Professor CHEMISTRY - XI (Subjective) 185

Chapter
ATOMIC STRUCTURE
5
5.1 SUB-ATOMIC PARTICLES OF ATOM
We are familiar with the nature of matter, which is made up of extremely small particles called atoms.
According to Dalton's theory, atoms were considered to be ultimate particles which could not be divided any
further. Our ideas about structure of atom have undergone radical changes over the years. A number of
subatomic particles have been discovered. The experiments which led to the discovery of electron, proton and
neutron are described below.
5.1.1 Discovery of Electron (Cathode Rays) (L.Q)
(LHR-2005,08, FSD-2006, GUJ-2006)
A gas discharge tube is fitted with two metallic electrodes
acting as cathode and anode. The tube is filled with a gas, air or
vapours of a substance at any desired pressure. The electrodes are
connected to a source of high voltage. The exact voltage required
depends upon the length of the tube and the pressure inside the
tube. The tube is attached to a vacuum pump by means of a small
side tube so that the conduction of electricity may be studied at any
value of low pressure Fig (5.1).
It is observed that current does not flow through the gas at
ordinary pressure even at high voltage of 5000 volts. When the
pressure inside the tube is reduced and a high voltage of 5000-10000 volts is applied, then an electric discharge
takes place through the gas producing a uniform glow inside the tube. When the pressure is reduced further to
about 0.01 torr, the original glow disappeares. Some rays are produced which create fluorescence on the glass
wall opposite to the cathode. These rays are called cathode rays. The colour of the glow or the fluorescence
produced on the walls of the glass tube, depends upon the composition of glass.
5.1.2 Properties of Cathode Rays (L.Q)
BHR-2014, MLT-2014, LHR-2015, FSD-2012)
To study the properties of cathode rays systematic investigations were made by many scientists. They
established the following properties of cathode rays.
1. Cathode rays are negatively charged. In 1895, J Perrin
showed that when the cathode rays passed between the
poles of the magnet, the path of the negatively charged
particles was curved downward to point 2 by the magnetic
field. Fig (5.2)
In 1897, J. Thomson established their electric charge by
the application of electric field, the cathode ray particles
were deflected upwards (towards the positive deflection
plate) to point 3. Fig. (5.2)
Thomson found that by carefully controlling the charge on
the plates when the plates and the magnet were both
around the tube, he could make the cathode rays strike the
tube at point 1 again Fig.(5.2). In other words, he was able
to cancel the effect of the magnetic field by applying an electric field that tended to bend the path of the
cathode rays in the opposite direction.
2. They produce a greenish fluorescence on striking the walls
186 Chapter # 5 (Atomic Structure)
of the glass tube. These rays also produce fluorescence in rare earths and minerals. When placed in the
path of these rays, alumina glows red and tin stone yellow.
S.Q How will you prove that cathode rays travel in a straight line? (BHR-2017)
3. Cathode rays cast a shadow when an opaque object is placed in their path. This proves that they travel
in a straight line perpendicular to the surface of cathode Fig (5.3).

4. These rays can drive a small paddle wheel placed in their path.
This shows that these rays possess momentum. From this
 S.Q. Cathode rays are
material particles? (D.G.K-
observation, it is inferred that cathode rays are not rays but 2014,16,17, MLT-2009,16,
material particles having a definite mass and velocity Fig LHR-2007,16, GUJ-
(5.4). 2008,15)

5. Cathode rays can produce X-rays when they strike an anode particularly with High voltage large
atomic mass Fig (5.18).
6. Cathode rays can produce heat they fall on matter e.g. when cathode rays from a concave cathode are
focused on a platinum foil, it begins to glow.
7. Cathode rays can ionize gases.
8. They can cause a chemical change, because they have a reducing effect.
9. Cathode rays can pass through a thin metal foil like aluminum or gold foil.
10. The e/m value of cathode rays shows that they are simply electrons.
J.J. Thomson concluded from his experiments that cathode rays consist of streams of negatively charged
particles. Stoney named these particles as electrons. Thomson also determined the charge to mass ratio (e/m)
of electrons. He found that the e/m value remained the same no matter which gas was used in the discharge
tube. He concluded that all atoms contained electrons.
S.Q Narrate four properties of cathode rays. (MLT-2017, RWP-2016, LHR-2014, 17)
Ans. 1. Cathode rays produce heat when they fall on matter.
2. These ray can ionize gases.
3. They can cause a chemical change, because they have reducing effect.
4. Cathode rays can pass throw a thin metal foil.
S.Q1 Why e/m value of the cathode rays is just equal to that of electron? (RWP-20017, DGK-2012,
SRG-2009, FSD-2007)
Ans. Cathode ray is composed of extremely small negatively charged particles which are infect electrons.
Professor CHEMISTRY - XI (Subjective) 187
Therefore the value of e/m of electrons and cathode ray are just equal to each other.
S.Q2 Why cathode rays have reducing effect (or can cause chemical change)? (D.G. Khan-2010: MLT-
2011)
Ans. The cathode rays are negatively charged. So, their addition causes reduction of a substance. Thus, these
can cause a chemical change.
S.Q3 What is cathode ray tube? (FSD-2017: MLT-2017)
• It is a glass tube having two metallic electrodes sealed into it.
• It may contain a gas, air or vapours of any substance at any pressure.
• The tube can be connected to a vacuum pump to maintain any low pressure.
• The electrodes are connected to a high voltage battery. The exact voltage required depends upon
the length of the tube and the pressure inside it.
• A slit can be used in it to get a sharp beam of radiations.
S.Q4 How will you prove that cathode rays travel in a straight line? (BHR-2017; FSD- 2017)
Ans. In 1869. Hittorf showed that Cathode rays travel in a straight line.
He found that cathode rays produce a sharp shadow of an opaque object placed in their path. It shows
that these rays travel in a straight line, perpendicular to the surface of cathode.
S.Q5 Which observations tell the presence of cathode rays in the discharge tube? (FSD-2008)
Ans. Cathode rays produced in the discharge tube fall upon the surface of the glass tube just opposite to the.
cathode surface giving fluorescence. Fluorescence has different colours which depends upon the nature
of the glass tube.
S.Q6 Why the cathode rays are produced in the discharge tube by applying a high voltage?
Ans. When the voltage of 5000 - 10000 volts is applied at the pressure of around 0.01 torr, then a glow
appears and cathode rays travel from cathode towards the anode in the discharge tube. High voltage is
necessary to break the molecules of the gas into atoms and to remove the electrons from outermost orbitals.
S.Q7 How various experiments conducted in the cathode ray tube show that cathode rays are material
particles with the negative charge on them? (LHR-07, GRW-08, B.P-2008, FSD-2009, MLT-2009)
Ans. Cathode rays rotate a pin wheel. The vans of the pin wheel get the momentum from the particles of the
cathode rays and get the movement. When these rays are passed through the electrical field, they are
deflected the positive plate.
S.Q8 Why is it necessary to decrease the pressure in the discharge tube to get the cathode rays? (FSD-
2007, SRG-2010, GRW-2012, LHR-2012)
Ans. The pressure in discharged tube is decreased to allow the cathode rays and anode rays to move freely
from one electrode to the other. In this way the possibility of collisions between rays and the gas
molecules, are minimized.
S.Q9 Whichever gas is used in the discharge tube, the nature of the cathode rays remains the same.
Why? (LHR-2009, D.G. Khan- 2011, D. G. Khan -2012)
Ans. All the gases are consisted of atoms or molecules. They have electrons in outermost orbitals. These
electrons are detached by the high voltage and due to collisions, these electrons become free. They are
repelled by the cathode and attracted towards the anode. That is why, they are called cathode rays. They
are always electrons and nothing else.
MCQs
1. The negative charge on the cathode rays was discovered by (LHR-2005, GUJ-2009)
(a) J.J. Thomson (b) Rutherford (c) E.Goldstein (d) Chadwick
188 Chapter # 5 (Atomic Structure)
2. Negative charge on cathode rays was established by: (GRW-2009)
(a) William Crook (b)J Perin (c) J.J. Thomson (d) Hittrof
3. The e/m value for positive, rays is maximum for: (GRW-2009: BHR-2015)
(a) hydrogen (b) helim (c) oxygen (d) nitrogen
4. Cathode rays cause a chemical change because they have effect. (RWP-2013)
(a) Oxidizing (B) Conducting (c)  Reducing (d) Diffusing.
5.1.3 Discovery of Proton (Positive Rays) (L.Q)
(LHR-2003, BHR-2005,07,08, RWP-2005,GUJ-2014,15, MLT-2008, SRG-2010,
In 1886, German physicist, E. Goldstein took a discharge tube provided with a cathode having
extremely fine holes in it. When a large potential difference is applied between electrodes, it is observed that
while cathode rays are travelling away from cathode, there are other rays produced at the same time. These rays
after passing through the perforated cathode produce a glow
on the wall opposite to the anode. Since these rays pass
through the canals or the holes of cathode, they are called
canal rays. These rays are named as positive rays owing to the
fact that they carry positive charge Fig (5.5).
Reason for the Production of Positive Rays (LHR-2013,
D.G.K-2014, 15, AZK-2008)
These positive rays are produced, when high speed cathode
rays (electrons) strike the molecules of a gas enclosed in the
discharge tube. They knock out electrons from the gas
molecules and positive ions are produced, which start moving towards the cathode Fig (5.5).
M + e–  M+ + 2e–
5.1.4 Properties of Positive Rays
1. They are deflected by an electric as well as a magnetic field showing, that these are positively charged.
2. These rays travel in a straight line in a direction opposite to the cathode rays.
3. They produce flashes on ZnS plate.
4. The e/m value for the positive rays is always smaller than that of electrons and depends upon the nature
of the gas used in the discharge tube. Heavier the gas, smaller the e/m value. When hydrogen gas is used in
the discharge tube, the e/m value is found to be the maximum in comparison to any other gas because the value
of 'm' is the lowest for the positive particle obtained from the hydrogen gas. Hence the positive particle obtained
from hydrogen gas is the lightest among all the positive particles. This particle is called proton, a name
suggested by Rutherford.
The mass of a proton is 1836 times more than that of an electron.
S.Q10 The e/m value of positive rays obtained from hydrogen gas is 1836 times less than that of cathode
rays, Justify it. (FSD-2010, GRW-2007, 11, LHR-2007)
Ans. The hydrogen atom contains only two fundamental particles i.e., one proton and one electron. When
hydrogen gas is used in the discharge tube, the positive rays particles are just protons and cathode rays
particles are electrons, Since, a proton is 1836 times heavier than an electron, therefore e/m value for
positive rays obtained from hydrogen is 1836 times lesser than that of cathode rays.
S.Q11 Why the properties of positive rays depend upon the nature of the gas? (RWP-2007)
Ans. As positive rays are formed by ionization of gas molecules inside the discharge tube, every gas has
different nature of positive ion produced. Therefore e/m of positive rays depends upon nature of gas.
Lighter the gas, greater the value of e/m.
S.Q12 Which observation tells the presence of positive rays in discharge tube? (LHR-2007, DGK-2008,
FSD-2008)
Ans. When a porous cathode is used in discharge tube then a glow produced on the wall opposite to cathode
Professor CHEMISTRY - XI (Subjective) 189
rays and also have opposite charge therefore these are called positive rays.
S.Q13 Write properties of positive rays. (GRW-2011: LHR-2013. FSD-2016: D.G. Khan-2017)
(i) These rays travel in a straight line in a direction opposite to the cathode rays.
(ii) They produce flashes on striking ZnS plate.
(iii) These rays are deflected in an electric and magnetic field in a way that shows their positive charge.
(iv) The charge to mass ratio depends upon nature of gas.
S.Q14 Why the positive rays are also called canal rays? Give its reason. (MLT-2007, SRG-2010, GRW-
2010, M. Pure- 2012, GRW-2012)
Ans. They are detected by allowing pass through the canals of cathode. These canals are the holes in the
cathode material.
S.Q15 The e/m values of positive rays for different gases are different, but those for cathode rays the e/m
values are same. Justify it. (Rwp-2008, LHR- 2010, Rwp-2011, MLT-2012)
Ans. The nature of particles of positive rays in a discharge tube depend upon the nature of the gas because the
nucleus of every gas has its own number of protons and neutrons. Greater the number of protons and
neutrons in the nucleus of an atom or nuclei of the molecule, smaller the e/m values.
In the case of cathode rays which are always electrons, e/m values remain the same.
S.Q16 The e/m value of the positive rays obtained from the hydrogen gas is 1836 times less than that of
cathode rays. Justify it. (LHR-2007, FSD-2010, GRW-2011, MTN-2012)
Ans. When we use hydrogen gas in the discharge tube, the positive rays are consisted of single protons. The
proton is 1836 times heavier than that of electron. So its e/m value is 1836 times smaller.
S.Q17 Why the anode rays depend upon the nature of the gas? (FSD-2004)
Ans. Anode rays are those particles which are consisted of rest of the atom or molecule after the removal of
one electron. The mass of every anode ray particle depends upon the nature of the gas, so the anode rays
for all gaseous substances are different.
MCQs
1. A proton is identical with (BHR-2005)
(a) ionized hydrogen molecule (b) ionized hydrogen atom
(c) -particle (d) hydronium ion
2. The mass of proton in kg is (MLT-2008)
(a) 9.110–10 kg (b) 6.110–18 kg (c) 1.672610–27 kg (d) 3.110–31 kg
3. The e/m value for the +ve rays is maximum for (SRG-2005, MLT-2007, LHR-2008, GUJ-2009)
(a) Hydrogen (b) Helium (c) Oxygen (d) Nitrogen
4. Positive rays were discovered by:(MTN-2011, AJK-2017).
(a) J.J. Thomson (b) Rutherford (c) William Crooks (d) Eugene Gold Stein
5. The positive particle produced in the discharge tube from Hydrogen gas was named Proton by:
(MTN-2013)
(a) Millikan (b) Goldstein (c) Rutherford (d) Chadwick
6. The nature of anode rays (or positive rays) depend on (RWP-09: SHW-14, MLT-16, RWP-2017).
(a) The nature of the electrode (b) The nature of the residual gas
(c) The nature of the discharge tube (d) All of above
5.1.5 Discovery of Neutron (L.Q)
BHR-2004, 07, MLT-2006, RWP-2007, GUJ-2011,14, FSD-2014, D.G.K-2010, MLT-2012,17)
Proton and electron were discovered in 1886 and their properties were completely determined till
1895. It is very strange to know that upto 1932 it was thought that an atom was composed of only electrons and
protons. Rutherford predicted in 1920 that some kind of neutral particle having mass equal to that of proton
190 Chapter # 5 (Atomic Structure)
must be present in an atom, because he noticed that atomic masses of atoms could not be explained,if it were
supposed that atoms had only electrons and protons.
Chadwick discovered neutron in 1932 and was awarded Nobel prize in Physics in 1935.
Experiment
A stream of a-particles produced from a polonium source was directed at beryllium ('Be) target. It was
noticed that some penetrating radiation were produced. These radiations were called neutrons because the
charge detector showed them to be neutral Fig (5.6). The nuclear reaction is as follows.
4He + 9Be  12C + 1n
(-particle)

