(i) most of the α– particles passed through
the gold foil undeflected.
(ii) a small fraction of the α–particles was
deflected by small angles.
(iii) a very few α– particles (∼1 in 20,000)
bounced back, that is, were deflected by
nearly 180°.
A. Rutherford’s scattering experiment On the basis of the observations,
Rutherford drew the following conclusions
regarding the structure of atom :
(i) Most of the space in the atom is empty
as most of the α–particles passed
through the foil undeflected.
(ii) A few positively charged α– particles were
deflected. The deflection must be due to
enormous repulsive force showing that
the positive charge of the atom is not
spread throughout the atom as Thomson
had presumed. The positive charge has
to be concentrated in a very small volume
that repelled and deflected the positively
charged α– particles.
B. Schematic molecular view of the gold foil
(iii) Calculations by Rutherford showed that
Fig.2.5 Schematic view of Rutherford’s scattering the volume occupied by the nucleus is
experiment. When a beam of alpha (α) negligibly small as compared to the total
particles is “shot” at a thin gold foil, most volume of the atom. The radius of the
of them pass through without much effect. atom is about 10–10 m, while that of
Some, however, are deflected. nucleus is 10–15 m. One can appreciate
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this difference in size by realising that if earlier protons and neutrons present in the
a cricket ball represents a nucleus, then nucleus are collectively known as nucleons.
the radius of atom would be about 5 km. The total number of nucleons is termed as
On the basis of above observations and mass number (A) of the atom.
conclusions, Rutherfor d proposed the mass number (A) = number of protons (Z)
nuclear model of atom (after the discovery of + number of
protons). According to this model : neutrons (n) (2.4)
(i) The positive charge and most of the mass 2.2.4 Isobars and Isotopes
of the atom was densely concentrated The composition of any atom can be
in extremely small region. This very small represented by using the normal element
portion of the atom was called nucleus symbol (X) with super-script on the left hand
by Rutherford. side as the atomic mass number (A) and
(ii) The nucleus is surrounded by electrons subscript (Z) on the left hand side as the
that move around the nucleus with a atomic number (i.e., AZ X).
very high speed in circular paths called Isobars are the atoms with same mass
orbits. Thus, Rutherford’s model of atom number but different atomic number for
14 14
resembles the solar system in which the example, 6 C and 7 N. On the other hand,
nucleus plays the role of sun and the atoms with identical atomic number but
electrons that of revolving planets. different atomic mass number are known as
Isotopes. In other words (according to
(iii) Electrons and the nucleus are held
equation 2.4), it is evident that difference
together by electrostatic forces of
between the isotopes is due to the presence
attraction.
of different number of neutrons present in
2.2.3 Atomic Number and Mass Number the nucleus. For example, considering of
The presence of positive charge on the hydrogen atom again, 99.985% of hydrogen
nucleus is due to the protons in the nucleus. atoms contain only one proton. This isotope
1
As established earlier, the charge on the is called protium( 1H). Rest of the percentage
proton is equal but opposite to that of of hydrogen atom contains two other isotopes,
electron. The number of protons present in the one containing 1 proton and 1 neutron
2
the nucleus is equal to atomic number (Z ). is called deuterium ( 1 D, 0.015%) and the
For example, the number of protons in the other one possessing 1 proton and 2 neutrons
3
hydrogen nucleus is 1, in sodium atom it is is called tritium ( 1 T ). The latter isotope is
11, therefore their atomic numbers are 1 and found in trace amounts on the earth. Other
11 respectively. In order to keep the electrical examples of commonly occuring isotopes are:
neutrality, the number of electrons in an carbon atoms containing 6, 7 and 8 neutrons
atom is equal to the number of protons besides 6 protons ( 12 13 14
6 C, 6 C, 6 C ); chlorine
(atomic number, Z ). For example, number of atoms containing 18 and 20 neutrons besides
electrons in hydrogen atom and sodium atom 17 protons ( 17
35 37
Cl, 17 Cl ).
are 1 and 11 respectively. Lastly an important point to mention
Atomic number (Z) = number of protons in regarding isotopes is that chemical properties
the nucleus of an atom of atoms are controlled by the number of
electrons, which are determined by the
= number of electrons number of protons in the nucleus. Number of
in a nuetral atom (2.3) neutrons present in the nucleus have very
While the positive charge of the nucleus little effect on the chemical properties of an
is due to protons, the mass of the nucleus, element. Therefore, all the isotopes of a given
due to protons and neutrons. As discussed element show same chemical behaviour.