Actually a-particles and the nuclei of Be are re-arranged and extra neutron is emitted.
5.1.6 Properties of Neutron
1. Free neutron decays into a proton (1P) with the emission of an electron (0e) and a
neutrino (0n).
1n  1P + 0e + 0n
2. Neutrons cannot ionize gases.
3. Neutrons are highly penetrating particles.
4. They can expel high speed protons from paraffin, water, paper and cellulose.
5. When neutrons travel with an energy 1.2 Mev, they are called fast neutrons but with energy below 1ev
are called slow neutrons. Slow neutrons are usually more effective than fast ones for the fission
purposes.
6. When neutrons are used as projectiles, they can carry out the nuclear reactions. A fast neutron ejects an
-particle from the nucleus of nitrogen atom and boron is produced, alongwith and -particles.
N + 1n  B + He
7. When slow moving neutrons hit the Cu metal then y radiations are emitted. The radioactive Cu is
converted into Zn
Cu + 1n  Cu + hv ( -radiations)
Cu  Zn + e
Actually, neutron is captured by the nucleus of Cu and Cu is produced. This radio active Cu emits an
electron ((-particle) and its atomic number increases by one unit. Because of their intense biological effects
they are being used in the treatment of cancer.
S.Q18 Why the neutrons are used as projectiles?
Ans. "The particles, which hit the nucleus and can change its nature called projectiles". A projectile must be
charge less, otherwise be captured or repelled by the nucleus. As the neutron has no therefore, it is used
as projectile.
S.Q19 What happens when paraffin wax is bombarded with neutron?
Professor CHEMISTRY - XI (Subjective) 191
Ans. Paraffin wax is a hydrocarbon, when neutrons strike w hydrocarbon; it knocks out the smaller entities
like 'H' by 1 C – H bonds. So in this encounter (attack), protons will be ejected out with high speed.
S.Q20 Write two equations of nuclear reactions. (BHR—2007, FSD-2011,13)
Ans. (i) 4He + 9Be  12C + 1n
(ii) 14N + 1n  11B + 4He
S.Q21 Complete: (a) 4He + 9Be  (b) 14He + 1n  (FSD-2011)
Ans. (a) 4He + 9Be  12C + 1n
(b) 14He + 1n  11B + 4He
S.Q22 Write down nuclear reactions involved in the, conversion of Cu into Zn. (GRW-2014: FSD-2016.
(D.G. Khan-2017: RWP-2017)
OR
How the emission of a -particle results in the increase of atomic number of an element? (RWP-2013)
Ans. Slow moving neutrons produce - radiations on striking Cu metal. In this process radioactive 66Cu is
converted into 66Zn. Firstly, neutron is captured by the nucleus of 65Cu and 66Cu is produced. This
radioactive 66Cu emits an electron (-particle) and its atopmic number is increased by one unit.
1n + 65Cu  66Cu + hv (-radiations)
66Cu  66Zn + 0e
S.Q23 How neutrons are used in the treatment of cancer?' (BHR-2012)
Ans. Neutrons are used in the treatment of cancer due to their high biological activity. In these treatment fast
neutrons with energy, 60 – 70 MeV are used. The neutron destroys cancerous cells by direct effect on
nuclear structures.
S.Q24 Differentiate between slow and fast neutron (RWP-2017: GRW-2017)
Ans. i. Neutrons travelling with 1.2 MeV energy are called fast neutrons
ii. Neutrons travelling with energy less than 1eV are called slow neutrons.
iii. Slow neutrons are more effective than fast ones for the nuclear fission process.
S.Q25 What particles are formed by the decay of free neutrons? (Rwp-2005, FSD-2008, Rwp-2008,
MTN-2008, B.P. 2008, SRG-2009, SRG-2015,07,13, BHW-2017, MTN-2015, LHR-2014,17)
Ans. A free neutron decays into proton, electron and a neutrino.
1
n0  P + e + 0n
neutron proton electron neutrino
S.Q26 How the slow neutrons prove to be more effective than the fast neutrons? (Mirpure-2004,
MTN-2008, B.P-2008)
Ans. When the travelling neutrons have energy below one electron volt then they are called slow neutrons.
They are more effective in fission processes. Slow neutrons hit the copper metal and y-radiations are
emitted, giving us a new isotope of copper.
1
0n + 65Cu 66Cu + hv (radiations)
66Cu  66Zn + 1e0
S.Q. Give any two properties of neutrons.
(a) Neutrons can not ionize a gas.
(b) They are highly penetrating particles.
MCQs
1. Which of the followings has the same No. of electrons as -particles? (MLT-2005)
(a) Li+ (b) H+ (c) He+ (d) Be+2
192 Chapter # 5 (Atomic Structure)
2. He number of neutrons present on 19K39 is (FSD-2011)
(a) 39 (b) 18 (c) 20 (d) 19
3. The number of neutron present in (2011)
(a) 39 (b) 18 (c) 20 (d) 19
4. Neutron was discovered by (LHR-201 l, SRG-2014)
(a)  Chadwick (b) C.D Andersen (c) Rutherford (d) Goldstein.
5.1.7 Measurement of Value of Electron (L.Q)
(LHR-13,14,16,SRG-05,MLT-05,MLT-07,FSD-
2007,08, D.G.K-2014, SHW-2016, BHR-2015,16)
In 1897, J.J Thomson devised an instrument to
measure the e/m value of electron. The apparatus consists of
a discharge tube shown in Fig. (5.7). The cathode rays are
allowed to pass through electric and magnetic fields. When
both the fields are off then a beam of cathode rays,
consisted of electrons, produces bright luminous spot at P1
on the fluorescent screen. The north and south poles of
magnetic field are perpendicular to the plane of paper in the
diagram. The electrical field is in the plane of paper. When
only magnetic field is applied, the cathode rays are deflected in a circular path and fall at the point P3. When
only electric field is applied, the cathode rays produce a spot at P2. Both electric and magnetic fields are then
applied simultaneously and their strengths adjusted in such a way that cathode rays again hit the point P1.
In this way by comparing the strengths of the two fields one can determine the e/m value of electrons. It
comes out to be 1.7588  1011 coulombs kg–1. This means that
1 kg of electrons have 1.7588  1011 coulombs of charge.
5.1.8 Measurement of Charge on Electron - Millikan's
Oil Drop Method (L.Q)
LHR-2014, 15, 16, SHW-2015, BHR-2015, FSD-2007,
MLT-2007, SRG-2005)
In 1909, Millikan determined the charge on electron by
a simple arrangement. The apparatus consists of a metallic
chamber. It has two parts. The chamber is filled with air, the
pressure of which can be adjusted by a vacuum pump. There are
two electrodes A and A'. These electrodes are used to generate
an electrical field in the space between the electrodes. The upper electrode has a hole in it as shown in Fig (5.8).
A fine spray of oil droplets is created by an atomizer. A few droplets passes through the hole in the top
plate and into the region between the charged plates, where one of them is observed though a microscope. This
droplet; when illuminated perpendicularly to the direction of view, appears in the microscope as a bright speck
against a dark background. The droplet falls under the force of gravity without applying the electric field. The
velocity of the droplet is determined. The velocity of the droplet (V1) depends upon its weight, mg.
V1  mg ….. (1)
where 'm' is the mass of the droplet and 'g' is the acceleration due to gravity. After that the air between the
electrodes is ionized by X-rays. The droplet under observation takes up an electron and gets charged. Now,
connect A and A to a battery which generates an electric field having a strength, E. The droplet moves upwards
against the action of gravity with a velocity (v2).
V2  Ee-mg ….. (2)
where 'e' is the charge on the electron and Ee is the upward driving force on the droplet due to applied electrical
field of strength E.
Dividing equation (1) by (2)
= ….. (3)
Professor CHEMISTRY - XI (Subjective) 193
The values of and V2 are recorded with the help of microscope. The factors like g and E are also known. Mass
of the droplet can be determined by varying the electric field in such a way that the droplet is suspended in the
chamber. Hence 'e' can be calculated.
By changing the strength of electrical field, Millikan found that the charge on each droplet was different.
The smallest charge which he found was 1.59  10–19 coulombs, which is very close to the recent value of
1.6022  10–19 coulombs. This smallest charge on any droplet is the charge of one electron. The other drops
having more than one electron on them, have double or triple the amount of this charge. The charge present on
an election is the smallest charge of electricity that has been measured so far.
S.Q27 How the mass of electron is calculated by using e/m value? (LHR-2012,13,14,15,17, FSD-2011,17,
MLT-2011,2013,17, BHR-2011,2015, RWP-2013,16)
OR How change to mass (e/m) ratio of electron is measured?
Ans. Mass of Electron
The value of charge on electron is 1.602 10–19 coulombs, while e/m of electron is 1.7588  1011
coulombs kg–1. So,
= = 1.7588  1011 coulombs kg–1
Mass of electron =
Rearranging
Mass of electron = 9.1095  10–31 kg
Properties of Fundamental Particles (S.Q)
The Table (5.1) shows the properties of three fundamental particles electron, proton and neutron present
in an atom. Table (5.1) Properties of three fundamental particles
Particle Charge Relative Mass Mass
(coul) charge (kg) (amu)
Proton + 1.6022  10 19
+1 1.6726  10 –27
1.0073
Neutron 0 0 1.6750  10–27 1.0087
Electron –1.6022  10"19 –1 9.1095 1031 5.4858  10–4