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STRUCTURE OF ATOM 33
Problem 2.1 playing the role of the massive sun and the
electrons being similar to the lighter planets.
Calculate the number of protons, Further, the coulomb force (kq1q2/r2 where q1
neutrons and electrons in 80 35 Br
. and q2 are the charges, r is the distance of
Solution separation of the charges and k is the
In this case, 80
35 Br , Z = 35, A = 80, species proportionality constant) between electron and
is neutral the nucleus is mathematically similar to the
Number of protons = number of electrons m1m 2
= Z = 35 gravitational force G. 2 where m1 and
r
Number of neutrons = 80 – 35 = 45, m 2 are the masses, r is the distance of
(equation 2.4) separation of the masses and G is the
gravitational constant. When classical
Problem 2.2
mechanics* is applied to the solar system,
The number of electrons, protons and it shows that the planets describe well-defined
neutrons in a species are equal to 18, orbits around the sun. The theory can also
16 and 16 respectively. Assign the proper calculate precisely the planetary orbits and
symbol to the species. these are in agreement with the experimental
Solution measurements. The similarity between the
The atomic number is equal to solar system and nuclear model suggests
number of protons = 16. The element is that electrons should move around the nucleus
sulphur (S). in well defined orbits. However, when a body
is moving in an orbit, it undergoes acceleration
Atomic mass number = number of
protons + number of neutrons (even if the body is moving with a constant
speed in an orbit, it must accelerate because
= 16 + 16 = 32 of changing direction). So an electron in the
Species is not neutral as the number of nuclear model describing planet like orbits is
protons is not equal to electrons. It is under acceleration. According to the
anion (negatively charged) with charge electromagnetic theory of Maxwell, charged
equal to excess electrons = 18 – 16 = 2. particles when accelerated should emit
32 2–
Symbol is 16 S . electromagnetic radiation (This feature does
Note : Before using the notation X , findA
Z
not exist for planets since they are uncharged).
out whether the species is a neutral Therefore, an electron in an orbit will emit
atom, a cation or an anion. If it is a radiation, the energy carried by radiation
neutral atom, equation (2.3) is valid, i.e., comes from electronic motion. The orbit will
number of protons = number of electrons thus continue to shrink. Calculations show
= atomic number. If the species is an ion, that it should take an electron only 10–8 s to
deter mine whether the number of spiral into the nucleus. But this does not
protons are larger (cation, positive ion) happen. Thus, the Rutherford model
or smaller (anion, negative ion) than the cannot explain the stability of an atom.
number of electrons. Number of neutrons If the motion of an electron is described on the
basis of the classical mechanics and
is always given by A–Z, whether the
electromagnetic theory, you may ask that
species is neutral or ion.
since the motion of electrons in orbits is
leading to the instability of the atom, then
2.2.5 Drawbacks of Rutherford Model
why not consider electrons as stationary
Rutherford nuclear model of an atom is like a around the nucleus. If the electrons were
small scale solar system with the nucleus stationary, electrostatic attraction between
* Classical mechanics is a theoretical science based on Newton’s laws of motion. It specifies the laws of motion of macroscopic
objects.
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the dense nucleus and the electrons would 19th century when wave nature of light was
pull the electrons toward the nucleus to form established.
a miniature version of Thomson’s model of Maxwell was again the first to reveal that
atom. light waves are associated with oscillating
Another serious drawback of the electric and magnetic character (Fig. 2.6).
Rutherford model is that it says nothing Although electromagnetic wave motion is
about the electronic structure of atoms i.e., complex in nature, we will consider here only
how the electrons are distributed around the a few simple properties.
nucleus and what are the energies of these (i) The oscillating electric and magnetic
electrons. fields produced by oscillating charged
2.3 DEVELOPMENTS LEADING TO THE particles are perpendicular to each other
BOHR’S MODEL OF ATOM and both are perpendicular to the
direction of propagation of the wave.
Historically, results observed from the studies
Simplified picture of electromagnetic
of interactions of radiations with matter have
wave is shown in Fig. 2.6.
provided immense information regarding the
structure of atoms and molecules. Neils Bohr
utilised these results to improve upon the
model proposed by Rutherf o rd. Two
developments played a major role in the
formulation of Bohr’s model of atom. These
were:
(i) Dual character of the electromagnetic
radiation which means that radiations
possess both wave like and particle like
properties, and
(ii) Experimental results regarding atomic
spectra which can be explained only by Fig.2.6 The electric and magnetic field
assuming quantized (Section 2.4) components of an electromagnetic wave.
These components have the same
electronic energy levels in atoms.
wavelength, fr equency, speed and
2.3.1 Wave Nature of Electromagnetic amplitude, but they vibrate in two
Radiation mutually perpendicular planes.
James Maxwell (1870) was the first to give a (ii) Unlike sound waves or water waves,
comprehensive explanation about the electromagnetic waves do not require
interaction between the charged bodies and medium and can move in vacuum.
the behaviour of electrical and magnetic fields (iii) It is now well established that there are
on macroscopic level. He suggested that when many types of electromagnetic
electrically charged particle moves under radiations, which differ from one another
accelaration, alternating electrical and in wavelength (or frequency). These
magnetic fields are produced and constitute what is called
transmitted. These fields are transmitted in electromagnetic spectrum (Fig. 2.7).
the forms of waves called electromagnetic Different regions of the spectrum are
waves or electromagnetic radiation. identified by different names. Some
Light is the form of radiation known from examples are: radio frequency region
early days and speculation about its nature around 106 Hz, used for broadcasting;
dates back to remote ancient times. In earlier microwave region around 1010 Hz used
days (Newton) light was supposed to be made for radar; infrared region around 1013 Hz
of particles (corpuscules). It was only in the used for heating; ultraviolet region
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around 1016Hz a component of sun’s at the same speed, i.e., 3.0 × 10 8 m s–1
radiation. The small portion around 1015 (2.997925 × 108 m s –1, to be precise). This is
Hz, is what is ordinarily called visible called speed of light and is given the symbol
light. It is only this part which our eyes ‘c‘. The frequency (ν ), wavelength (λ) and velocity
can see (or detect). Special instruments of light (c) are related by the equation (2.5).
a re required to detect non-visible c=ν λ (2.5)
radiation.
The other commonly used quantity
(iv) Different kinds of units are used to specially in spectroscopy, is the wavenumber
represent electromagnetic radiation.
(ν ). It is defined as the number of wavelengths
These radiations are characterised by the
properties, namely, frequency ( ν ) and per unit length. Its units are reciprocal of
wavelength unit, i.e., m–1. However commonly
wavelength (λ).
used unit is cm–1 (not SI unit).
The SI unit for frequency (ν ) is hertz
(Hz, s–1), after Heinrich Hertz. It is defined as Problem 2.3
the number of waves that pass a given point The Vividh Bharati station of All India
in one second. Radio, Delhi, broadcasts on a frequency
Wavelength should have the units of of 1,368 kHz (kilo hertz). Calculate the
length and as you know that the SI units of wavelength of the electromagnetic
length is meter (m). Since electromagnetic radiation emitted by transmitter. Which
radiation consists of different kinds of waves part of the electromagnetic spectrum
of much smaller wavelengths, smaller units does it belong to?
are used. Fig.2.7 shows various types of
Solution
electro-magnetic radiations which differ from
The wavelength, λ, is equal to c/ν , where
one another in wavelengths and frequencies.
c is the speed of electromagnetic
In vaccum all types of electromagnetic radiation in vacuum and ν is the
radiations, regardless of wavelength, travel
ν
(a)
(b)
Fig. 2.7 (a) The spectrum of electromagnetic radiation. (b) Visible spectrum. The visible region is only
a small part of the entire spectrum .
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