MCQs
1. Mass of electron is (LHR- 2011).
(a) 9.1095  1031 kg (b) 9.1095  1031 kg
(c) 9.1095  10 kg–27
(d) 9.1095  10–31 kg
2. The change of one gram of electron is (MDCAT-2010)
(a) 1.7588  10–11 (b) 1.7588  1011 (c) 1.602  10–19 (d) 1.7588  108
5.2 Rutherford's Model of Atom (Discovery of Nucleus) (L.Q)
RWP-2014, SRG-2008, LHR-2005, 2017, FSD-2007,17, D.G.K-2006, GUJ-2008)
In 1911, Lord Rutherford performed a classic experiment. He studied the scattering of high speed -
particles, which were emitted from a radioactive metal (radium or polonium).
A beam of -particles was directed onto a gold foil of
0.00004 cm thickness as target through a pin-hole in lead plate,
Fig (5.9).
A photographic plate or a screen coated with zinc
sulphide was used as a detector. Whenever, an -particle struck
the screen, a flash of light was produced at that point. It was
observed that most of the particles went through the foil
undeflected. Some were deflected at fairly large angles and a few
were deflected backward. Rutherford proposed that the
rebounding particles must have collided with the central heavy
portion of the atom which he called as nucleus.
194 Chapter # 5 (Atomic Structure)
On the basis of these experimental observations, Rutherford proposed the planetary model (similar to the
solar system) for an atom in which a tiny nucleus is surrounded by an appropriate number of electrons. Atom as
a whole being neutral, therefore, the nucleus must be having the same number of protons as there are number of
electrons surrounding it.
In Rutherford's model for the structure of an atom, the outer electrons could not be stationary. If they
were, they would gradually be attracted by the nucleus till they
ultimately fall into it. Therefore, to have a stable atomic structure,
the electrons were supposed to be moving around the nucleus in
closed orbits. The nuclear atom of Rutherford was a big step ahead
towards understanding the atomic structure, but the behaviour of
electrons remained unexplained in the atom.
Rutherford's planet-like picture was defective and
unsatisfactory because the moving electron must be accelerated
towards the nucleus Fig (5.10).
Therefore, the radius of the orbiting electron should become
smaller and smaller and the electron should fall into the nucleus.
Thus, an atomic structure as proposed by Rutherford would collapse.
S.Q28 How nucleus was discovered? (GUJ-2008)
Ans. Rutherford passed the a-particles through the gold foil. Most of the particles passed un-deflected. Only
few of them were deflected at certain angles. Some were re-bounced back on their original path. He
concluded that most part of the atom is empty from which the -particles were passed without
hindrance. A very small portion deflected the a-particle. This heavy central part of atom is nucleus.
S.Q29 How did Rutherford's mode) of an atom first of all proved the existence of nucleus of the atom?
(GRW-2008)
Ans. Rutherford observed that most of the a-particles passed straight through the gold foil without any
deflection from the path. Few of them were deflected at some angle more than 909 and a few were
deflected back on the original path. He concluded that the atom contains heavy and positively charged
part at the center. This heavy part at the center is called nucleus.
S.Q30 What are the defects of Rutherford's atomic model? (MLT-2007, 2008, Rwp- 2009, MLT-2009,
FSD.-2009, SRG-2010, RWP- 2010, LHR-2011, RWP-2011, MTN-2011, FSD-2009,13, GUJ-2013,
17, 09, 16, BHW-2016, 17, DGK-2016, 10, LHR-2015, 17, RWP-2017, 14, 16, 09)
Ans. (i) It is based on the laws of the motion and the gravitation. These laws are not for the charged bodies
like electrons.
(ii) The revolving electron should emit the energy continuously and by producing a spiral path, it
should ultimately fall into the nucleus. But actually the atoms don't do it.
(iii) The atom should give continuously spectra, but they give the line spectra.
5.3 PLANCK'S QUANTUM THEORY (L.Q) (D.G.K-2006, FSD-2010)
Max Planck proposed the quantum theory, in 1900 to explain the emission and absorption of
radiation. According to his revolutionary theory, energy travels in a discontinuous manner and it is composed of
large number of tiny discrete units called quanta. The main points of his theory are:
(i) Energy is not emitted or absorbed continuously. Rather, it is emitted or absorbed in a discontinuous
manner and in the form of wave packets. Each wave packet or quantum is associated with a definite
amount of energy. In case of light, the quantum of energy is often called photon.
(ii) The amount of energy associated with a quantum of radiation is proportional to the frequency (v) of the
radiation. Frequency is the number of waves passing through a point per second.
Ev
E = hv …… (4)
Professor CHEMISTRY - XI (Subjective) 195
Where 'h' is a constant known as Planck's constant and its value is 6.626  10–34JS. It is, in fact, the ratio
of energy and the frequency of a photon.
(iii) A body can emit or absorb energy only in terms of quanta.
E = hv
The frequency 'v ' is related to the wavelength of the photon as
v = c/
Greater the wavelength, smaller the frequency of photon
So. E = hc/ …. (5)
Wavelength is the distance between the two adjacent crests or troughs and expressed in A, nm or
pm. (1A=10–10m, l nm = 10–9m, 1pm = 10–12m)
Greater the wavelength associated with the photon, smaller is its energy. Wave number (–) is the
number of waves per unit length, and is reciprocal to wavelength.
– = 1/
Putting the value of X in equation (5)
E=hc– …. (6)
So, the energy of a photon is related to frequency, wavelength and wave number.
Greater the wave number of photons, greater is the energy associated with them. The relationships of
energy, frequency, wavelength, wave number about the photon of light are accepted by scientists and used by
Bohr in his atomic model.
S.Q31 Define wavelength and wave number (GUJ-2011)
Ans. Wavelength: The distance between the two adjacent crests or, troughs is known as wavelength. It is
expressed in nm or Angstrom(1o = 10–10 m) .
Wave number: It is the number of waves per unit length and is reciprocal of wavelength.
Mathematically,
J = 1/
S.Q32 How energy of photon can be calculated from the measurement of frequency, wavelength and
wave number of the photon. (GUJ-2006, BHR-2008)
Ans. According to Plank's quantum theory.
Ev
or E = hv
or E = nhv, where n = 1,2,3…….
The ‘v’ is related to the wavelength of the photon as
v = c/ 
so E = hc /  ….. (1)
v=1/
Putting the value of 1/, in eq(1)
E = hc v
So, the energy of a photon is related to frequency, wavelength and wave number
S.Q33 Give postulates of Planck’s theory.
OR
What is Plan’s theory (RWP-2009), LHR-2013, 14, SRG-2016, SHW-2017, SRG-2017, LHR-2017)
Ans. (i) Energy is not emitted or absorbed continuously. It is emitted or absorbed in a discontinuous
manner in the form of wave packets called quanta. In case of light, the quantum of energy is often called
photon.
(ii) Each wave packet or quantum has a definite amount of energy.
196 Chapter # 5 (Atomic Structure)

S.Q34 Give the relationship between energy and frequency. (BHR-2008)

OR
Derive the formula for frequency of photon (D.G. Khan -2010)
Ans. According to Plank's Quantum Theory, the energy of the quantum is directly related to the frequency of
radiation by the equation
Ev or E = hv
where E = Energy of the quantum v = Frequency of radiation h = Planck's constant = 6.625 10 Js
S.Q35 Prove that E=hc– (D.G. Khan -2014: FSD-2017)
Ans. According to Plank's quantum theory
E = hv (1)
where E = Energy of the quantum v = Frequency of radiation
Since c = v or v = c/ (2).
where c = velocity of light = 3  10 ms 8 –1
 = wavelength of any light radiation
Put eq. 2 in eq. 1
E = h c/ (3)
 is related to the wave number i.e.; – as
 = 1/v (4)
Put eq. 4 in eq. 3 E = hcv
E = hc – (5)
S.Q36 Differentiate between (or What is) frequency and wave number (D.G. Khan -2007: MTN-2010,
2015, GRW-2011.2015: LHR- 2016)
Ans. Frequency: It is the number of waves, which passes through a given point in one second. It is denoted by
v. Its units are cycles s–1'or s–1 or Hertz (Hz).
Wave Length: It is the distance between two adjacent crests or troughs in a beam of radiation.
It is denote by A. Its units are meter (m), nanometer (nm) or angstrom (A) etc.
1 o = 10–10m, 1 nm=10–9m, 1 pm =10–12m
Frequency and wavelength are related to each other as
c = v or v=c/
where c = velocity of light = 3  10 ms–1  = wavelength of any light radiation
8

MCQs
1. The value of Plank’s constant ‘h’ is (LHR-2010)
(a) 6.625  10–24 cal (b) 6.625  10–34 Jsec
(c) 6.62  10 kJ
–34
(d) 6.625  10–34 kcal
2. Angstrom is the unit of (Lahore Board, 2009)
(a) time (b) length (c) Mass (d) Frequency
3. Properties of waves are: (FSD-2009).
(a) Wave length (b) Wave number (c) Frequency (d) All
5.4 BOHR'S MODEL OF ATOM (L.Q)
(LHR-15,17, RWP-16, SHW-16, FSD-15, 16, MLT-2015, GUJ-2014, SRG-2005, BHR-2005, 2017)
Bohr made an extensive use of the quantum theory of Planck and proposed that the electron, in the
hydrogen atom, can only exist in certain permitted quantized energy levels. The main postulates of Bohr's
theory are:
(i) Electron revolves in one of the circular orbits outside the nucleus. Each orbit has a fixed energy and a
quantum number is assigned to it.
Professor CHEMISTRY - XI (Subjective) 197
(ii) Electron present in a particular orbit neither emits nor absorbs energy while moving in the same fixed
orbits. The energy is emitted or absorbed only when an electron jumps from one orbit to another.
(iii) When an electron jumps, the energy change AE is given by the Planck's equation
E = E2 – E1 = hv …. (7)
Where E is the energy difference of any two orbits with energies E 1 and E2. Energy is absorbed by the
electron when it jumps from an inner orbit to an outer orbit and is emitted when the electron jumps from
outer to inner orbit. Electron can revolve only in those orbits having a fixed angular momentum
(mvr). The angular momentum of an orbit depends upon its quantum number and it is an integral
multiple of the factor h/2 i.e.
mvr = …. (8)
Where n = 1,2,3
The permitted values of angular momenta are, therefore, , , …..
The electron is bound to remain in one of these orbits and not in between them. So, angular momentum
is quantized.
S.Q37 Why the energy of electron becomes zero at infinite distance?
Ans. We know that
E = – 2.178  10–18 J  1/n2
At infinite distance n =  so, E = – 2.178  10–18 J  l/2
Since, l/oo = 0, so E = 0
It means that at infinite distance, the pull of nucleus bee minimum and the electron at that distance
becomes stationary a energy becomes zero.
S.Q38 Why the velocity of electron decreases as the distance from nucleus increases?
Ans. We know from Bohr's theory
r = Ze2/4omv2 or r  1/v2
The distance is inversely proportional to the square of the velocity of electron. The velocity is highest
near the nucleus in 1st orbit lowest in the last orbit. The velocity becomes zero to infinite distance.
S.Q39 According to Bohr's model, the angular momentum of moving electron is a quantized. Justify it.
Ans. Bohr's said that the angular momentum 'mvr' of the moving electron is integral multiple of
mvr =
when 'n' is simple multiple or integral multiple. It is basically number of orbits so,
mvr = , , , …..
It means that, there are quantum jumps in the angular momentum values.
Derivation of Radius and Energy of Revolving Electron in nth Orbit. (L.Q)
(FSD-2015, 16, 17, BHR-2005, 06, 12, 14, LHR-2005, MLT-2005,
SRG-2005, 14, SHW-2016, GUJ-2014, 2016, MLT-2012, 15, 16,
D.G.K-2011,15)
By applying these ideas, Bohr derived the expression for the
radius of the nth orbit in hydrogen atom.
For a general atom, consider an electron of charge 'e' revolving
around the nucleus having charge Ze+. Z being the proton number
and e+ is the charge on the proton, Fig (5.11).
Let m be the mass of electron, r the radius of the orbit arid v
the velocity of the revolving electron. According to Coulombs law,
the electrostatic force of attraction between the electron and the
nucleus will be given by the following formula:
=
198 Chapter # 5 (Atomic Structure)
o is the vacuum permittivity and its value is 8.84  10–12C2J–1 m–1.This force of attraction is
balanced by the . Therefore, for balanced conditions, we can write
or =
mv2 = ….. (9)
Rearranging the equation (9)
R = …. (10)
According to equation (10), the radius of a moving electron is inversely proportional to the square of its
velocity. It conveys the idea, that electron should move faster nearer to the nucleus in an orbit of smaller
radius. It also tells, that if hydrogen atom has many possible orbits, then the promotion of electron to higher
orbits makes it move with less velocity.
The determination of velocity of electron is possible while moving in the orbit. In order to eliminate the
factor of velocity from equation (10), we use Bohr's postulate (iv). The angular momentum of the electron is
given by.
mvr =
Rearranging the equation of angular momentum
Taking square v =
Taking square v2 = …. (11)
2
Substituting the value of v from eq. (11) into eq. (10), we get
r =
Rearranging the above equation, we get
r = …. (12)
For hydrogen atom Z = 1, so the equation for radius of H-atom is
r = = ()n2 …. (13)
According to the equation (13), the radius of hydrogen atom is directly proportional to the square of
number of orbit (n). So, higher orbits have more radii and vice versa. The collection of parameters in
equation (13) is a constant factor.
When we put the value of o , h2 , m and e2 alongwith the units then the calculations show that it is
equal to 0.529  10–10 m or 0.529 o.( 10–10 m = 1o)
Hence r = 0.529 o (n2) …. (14)
By putting the values of n as 1,2,3,4 , the radii of orbits of hydrogen atom are
n = l r1 = 0.529 o n=4 r4 = 8.4o
n = 2 r2 = 2.11 o n=5 r5 = 13.22o
n = 3 r3 = 4.75 o
The comparison of radii shows that the distance between orbits of H-atom goes on increasing as we
move from 1st orbit to higher orbits. The orbits are not equally spaced.
r2 – r1 < r3 – r2 < r4 – r3 < …………..
The second orbit is four times away from the nucleus than first orbit, third orbit is nine times away and
similarly fourth orbit is sixteen times away.
Energy of Revolving Electron (L.Q)
(FED-2014, RWP-2008, MLT-2006, FSD-2011, AJK-2012)
The total energy of an electron in an orbit is composed of two parts, the kinetic energy which is equal to
mv2 and the potential energy. The value of potential energy can be calculated as follows.
The electrostatic force of attraction between the nucleus and the electron is given by . If the electron
moves through a small distance dr, then the work done for moving electron is given by
Professor CHEMISTRY - XI (Subjective) 199
dr because work = (force  distance)
The work done is the potential energy of electron, so
Work done = Epotential = …. (15)
The minus sign indicates that the potential energy of electron decreases, when it is brought from infinity
to a point at a distance 'r' from the nucleus. At infinity, the electron is not being attracted by any thing and the
potential energy of the system is zero. Whereas at a point nearer the nucleus, it will be attracted by the nucleus
and the potential energy becomes less than zero. The quantity less than zero is negative. For this reason, the
potential energy given by equation (15) is negative.
The total energy (E) of the electron, is the sum of kinetic and potential charges:
So, E = Ekinetic + Epotential
= mv2 – …. (16)
Now, we want to eliminate the factor of velocity from equation (16). So, from equation (9), substitute the value
of mv2 in eq. (16)
Since mv2 = …. (9)
E = –
Simplifying it, E = – …. (17)
Now substitute the value of r from eq (12) into eq (17) we get
Since r = …. (12)
Eo = …. (18)
Where En is the energy of nth orbit.
For hydrogen atom , the number of protons in nucleus is one, so( Z = l).
En = …. (19)
Eq.(19) gives the energy of electron revolving around the nucleus of hydrogen atom. The factors outside
the brackets in equation (19) are all constants. When the values of these constants are substituted along with
their units, then it comes out to be 2.178  10–18 J. The equation (19) can be written as,
En = –2.178 10–18 J …. (20)
This equation (20) gives the energy associated with electron in the nth orbit of hydrogen atom. Its
negative value shows that electron is bound by the nucleus i.e. electron is under the force of attraction of the
nucleus. Actually, the electron has been brought from infinity to distance r from the nucleus.
The value of energy obtained for the electron is in joules/atom. If, this quantity is multiplied by
Avogadro's number and divided by 1000, the value of En will become
En =  kJmol–1
En = – kJmol–1 …. (21)
This energy is associated with 1.008g of H-atoms i.e. with Avogadro's number of atoms of hydrogen.
Substituting, the values of n as 1,2,3,4,5, etc. in equation (21), we get the enerj associated with an electron
revolving in 1st, 2nd, 3rd, 4th and 5th orbits of H-atom.
E1 = – = –1313. 31 kJmol–1  E2 = – = –328.32 kJmol–1
E3 = – = – 145.92 kJmol–1  E4 = – = – 82.08 kJmol–1
E5 = – = – 52.53 kJmol–1
E = – = 0 kJmol–1 (electron is free from the nucleus)
The values of energy differences between adjacent orbits can be calculated as follow
E2 – E1 = (–328.32) – (–1313.31) = 984.99 kJmol–1
E3 – E2 = (–145.92) – (–328.32) = 182.40 kJmol–1
E4 – E3 = (–82.08) – (–145.92) = 63.84 kJmol–1
200 Chapter # 5 (Atomic Structure)
The differences in the values of energy' go on decreasing
from lower to higher orbits.
E2 – E1 > E3 – E2 > E4 – E3 > ………
The energy difference between first and infinite levels of
energy is calculated as:
E – E1 = 0 – (–1313.31) = 1313.31 kJmol–1
1313.31 kJmol–1 is the ionization energy of hydrogen.
This value is the same as determined experimentally.
These values show that the energy differences between
adjacent orbits of Bohr's model of hydrogen atom go on
decreasing sharply. Keep in mind, that distances between adjacent
orbits increase. The Fig (5.12; makes the idea clear.
S.Q40 Difference between atomic emission spectra and atomic absorption spectra.
(D.G.K-2010, SHW-2017, BHR-2005,17, SRG-2011, MLT-2012,16, LHR-2014)
Atomic emission spectra Atomic absorption spectra
1 It is formed when the substance is in the 1 It is formed when the substance is in the
excited state. unexcited state.
2 It is produced when the substance reaches 2 It is produced by gases and transparent
the gaseous or vapour state. liquids and solids.
3 This spectrum consists of coloured lines 3 In the spectrum black lines are present at
present in black background. white background.
4 Energy element has characteristic pattern of 4 In this spectrum dark lines replace
coloured lines of specific wavelength coloured lines of specific wavelength of
emission spectrum.
5 When an excited electron jumps from higher 5 When electron absorb energy and moves to
to a lower energy, it emits energy which higher orbit, absorbed radiations are
forms coloured lines in emission spectra indicated by dark lines.
S.Q41 Why the electrons move faster in an orbit of smaller radius? (SRG-2013)
OR
S.Q42 Why the velocities of electrons in higher orbits are less than that in the lower orbits. (RWP- 2014)
Ans. According to Bohr's theory, the equation for velocity of an electron in any orbit is
V2 = or V2 
This equation shows that square of velocity of electron is inversely proportional to the radius of orbit (r).
It means electrons revolve faster in an orbit of smaller radius nearer to the nucleus. As the electron
moves to higher orbits of larger radius, its velocity decreases.
S.Q43 The radius of first orbit of hydrogen atom is 0.529o. Calculate the radius of 3rd orbit of hydrogen
atom (GRW-2013)
Ans. According to Bohr's theory, the equation for radius of orbit is
r = 0.529  n2
Thus, for 3rd orbit, n = 3
r3 = 0.529  32 = 4.75o
S.Q44 Why potential energy of an electron (or bonded electron) is negative in an orbit of atom?(BHR-
2011, SRG-2013)
Ans. According to Bohr's theory, Potential Energy = P.E. = . The minus sign indicates that the P.E. decreases
Professor CHEMISTRY - XI (Subjective) 201
when the electron is brought from infinity to distance 'r'. At infinity, the electron is not attracted by
anything, thus P.E. is zero. At a point nearer to the nucleus, electron is attracted by nucleus, thus P.E. is
less than zero i.e, negative.
S.Q45 Total energy of bonded electron is negative. Why? (GUJ-2010)
Ans. According to Bohr's theory, Total Energy = En =
The minus sign indicates that the energy decreases when the electron is brought from infinity to distance
'r'. At infinity, the electron is hot attracted by anything, thus energy is zero. At a point nearer to the
nucleus, electron is attracted by nucleus, thus energy is less than zero i.e. negative.
S.Q46 How do you justify that the distances between adjacent orbits of H n go on increasing from lower
to the higher orbits?
Ans. The equation for the radius of the H-atom, after putting the values of ;rent parameters for H-atom is as
follows
r = 0.529 (n2) Ao
If we put the value of "n" = 1, 2, 3, …., we can get the radii which show that the distances between
adjacent orbits go on increasing.
S.Q47 How do you justify that the radius of orbit in H-atom is directly portional to the square of number
of orbit?
Ans. When we derive the equation for radius of an atom according to Bohr's model, we get the following
equation
r = 0.529 A°
According to this equation, radius is directly proportional to square of iber of orbit. So when the number
of orbit increases the radius cases sharply. Second Bohr's orbit is four times away from the nucleus t the
1st orbit. Third orbit is nine times away.
S.Q48 How do you prove that the energy associated with the electron which' is revolving around the
nucleus of H-atom is negative? (GRW-2010, BHR-2011)
Ans. The expression for the potential energy of electron is
P.E =
The value of the kinetic energy is calculated from the equalization of force of attraction () and
centrifugal force,
So, mv2 = K.E =
When we add K.E. and P.E the total energy is negative.
Etotal = – = –
S.Q49 you come to know that the velocities of electrons in higher orbits are less than those in lower orbits
of hydrogen atom? (RWP-2008, D.G. Khan 2011, LHR-2012)
Ans. According to Bohr's proposals; the centrifugal force of the electron is equal to the force of attraction
between nucleus and electron.
E = – 2.18  10–18 J
Greater the value of 'n' greater the value of energy because energy is negative, inverse of n. It becomes
more and more, 'less' negative. The value of energy approaches zero, when n = 
S.Q50 The energy difference between adjacent levels goes on decreasing sharply. Why? (RWP-2007,
LHR-2015)
Ans. If we put the value of n as 1,2,3,4 we get the energies of various orbits of hydrogen atom. These values
are as follows:
E1 = – 2.18  10–18 J, E2 = – 0.54  10–18 J , E3 = – 0.24  10–18 J , E4 = – 0.14 
–18
10 J
As 'is clear from these values that energy differences between adjacent levels go on decreasing from
202 Chapter # 5 (Atomic Structure)
lower to the higher level.
S.Q51 Justify that the distance gaps between different orbits go on increasing from the lower to the
higher orbits. (FSD-2007, SRG-2009,16, LHR-2015, )
Ans. According to Bohr s model the radius of an orbit is proportional to the square of number of orbit.
r = 0.529 Ao
For hydrogen atom Z = 1
Putting the values
r = 0.529 Ao
r1 = 0.529 Ao
r2 = 2.4 Ao
r3 = 4.8 Ao
r4 = 8.4Ao
The difference of the adjacent orbit are such that
R2 – r1 < r3 – r2 < r4 – r3
S.Q52 How Bohr's model of H-atom can help us to justify the ionization potential of H-atom?(BHR-2008,
GRW-2010)
Ans. The formula for the energy difference between any two levels for H-atom is
E = +2.18  10–18 J
This is the equation for one atom of hydrogen. If we multiply this by Avogadro's number and divide by
1000, we get the following equation
E = +1313.315 kJ mol–1
If we put the values of n1 = 1 and n2 = , then we can get the E value for the ionization of H-atom
E = + 1313.315 = 1313.315 kJ mol–1
S.Q53 Hydrogen atom and He+ are monoelectronic system, but the size of He+ is much smaller than H.
Why? (MTN-2009)
Ans. Hydrogen atom and He+ ion have single electron in the valance shell He + has two protons in the nucleus,
so it will have greater force attraction. The size of He+ is smaller than H atom.
rHe+ = 0.529 A° = 0.2645 A°
S.Q54 Do you think that the size of Li+ is even smaller than He+? Justify with calculations.
Ans. The size of Li+ is even smaller than He+, because Li+ has three protons in the nucleus. It has only one
electron. So,
n = 1 and z=3
2+ o
rLi = 0.529 A° = A = 0.176A°
MCQs
1. Radius of second orbit of H-atom is (LHR-2008)
(a) 2o (b) 2.11o (c)
8.4o (d) 13.22o
5.5 SPECTRUM (S.Q + L.Q)
(LHR-03, BHR-2005, GUJ-2005, AJK-2005, MLT-2007,
D.G.K-2017, 2007, SRG-2010)
When a radiation of light is passed through a prism, the
radiation undergoes refraction or bending. The extent of bending
Professor CHEMISTRY - XI (Subjective) 203
depends upon the wavelength of the photons. A radiation of longer wavelength is bent to a smaller degree than
the radiation of a shorter wavelength. Ordinary, white light consists of radiation of all wavelengths, and so after
passing through the prism, white light is splitted up into radiations of different wavelengths.
The colours of visible spectrum are violet, indigo, blue, green, orange, yellow and red and their
wavelengths range from 400 nm to 750 nm. In addition to the visible region of the spectrum, there are seven
other regions. Ultraviolet, X-rays, y-rays and cosmic rays are towards the lower wavelength end of the
spectrum and they possess the photons with greater energies. On the other side of the visible region, there lies
infrared, microwave and radio frequency regions. Fig. (5.13) shows the continuity of wavelengths for all
types of regions of spectrum. Hence, a visual display or dispersion of the components of white lights when
it is passed through a prism is called a spectrum.
Spectrum is of two types.
(i) Continuous spectrum (ii) Line spectrum
5.5.1 Continuous Spectrum (S.Q)
In this type of spectrum, the boundary line between the colours cannot be marked. The colours diffuse
into each other. One colour merges into another without any dark space. The best example of continuous
spectrum is rainbow. It is obtained from the light emitted by the sun or incandescent (electric light) solids. It is
the characteristic of matter in bulk.
5.5.2 Atomic or Line Spectrum (S.Q) (SHW-2017, AJK-2017, RWP-2013, SRG-2014)
When an element or its compound is volatilized on a flame and the light emitted is seen through a
spectrometer, we see distinct lines separated by dark spaces. This type of spectrum is called line spectrum or
atomic spectrum. This is characteristic of an atom. The number of lines and the distance between them depend
upon the element volatilized. For example, line spectrum of sodium contains two yellow coloured lines
separated by a definite distance. Similarly, the spectrum of hydrogen consists of a number of lines of different
colours having different distances from each other. It has also been observed that distances between the lines for
the hydrogen spectrum decrease with the decrease in wavelength and the spectrum becomes continuous after a
certain value of wavelength Fig (5.14).

Atomic spectrum can also be observed when elements in gaseous state are heated at high temperature or
subjected to an electric discharge.
There are two ways in which an atomic spectrum can be viewed.
(i) Atomic emission spectrum
(ii) Atomic absorption spectrum
5.5.3 Atomic Emission Spectrum (S.Q)
When solids are volatilized or elements in their gaseous states are heated to high temperature or
subjected to an electrical discharge, radiation of certain wavelengths are emitted. The spectrum of this radiation
contained bright lines against a dark background. This is called atomic emission spectrum. Fig (5.15)
Energy being emitted
204 Chapter # 5 (Atomic Structure)

5.5.4 Atomic Absorption Spectrum (S.Q)

When a beam of white light is passed through a gaseous sample of an element, the element absorbs
certain wavelengths while the rest of wavelengths pass through it. The spectrum of this radiation is called an
atomic absorption spectrum. The wavelengths of the radiation that have been absorbed by the element appear as
dark lines and the background is bright, Fig (5.16).

It is interesting to note that the positions or the wavelengths of lines appearing in both emission and
absorption spectra are exactly the same. In emission spectrum, these lines appear bright because the
corresponding wavelengths are being emitted by the element, whereas they appear dark in absorption spectrum
because the wavelengths are being absorbed by the element.
S.Q55 What is the origin of line spectrum? (SRG-2009)
Ans. According to Bohr’s atomic model, the energy of an electron remains constant in an orbit. If it jumps to
higher orbit, it absorbs energy and during de-excitation it emits energy. Absorbed energy is in the form
of dark lines obtained in absorption spectrum while emitted energy is in the form of bright lines of
emission spectrum. In this way line spectrum is formed.
S.Q56 The energy associated with the violet colour is greater than the red colour in the visible region of
spectra. (LHR-2007)
Ans. The energy is inversely proportional to wavelength of the radiation. Since violet colour has shorter
wavelength (400-420 nm), so it has higher energy. Where as red colour has larger wavelength (630-750
nm), so it has low energy.
S.Q57 Define spectrum. Name its two types. (D.G. Khan-2012,15: MTN-2007, 09. LHR- 2009)
OR
What is spectrum? Give one example. (BHR-2009)
Ans. A visual display or dispersion of the components of white light, when it is passed through a prism is
called a spectrum. There are two types of spectrum
(i) Continuous Spectrum e.g. Rainbow (ii) Line Spectrum e.g. Atomic Spectrum
S.Q58 What is the origin of line spectrum? (SRG-2009: MTN-2017: D.G.Khan-2017: AJK-2017) Why
atomic spectrum is line spectrum? (LHR-2010)
Ans. In this, bright lines are separated by dark bands.
Origin of Atomic Emission Spectrum: When a substance is heated or subjected to electric discharge. It
Professor CHEMISTRY - XI (Subjective) 205
emits radiations of definite wavelengths. These radiations will produce bright lines on a dark screen as
shown in the figure.
S.Q59 polychromatic light split into various bands of light while passing the transparent glass prism?
(D.G. Khan-2016)
Ans. Light from sun and electric bulb consists of radiations of different wavelengths, i.e. polychromatic light
When this light is passed through a prism, it is separated into a band of different colours. It is because,
the light of longer wavelengths bend to a smaller degree while the light of shorter wavelengths bend to a
greater degree and thus different colours trained as shown in the figure.
S.Q60 Define or Differentiate between line spectrum and continuous spectrum.(DGK-2010: LHR-2014:
SRG-2011: MTN-2012.2016: BHR-2015.2016: BHR-2017: SHW-2017)
Ans.
Continuous spectrum Line spectrum
1 In this, coloured are diffused into other and 1 It consists of dark or bright lines separated
they are not separated. by bright or dark bands.
2 Each colour in the band has a range of 2 Each line in the spectrum has its own
frequencies. characteristic colour and frequency.
3 There is not sharp boundary between the 3 There is distance between the lines.
colours
4 It is characteristic of the molecules 4 It is characteristic of atoms.
5 Example: Rainbow 5 Example: Balmer series of hydrogen
spectrum.
S.Q61 The energy associated with, the violet colour is greater than the red colour in the visible region of
spectra. Why? (LHR-2007)
Ans. The photons of violet colour bend to the maximum extent after passing through the prism and their
range of wavelength is from 400 - 420 nm. They have, high energy and have shorter wavelengths. The
photons of the red colour have the longer wavelength ranging from 630 to 750 nm. These ^photons bend
in the prism to lesser extent.
S.Q62 Why the photographic plate is white and few dark lines are there in the line absorption spectra of
a substance? (SRG-2009, LHR-2010, 2011, BHR-2012)
Ans. Some of the photons are absorbed by the sample to excite the electrons of a substance from lower energy
levels to higher energy levels. These photons of light don't reach the photographic plate. Rest of the light
reaches the photographic plate, so the plate is white. Only those places are dark in the form of sharp
lines where the photon don't reach.
S.Q63 Why the photographic plate is dark and a few bright lines are there in the line emission spectra of
hydorgen? (SRG-2009, Rwp- 2010, SRG-2011, BHR-2012)
Ans. The sample of hydrogen is taken in a glass tube. Electric current is passed through the gas. Electrons of
the atoms or molecules are excited to higher energy levels. These electrons fall back to the original
levels and emit the photons of light. These emitted photons produce bright lines and rest of the plate is
dark.
5.5.5 Hydrogen Spectrum (S.Q)
Hydrogen-spectrum is an important example of atomic spectrum. Hydrogen is filled in a discharge
tube at a very low pressure a bluish light is emitted from the discharge tube. This light when viewed through a
spectrometer shows several isolated sharp lines.
These are called spectral lines. The wavelengths of these lines lie in the visible, ultraviolet and
206 Chapter # 5 (Atomic Structure)
infrared regions. These spectral lines can be classified into five groups called spectral series. These series
are named after their discoverers as shown below.
(i) Lyman series (U.V region) (ii) Balmer series (visible region)
(iii) Paschen series (I.R region) (iv) Brackett series (I.R region) (v) Pfund series (I.R region)
The first four series were discovered before Bohr's atomic model (1913). The wave numbers (m –1)
of the series of lines in hydrogen spectrum are given in Table (5.2).
It is seen from the Table (5.2) that as we proceed from Lyman series to Pfund series, the wave numbers
(m1) of spectral lines decrease. The lines of Balmer series have been given specific names as H , H, …. etc.
Table (5.2)Wave numbers (m–1) of various series of hydrogen spectrum.
Lyman series Balmer series Paschen series Brackett series Pfund series (I.R.
(U.V region) (Visible region) (I.R. region) (I.R. region) region)
82.20  105 15.21 l05(H line) 5.30  105 2.46  105 1.34  105
97.60  105 20.60  105 (H 7.80  105 3.80  105 2.14  105
102.70  105 line) 23.5 l05 (H 9.12  105 4.61  105
105.20  105 line) 24.35  9.95  105
106.20  105 105(H line) 25.18
107.10  105  105
5.5.6 Origin of Hydrogen Spectrum on the Basis of Bohr's Model (S.Q)
According to Bohr, electron in hydrogen atom may revolve in any orbit depending upon its energy.
When hydrogen gas is heated or subjected to an electric discharge, its electron moves from one of the lower
orbit to higher orbit, absorbing particular of energy.
Subsequently, when it comes back,
the same energy is released. This energy is
observed as radiation of particular
wavelengths in the form of bright lines seen
in the certain region of the emission
spectrum of hydrogen gas.
The spectral lines of Lyman series are
produced when the electron jumps from n 2 =
2, 3, 4, 5, to, n4 = 1 (Lyman did not know
this reason). Similarly, spectral lines of
Balmer series discovered in 1887 originated
when an electron jumps from n2 = 3, 4, 5, 6,
to n1 = 2 orbit.
In the same way, Paschen, Brackett
and Pfund series of lines are produced as a
result of electronic transitions from higher
orbits to 3rd, 4th and 5th orbits, respectively Fig (5.17).
Calculations of Wave Numbers .of photons of Various Spectral Series by Bohr’s Theory
The wavelength (, ) or wave number (–) of a spectral line depends on the quantity of energy emitted by
the electron. Suppose, an electron jumps from n2 to n, and emits a photon of light. According to Bohr's equation
of energy
E1 =
E2 =
E1 and E2 are the energies of electrons in n1 and n2 respectively. The energy difference between the two can be
calculated as follows:
Professor CHEMISTRY - XI (Subjective) 207
E =E2 – E1 = Joules …. (22)
For H-atom; Z = 1
and = 2.18  10–18 J (by putting the values of constants)
E = 2.18  10–18 Joules …. (23)
With the help of equation (23), the energy difference between any two orbits of H- atom can be
calculated where n, is the lower level and n, is higher level. It is not necessary that n, and n, are adjacent orbits.
Since E = hv
Therefore hv =
v = Hz … (24)
Frequency (v) has the units of the cycles s or Hz. (1 Hz = 1 cycle s–1)
–1

Equation (24) gives us the frequency of a photon emitted, when electron jumps from higher orbit to
lower orbit in H-atom. The frequency values go on decreasing between adjacent levels.
Calculation of Wave Number
Since v = c–
Putting in equation (24)
Therefore c– =
– = m–1 … (25)
The value of the factor in eq. (25) has been calculated to be 1.09678  107m–1.
This is called Rydberg constant. Putting Z = 1 for hydrogen atom, the equation (25) becomes.
– = 1.09678  107 m–1
Equation (26) gives the values of wave number of photons emitted or absorbed when the electron jumps
between n1 and n2 orbits.
Let us calculate, the wave numbers of lines of various series.
Lyman Series: Fig. (5.17)
First line n1 = l(lower orbit), n2 = 2 (higher orbit)
– = 1.09678  107 = 82.26  105 m–1
Second line n1 = 1 n2 = 3
– = 1.09678  107 = 97.49  105 m–1
Limiting line n1 = 1 n2 = 
– = 1.09678  107 = 109.678  105 m–1
Limiting line is developed, when electron jumps from infinite orbit to, n = 1
The values of all these wave numbers lie in the U.V region of the spectrum. It means that when electron
of H-atom falls from all the possible higher levels to n = 1, then the photons of radiation emitted lie in the range
of U.V region.
Balmer Series: Fig (5.17)
First line n1 = 2 n2 = 3
– = 1.09678  107 = 15.234  105 m–1
Second line n1 = 2 n2 = 4
– = 1.09678  107 = 20.566  105 m–1
Third line n1 = 2 n2 = 5
– = 1.09678  107 = 23.00  105 m–1
Limiting line n1 = 2 n2 = 
– = 1.09678  107 = 27.421  105 m–1
The limiting line of Balmer series lies in U.V region, while other lines fall in visible region. Similarly,
we can calculate the wave numbers for all the lines of Paschen, Brackett and Pfund series. These three series of
208 Chapter # 5 (Atomic Structure)
lines lie in the infrared region.
S.Q65 What are fine structures?
Ans. When the spectrum of H-atom is observed by high resolving spectrometer; then individual spectral lines
are replaced by several very fine lines. These are called fine structures of spectrum. For example, when
H–line in Balmer series is observed, instead of single line, five component lines (fine structures) are
formed.
S.Q What is the origin of hydrogen spectrum on the basis of Bohr's model? (FSD-2010, GUJ-
2017)
Ans. According to Bohr's electrons is H-atom revolve in orbit depending upon its energy. When hydrogen gas
is entered its electrons move from lower orbit to higher orbit absorbing particular wavelength.
Subsequently when this electron back to same energy it release energy in form of bright lights.
S.Q66 Calculate the wave number of photon, when the electron jumps from n = 5 to n = 2. (SHW-2015)
Ans. – = 1.09678  10+7
– = 1.09678  10+7
– = 1.09678  10+7 [–0.21]
– = –0.23032  107
– = –2.3032  106 m–1
S.Q67 What is the origin of hydrogen spectrum? (D.G. Khan-2010: MLT-2010, 2017, MLT-2015)
OR
Write names of spectral series of hydrogen spectrum. (LHR- 2011, 17)
Ans. When hydrogen is filled in a discharge tube at a very low pressure, it emits bluish light. This light when
seen with spectrometer shows many lines called spectral lines. These lines can be classified into five
groups called spectral series.
(i) Lyman series (U.V. region) (ii) Balmer series (Visible region) (iii) Paschen series (I.R. region)
(iv) Brackett seriesfl.R. region) (v) Pfund series(I.R. region)
S.Q68 What is Lyman series? In which region it lies? (RWP-2011: D.G. Khan-2015: MLT-2016)
Ans. According to Bohr's theory, when electrons jump from higher orbits to the first orbit in an hydrogen
atom it emits a series radiations. This series is called Lyman series. It lies in ultraviolet region.
S.Q69 Write down the equation for energy difference of two orbits of H-atom (BHR-2010)
Ans. The equation is
E =
Where E = Energy difference between two orbits, n 1 = lower energy orbit, n2 = higher energy orbit,
m = mass of electron, Z = atomic number of atom, e = charge on electron, o = permittibility of vaccum,
h = Planck’s constant. Putting values of constants and for hydrogen atom Z = 1, we can write.
E = 2.18  10–18 J J
S.Q70 How the value of the Redberg's constant can be justified from Bohr’s equation?
Ans. The constant outside the brackets was called Redberg's constant and v denoted by "R". Its value was
deduced by the back calculations from 1 experimental data of Lyman and Balmer series. Anyhow, the
structure atom was not clear at that time.
Bohr have the following relationship for the wave number
– = m–1
The solved factor outside the brackets comes out equal to Redberg’s constant i.e.,
= 1.09678  10–7 m–1
S.Q71 Write down the equation for energy difference of two orbits of hydrogen atom.
Professor CHEMISTRY - XI (Subjective) 209
Ans. A formula for energy difference of any two orbits of hydrogen atom give by Bohr is
E =
n1 is the lower orbit and n2 is higher orbit. Other factors are constant for an atom.
S.Q72 How Bohr's model justifies the H-spectra. (FSD-2010, LHR-2011)
Ans. The Bohr's equation of v gives us the values of wave numbers as were measured by Lymann, Balmer,
Paschen, Bracket and Pfund.
S.Q73 What is H  line in hydrogen spectrum? (BHR-2011)
Ans. This is the first line of Balmer series. It is produced due to the jumping of electrons from n = 3 to n = 2.
This line lies in the visible region.
S.Q74 Indicate the limiting line of Balmer series.
Ans. When the electrons jump from an infinite orbit to n = 2 of hydrogen atom, then this line on the
photographic plate is called the limiting line. It has high energy and lies in the U.V; region".
S.Q75 How is atomic emission spectrum obtained?(BHR-2005, RWP-2005)
Ans. The substance is heated in a glass tube by the electrical spark. The electrons are excited to higher energy
levels and when they come back, they emit the photons of light. These emitted photons are recorded on
the photographic plate. The whole plate is dark alongwith the few bright lines. These bright lines is
called line emission spectrum of the substance.
MCQs
1. Paschen, Brackett and Pfund series lie in (SRG-2010).
(a) UV region (b) visible region (c) IR region (d) microwave region
2. Lines of Paschen series are produced when electrons jump from higher orbits to ……. Orbit.
(GRW-2008)
(a) 1st (b) 2nd (c) 3rd (d) 4th
3. Balmer series in hydrogen spectrum lies in the region: (GRW-2011)
(a) ultraviolet (b) visible (c) Infrared (d) Microwave
4. Lyman series lies in (MTN-2011,FSD-2015).
(a) UV region (b) Visible region (c) IR region (d) Microwave region
5. Angstrom is the unit of (Lahore Board, 2009)
(a) time (b) length (c) Mass (d) Frequency
6. Lyman series occur in: (LHR-2007: SRG-2014: FSD-2015: D.G. Khan -2017)
(a) visible region (b) U.V. region (c) I R. region (d) None of these
7. Balmer series is found in (FSD-2007)
(a) I.R. region (b) U.V region (c) visible region (d) None of these
8. The wavelength of Lyman series lies in the region (SRG-2010).
(a) U.V (b) Visible (c) I.R (d) None of above
9. Value of the Redberg's constant is (D.G. Khan -2010)
(a) 1.7904  107 m–1 (b) 1.9768 107 m–1
(c) 1.09678 107 m–1 (d) 1.6  107 m–1
10. The limiting line of Balmer Series lies in the region (SRG-2011).
(a) Visible (b) U.V (c) Near I.R (d) Far I.R
11. Lyman Series lies in spectral region (SRG-2013)
(a) Infrared (b) Ultraviolet (c) Visible (d) None of these
12. Splitting of spectral lines in closely spaced lines in presence of magnetic field is called
(MCAT-2009)
210 Chapter # 5 (Atomic Structure)
(a) Stark Effect (b) Zeeman Effect (c) Photoelectric Effect (d) Compton
Effect
5.5.7 Defects of Bohr’s Atomic Model (L.Q)
GUJ-2008,14, D.G.K-2007,16, LHR-2014, SRG-2014, BHR-2004, 07, RWP-2005, LHR-2011, FSD-
2014, GUJ-2006, MLT-2009)
1. Bohr’s theory can successfully explain the origin of the spectrum of H-atom and ions like He +1, Li+1 and
Be+3, etc. These are all one electron systems. But this theory is not able to explain the origin of the
spectrum of multi-electrons or poly-electrons system like He, Li and Be, etc.
2. When the spectrum of hydrogen gas is observed by means of a high resolving power spectrometer, the
individual spectral lines are replaced by several very fine lines, i.e. original lines are seen divided into
other lines. The H- line in the Balmer series is found to consist of five – component lines. This is
called fine structure or multiple structure. Actually, the appearance of several lines in a single line
suggests that only one quantum number is not sufficient to explain the origin of various spectral lines.
3. Bohr suggested circular orbits of electrons around the nucleus of hydrogen atom, but researches have
shown that the motion of electron is not in a single plane, but takes place in three dimensional space.
Actually, the atomic model is not flat.
4. When the excited atoms of hydrogen (which give an emission line spectrum) are placed in a magnetic
field, its spectral lines are further split up into closely spaced lines. This type of splitting of spectral lines
is called Zeeman effect. So, if the source which is producing the Na – spectrum is placed in a weak
magnetic field, it causes the splitting of two lines of Na into component lines. Similarly, when the
excited hydrogen atoms are placed in an electrical field, then similar splitting of spectral lines takes
place which is called “Stark effect”. Bohr’s theory does not explain either Zeeman or Stark effect.
However, in 1915, Sommerfeld suggested the moving electrons might describe in addition to the
circular orbits elliptic orbits as well wherein the nucleus lies at one of the oci of the ellipse.
S.Q76 Give two defects of Bohr’s atomic model. (FSD-2012,15, GRW-2014, SHW-2014
Ans. (l) This model does not explain stark and Zeeman’s effect.
(2) It only applicable on Hydrogen and small element like He+, Li+2, Be–3 etc.
S.Q77 Differentiate/Describe/Define Stark and Zeeman effects (FSD-2011: GUJ- 2009, 10: D.G. Khan -
2008, 11: BHR-2012: LHR-2008, 15. RWP-2007, 15, 17: MLT-2008, 2013, 2015, 2017: SRG-2012,
2013, 2017: BHR-2016)
Ans. When the spectrum of atom is taken in the magnetic field, some new lines are created. This is called
Zeeman effect. E,g. when Na spectrum is taken in a weak magnetic field, its single, line is split up into
two component lines.
Similarly, when emission spectrum of excited H-atom is taken in an electrical field, lines are split up
into component lines. This is called stark effect.
Bohr’s theory cannot explain Zeeman effect and Starks effect.
S.Q78 What is Zeeman effect? (RWP-2007, GUJ-2009, 2010, D.G. Khan -2011, FSD-2011, BHR-2012,
SRG-2017, RWP-2015)
Ans. When the light of spectral lines is passed through the magnetic field, then .he one spectral line is splitted
up into many spectra lines. This splitting of that spectral line cannot be explained by Bohr’s theory.
S.Q79 What is starch effect? (MTN-2008. GUJ-2009, 2010, D.G. Khan-2011, FSD-2010,11, BHR-2012,
LHR-2016, SHW-2015, RWP-2015, SRG-2017)
Ans. When the light of spectral lines is passed through the electrical field, then the one spectral line is split up
into many spectra lines. This splitting of the spectral line cannot be explained by Bohr’s theory.
Professor CHEMISTRY - XI (Subjective) 211

MCQs
1. Splitting of spectral lines, when excited atoms are subjected to strong electric field is called
(DGK-2009)
(a) Zeeman effect (b) Stark effect (c) Photoelectric effect (d) Compton effect

5.6 X-RAYS AND ATOMIC NUMBER (L.Q)

(SHW-2014, FSD-2013, BHR-2014)
X-rays are produced when rapidly moving electrons
collide with heavy metal anode in the discharge tube.
Energy is released in the form of electromagnetic waves
when the electrons are suddenly stopped. In the discharge
tube, the electrons produced by a heated tungsten filament
are accelerated by high voltage Fig. (5.18). It gives them
sufficient energy to bring about the emission of X-rays on
striking the metal target. X-rays are emitted from the target
in all directions, but only a small portion of them is used for
useful purposes through the windows. The wavelength of
X-rays produced depends upon the nature of the target
metal. Every metal has its own characteristic X-rays.
The X-rays are passed through a slit in platinum plate and then emerged through aluminum window.
This is thrown on a crystal of K4[Fe(CN)6], which analyses the X-ray beam. The rays are diffracted from the
crystal and are obtained in the form of line spectrum of X-rays. This is allowed to fall on photographic plate.
This line spectrum is the characteristic of target material used. This characteristic X-rays spectrum has discrete
spectral lines. These are grouped into K-series, L-series and M-series, etc. Each series has various line as K ,
K, L L, M, M, etc.
A systematic and comprehensive study of X-rays was undertaken by Moseley in 1913-1914. His
researches covered a range of wavelengths 0.04 – 8o. He employed thirty eight different elements from
aluminium to gold, as target in X-rays tube. Moseley was able to draw the following important conclusions
from a detailed analysis of the spectral lines which he obtained.
(ii) The spectral lines could be classified into two distinct groups. One of shorter wavelengths are
identified by K-series and the other of comparatively longer wavelengths are identified by L-series.
(ii) If the target element is of higher atomic number the wavelength of X-rays becomes shorter.
(iii) A very simple relationship was found between the frequency (v) of a particular line of X-rays and the
atomic number Z of the element emitting it.
= a(Z – b) … (27)
Here ‘a’ and ‘b’ are the constants characteristic of the metal under consideration. This linear equation (27) is
known as Moseley’s Law. ‘a” is proportionality constant and ‘b’ is called screening constant of the metals.
This law states that the frequency of a spectral line in X-ray spectrum varies as the square of
atomic number of an element emitting it. This law convinces us that it is the atomic number and not the
atomic mass of the element which determines its characteristic properties, both physical and chemical. If value
of for K-series are plotted against Z, then a straight line is obtained.
Importance of Moseley Law (S.Q) (FSD-2014)
(iv) Moseley arranged K and Ar, Ni and Co in a proper way in’ Mendeleev’s periodic table.
(ii) This law has led to the discovery of many new elements like Tc(43 .Pr(59), Rh(45).
(iii) The atomic number of rare earths have been determined by this law.
S.Q81 What are X-rays? How they are produced? (SRG- 2007: D.G. Khan-2007: RWP- 2012: SHW-
2016: BHR-2017: MTN-2017)
212 Chapter # 5 (Atomic Structure)
OR
What Is the origin of emission of X-ravs? (Rawalpindi Board. 2014)
Ans. When fast moving electrons strike a heavy metal anode surface in a discharge tube, some highly
energetic rays produced. These rays are called X-rays.
Origin of X-rays: In a gas discharge tube, electrons produced by heated tungsten filament are
accelerated by high voltage. This gives them sufficient energy. Thus, when an electron suddenly stops
on collision, energy is released in the form of electromagnetic waves called X-rays.
S.Q82 How the K-series, L-series and M-series of X-rays spectrum are produced? (LHR- 2013)
Ans. When X-rays are generated, they emit in all directions. These are passed through a slit and then through
aluminum window. These are then thrown on a crystal of [Fe(CN) 6]. The rays are diffracted from the
crystal and a line spectrum of X – rays is obtained. This is taken on a photographic plate. This spectrum
has separate spectral lines. These lines © grouped into K-series, L-series and M-series. Each series has
various lines as K , K , L, L, M, M etc.
S.Q83 The x-rays produced in a discharge tube experiment are characteristic of the target metal. Justify
it. (RWP-2012)
Ans. The X-rays which are emitted from the surface of the metal depend upon the atomic number of the
metal. Greater the number of protons in the nucleus of metal atom greater the forces of attraction for the
inner- electrons. Greater the energy differences, smaller the wavelength of x-rays.
S.Q84 What is Moseley’s law? (FSD-2008, 2010, 2018, 2007, FSD-2007, MTN-2007, Rwp-2007, FSD-
2008, LHR-2009, GRW-2009, SRG-2010, FSD-2010, Rwp-2010, LHR-2011, FSD-2012, M. Pure-
2012, LHR-2012, D.G. Khan -2012, R. RWP-2012)
Ans. Moseley’s law is the relationship between the frequency of a line of spectrum of x-rays with the atomic
number of the target metal.
= a(Z – b)
where ‘a’ and ‘b’ are constants. This is an equation of straight line, v is frequency and Z is atomic
number of target metal and ‘b’ is screening constant.
S.Q85 Why do we say that the graphs obtained from the Moseley’s law are straight lines? (LHR-2009,
FSD-2010, Rwp-2010)
Ans. According to Moseley’s law, the square root of the frequency of the spectral lines of characteristic x-ray
spectrum of an element varies directly to the atomic number of the element producing the spectrum.
Mathematically
= a(Z – b)
‘a’ and ‘b’ are constants. When is plotted against “Z” then the straight line is obtained.
5.7 WAVE-PARTICLE NATURE OF MATTER (DUAL NATURE OF MATTER) (L.Q)
(LHR-2006, GUJ-2005, LHR-2005, MLT-2005, BHR-2005)
Planck's quantum theory of radiation tells us that light shows a dual character. It behaves both as a
material particle and as a wave. This idea was extended to matter particles in 1924 by Louis de- Broglie.
According to de-Broglie, all matter particles in motion have a dual character. It means that electrons, protons,
neutrons, atoms and molecules possess the characteristics of both the material particle and a wave. This is called
wave-particle duality in matter. de-Broglie derived a mathematical equation which relates the wavelength (k) of
the electron to the momentum of electron.
 = …. (28)
Here  = de -Broglie's wavelength,
m = mass of the particle
v = velocity of electron
According to this equation, the wavelength associated with an electron is inversely proportional to its
Professor CHEMISTRY - XI (Subjective) 213
momentum (mv).
This equation is derived as follows.

According to Planck's equation

E = hv …. (4)
According to Einstein's mass energy relationship
E = mc2 …. (29)
Where 'm' is the mass of the material particle which has to convert itself into a photon, 'and c' is the
velocity of photon. Equating two values of energy;
hv = mc2
Since v =
So = mc2 or  = …. (30)
According to equation (30), the wavelength of photon is inversely proportional to the momentum of
photon. Considering that nature is symmetrical, we apply this equation (30) to the moving electron of mass 'm'
and velocity V. This idea gives us the de-Broglie's equation (28)
= …. (28)
According to equation (28), the wavelength of electron is inversely proportional to momentum of
electron. Now, consider an electron which is moving with a velocity of 2.188  106 ms–1 in the first orbit of
Bohr's model of hydrogen atom. Then, wavelength associating with it, can be calculated with the help of
equation (28).
h = 6.626  10–34 Js
me = 9.108  10–34 kg
 = Since (J = kg m2 s–2)
 = 0.33  10–9 m (10–9 m = 1 nm)
 = 0.33 nm
This value of wavelength (A,) of electron while moving in the first orbit of H-atom is comparable to the
wavelength of X-rays and can be measured.
If we imagine a proton moving in a straight line with the same velocity as mentioned for electron, it's
wavelength will be 1836 times smaller than that of electron. Similarly, an - particle moving with the same
velocity should have a wavelength 7344 times smaller as compared to that of electron. Now, consider a stone of
mass one gram moving with a velocity of 10 ms!, then its wavelength will be:
 =
= 6.626  10–32 m
This wavelength is so small, that it cannot be measured by any conceivable method. It means that
heavy material particles have waves associated with them, but they cannot be captured and we say that
the macroscopic bodies don't have the waves.
5.7.1 Experimental Verification of Dual Nature of Matter
In 1927, two American scientists, Davisson and Germer did an experiment to verify the wave nature of
moving electron. Electrons were produced from heated tungsten filament and accelerated by applying the
potential difference through charged plates. Davisson and Germer proved that the accelerated electrons undergo
diffraction, like waves, when they fall on a nickel crystal. In this way, the wave nature of electron got verified.
Davisson and Germer got the noble prize for inventing an apparatus to prove the matter waves and de Broglie
got the separate nobelprize for giving the equation of matter wave.
S.Q According to de Broglie equation only microscopic bodies have waves? Comment upon it? (BHR-
2007, SRG, MLT & BHR-2008)
Ans. de Broglie relates the wavelength (X) of the electron to the momentum of electron as,  = h/mv
214 Chapter # 5 (Atomic Structure)
The wavelength for a stone of mass 1 g moving with velocity o m/s will be:
 = = 6.626  l0–32m
This wavelength is so small that it cannot be measured and we say that the macroscopic bodies don't
have the waves. Similarly In case of electron moving with velocity of 2.188  l06 m/s, the wavelength
associated with it is 0.33  10–9 m. This value is comparable to the wave of X-rays and can be
measured.
S.Q86 How the wave nature of electron was verified experimentally? GRW-2014
Ans. Dauisson and Germer did an experiment to verify the wave nature of moving electron. They proved that
the accelerated electrons undergo diffraction, like waves, when they fall on a nickel crystal.
S.Q87 Write and explain de-Broglie's equation. (MLT-2008, 2010)
Ans. In 1924, a French scientist, Louis de Broglie, said that all matter particles in motion also have wave-like
properties. This is called wave-particle duality. The de-broglie equation is
 = =
where p = mv = momentum of particle, h = Planck's constant = 6.625  l0–34J s.
This equation shows that particle has both wavelength () and momentum (p). i.e., it has both wave and
particle properties. Thus, it has dual nature.
The wavelength of particle is inversely proportional to its momentum.
S.Q88 Electron has its dual nature. Justify. (SRG-2011)
OR
How Davission and Germer proved dual nature of matter. (BHR-2014: GRW- 2014: AJK-2015)
Ans. In 1924, a French scientist, Louis de Broglie, said that all matter particles in motion also have wave-like
properties. This i called wave-particle duality. He also calculate the wavelength of an electron.
In 1927, two American scientists, Davisson and Germer gave experimental verification of the wave
nature of electron.! bombarded a thin Ni foil with fast moving electrons. They observed that electron's
diffraction was similar to the X -1 diffraction.
Thus, Davisson and Germer verified de-broglie's idea and dual nature of electron.
S.Q89 How the idea of dual nature of matter was deduced from the dual nature of light? (BHR-2007,
MLT-2008, B.P- 2008, SRG-2011)
Ans. According to Planck's quantum theory and mass energy relationship, we can say that
 =
de-Broglie proposed that matter and energy should behave in a similar manner, because nature is
symmetrical. So, he says that the wavelength associated with the election is inversely proportional to the
momentum of the electron.
 =
MCQs
1. Properties of waves are (FSD-2009).
(a) Wave length (b) wave number (c) Frequency (d) All of these
2. De-Broglie's equation is characterized by (D. G. Khan - 2014, 2017)
(a) h = /mv (b) m = h/v (c) m = /hv (d)  = h/mv
3. Which particle has greater wavelength? (GRW-2016)
(a) electron (b) proton (c) neutron (d) -particle
5.8 HEISENBERG'S UNCERTAINTY PRINCIPLE (L.Q) (MLT-03, D.G.K-16, LHR-2014)
According to Bohr's theory, an electron is a material particle and its position as well as momentum
can be determined with great accuracy. But with the advent of the concept of wave nature of electron, it has
not been possible for us to measure simultaneously the exact position and velocity of electron. This was
suggested by Heisenberg, in 1927.
Professor CHEMISTRY - XI (Subjective) 215
Suppose, that x is the uncertainty in the measurement of the position and p is the uncertainty in the
measurement of momentum of an electron, then
x p  …. (31)
This relationship is called uncertainty principle. This equation shows that if x is small then p will be
large and vice versa. So, if one quantity is measured accurately then the other becomes less accurate. Hence,
certainty in the determination of one quantity introduces uncertainty in the determination of the other quantity.
The uncertainty principle is applicable only for microscopic particles like electrons, protons and neutrons, etc.
and has no significance for large particles, i.e. macroscopic particles.
Compton's effect can help us understand the uncertainty principle. Suppose, we wish to determine the
position of electron. Visible light cannot help us, because the wavelength of visible light is millions time large
as compared to the diameter of electron. For this purpose, we have to use X-rays which have very short
wavelength as compared to that of visible light. When this photon of X-rays strikes an electron, the
momentum of electron will change. In other words, uncertainty of momentum will appear due to change of
velocity of electron. Smaller the wavelength of X-rays, greater will be the energy of the photon. Hence, the
collision of X-rays with electron will bring about the greater uncertainty in momentum. So, an effort to
determine the exact position of electron has rendered its momentum uncertain. When we use the photons of
longer wavelength to avoid the change of momentum, the determination of the position of electron becomes
impossible.
S.Q90 State Heisenberg's uncertainty principle and write down its mathematical form/equation/formula
(GRW-2009: FSD-2012: MTN-2010, 2011, 2012, 2015: BHR-2009: LHR-2009, 2013, 2014, 016:
D.G. Khan-2008. 2015: BHR-2011: SHW-2015: RWP-2015)
Ans. It is impossible to determine simultaneously and precisely, both position and momentum of a small fast
mouing particle e.g. electron.
Let uncertainty in position is Ax and uncertainty in momentum is p , then
X.p 
To satisfy, this equation, it is clear that if uncertainty in position i.e., x is small, uncertainty in
momentum i.e., p will be large, and vice versa.
S.Q91 Heisenberg's uncertainty principle has no relation with Bohr's atomic model. Justify it. (Model
Paper-2006-07, BHR-2011, MTN-2012, FSD-2012)
Ans. Since the electron has wavy nature and paths are elliptical as well, so the simultaneous determination of
position and momentum is not possible. But Bohr's model does not accommodate the wavy nature of
electron. He says that the paths are fixed orbits and their orbits are planar. It means that Bohr's model is
very simple as compared to Heisenberg's uncertainty principle.
S.Q92 What is the function of principal quantum number? (AJK-05, GRW-2008, FSD-2009, MLT-2017,
SRG-2013)
Ans. Its values are whole numbers and never zero, negative or fractional. It gives us information about:
(i) energy of electron.
(ii) distance of electron from the nucleus.
S.Q93 What is the function of azimuthal quantum number? (SRG-08, 2011, D.G. Khan- 2012, FSD-2017,
SHW-2016)
Ans. This quantum number (l ) gives us the shape of the orbital.
For l = 0, s-orbital
/ =1, p-orbital
l = 2, d-orbital
l = 3, f-orbital
Its value also determine the energy of electron.
216 Chapter # 5 (Atomic Structure)

S.Q94 Calculate the number of electrons in s, p, d and f sub-shells from the formula.(SRG-2005)
Ans. The formula is 2(2l + 1)
For s-orbital 2(2  0 + 1) = 2 electrons
p-orbital 2(2  1 + 1) = 6 electrons
d-orbital 2(2  2 +1) = 10 electrons
f-orbital 2(2  3 + 0) = 14 electron
MCQs
1. Which equation correctly represents, the Heisenberg's uncertainty principle?
(FSD-2010, SRG-2014).
(a) X  P = (b) X  P >
(c) X  P  (d) X  P 
Concept of Orbital
Following this principle, the Bohr's picture of an atom does not appear to be satisfactory. In Bohr's atom,
the electrons are moving with specific velocities in orbits of specified radii, and according to uncertainty
principle, both these quantities cannot be measured experimentally. A theory involving quantities, which cannot
be measured does not follow the tradition of scientific work.
In order to solve this difficulty, Schrodinger, Heisenberg and Dirac worked out wave theories of the
atom. The best known treatment is that of Schrodinger. He set up a wave equation for hydrogen atom.
According to Schrodinger, although the position of an electron cannot be found exactly, the probability of
finding an electron at a certain position at any time can be found. The solution of the wave equation gives
probability of finding an electron present in a given small region of space. When the probability of finding the
electron at a distance r from the nucleus is calculated for the hydrogen atom in the ground state, Fig (5.19) is
obtained.
The maximum probability of finding the electron is at a distance of
0.053 nm. It is the same radius as calculated for the Bohr's first orbit.
There is a possibility that the electron is either closer to the nucleus or
outside the radius of 0.053 nm, where probability of finding electron
decreases sharply.
The volume of space in which there is 95% chance of finding
an electron is called atomic orbital.
The term orbital should not be confused with the term orbit as used
in the Bohr's theory. The orbital can be regarded as a spread of charge
surrounding the nucleus. This is often called the "electron cloud".
S.Q95 Comparison of orbit and orbital (RWP-2012, LHR-2008, GUJ-2007)
Orbit Orbital
1 It is a definite circular path at a definite 1 It is a space around the nucleus within
distance from the nucleus in which the which the probability of finding an electron
electron moves. with a certain energy is maximum.
2 An orbit shows an exact position of an 2 Orbital does not specify the exact position
electron in an atom. of an electron in an atom.
3 Orbit shows a certainty about the position of 3 According to uncertainty principle, one is
movement of an electron. not sure about the movement of an electron
in an orbit.
4 Orbit gives us the idea about the plane 4 Orbital gives the three dimensional motion
motion of electron. of an electron.
Professor CHEMISTRY - XI (Subjective) 217

5 The maximum number of electrons in an 5 An orbital cannot accommodate more than 2

orbit are given by 2n2. electrons.

S.Q96 What do you mean by orbital? (SRG-2008, LHR-2008)

Ans. The volume of space in which there is 95% chance of finding as electron is called atomic orbital.
The orbitals have no rigid boundary. They wave around the nu and the nucleus is buried in them.
S.Q97 What do you mean by orbit?
Ans. A definite circular path at a definite distance from the nucleus in which the electrons revolve with
definite energy is called orbit oi or energy level. Each orbit is given a specific number called principal
quantum number "n" which has values =1,2,3,4 …….. corresponding to K, L, M, N ……….shells.
S.Q98 Define atomic orbital. What is about the probability of finding electron between the two orbitals.
Ans. The volume of space in which there is 95% chance of finding ar electron is called atomic orbital. The
probability for finding the electron is zero between the two orbitals.
This space is called nodal plane.
S.Q99 What is atomic orbital? Draw the shape of p-orbital (LHR-2010,
2016: LHR-2017)
Ans. The volume of space in which chance of finding an electron is
maximum (95%) is called an orbital. In atoms different types of
orbitals are present e.g. s-orbitals, p-orbital, d-orbtial. F-orbital.
The p-orbitals have three possible orientations in space i.e. px, py and pz

MCQs
1. An orbital which is spherically symmetrical is called (LHR-2009)
(a) s-orbital (b) p-orbital (c) d-orbital (d) f-orbital
2. An orbital which is spherical and symmetrical is: (LHR-2009: GRW-2017).
(a) s-orbital (b) p-orbital (c) d-orbital (d) f-orbital
5.8.1 Quantum Numbers (L.Q)
(FSD-2004, 07, RWP-2007,16, RWP-2005, BHR-2005, MLT-2006,, SRG-2014, LHR-2015,16, GUJ-2016)
Schrodinger wave equation, has been solved for hydrogen atom. It may have different solutions.
Quantum numbers are the sets of numerical values which give the acceptable solutions to Schrodinger wave
equation for hydrogen atom.
An electron in an atom is completely described by its four quantum numbers. You know that a
complete address of a person comprises his name, city in which he lives, the block, street and the house number.
On the similar grounds, quantum numbers serve as identification numbers or labels, which completely describe
an electron. These quantum numbers specify position of electron in an atom.
There are four quantum numbers which can describe the electron completely.
(1) Principal quantum number (n)
(2) Azimuthal quantum number (l)
(3) Magnetic quantum number (m)
(4) Spin quantum number (s)
Let us discuss these quantum numbers one by one.
Principal Quantum Number (n) (L.Q) (FSD-2009, SRG-2005, 14, 15)
The different energy levels in Bohr's atom are represented by 'n'. This is called principal quantum
number by Schrodinger. Its values are non-zero, positive integers upto infinity.
218 Chapter # 5 (Atomic Structure)
n = 1,2,3,4,5, ………
The value of n represents the shell or energy level in which the electron revolves around the nucleus.
Letter notations K, L, M, N, etc are also used to denote the various shells. For example, when n =1, it is called
K shell, for n = 2, it is L shell and so on. The values of n also determine the location of electron in an atom, i.e
the distance of electron from the nucleus, greater the value of 'n' greater will be the distance of electron from the
nucleus. It is a quantitative measure of the size of an electronic shell, 'n' also provides us the energy of electron
in a shell. Bohr's results help us to know the relationships of distance and energy of electron.
Azimuthal Quantum Number (l ) (L.Q) (LHR-2016, SRG-2014,15, RWP-2005, 16, BHR-2008)
It has already been mentioned in the defects of Bohr's model that a spectrometer of high resolving power
shows that an individual line in the spectrum is further divided into several very fine lines. This thing can be
explained by saying that each shell is divided into subshells. So, only principal quantum number (n) is not
sufficient to explain the line spectrum. There is another subsidiary quantum number called azimuthal quantum
number and is used to represent the subshells. The values of azimuthal quantum number (0 are
l = 0,1,2,3, ……….. (n–1)
Its value depends upon n. These values represent different subshells, which are designated by small
letters, s, p, d, f. They stand for sharp, principal, diffused and fundamental, respectively. These are the
spectral terms used to describe the series of lines observed in the atomic spectrum. The values of azimuthal
quantum number always start from zero.
A subshell may have different shapes depending upon the value of 'l'. It may be spherical, dumb-bell, or
some other complicated shaps. The value of ‘l’ is related to the shape of the subshell as follows:
l=0 s-subshell spherical
l=1 p- subshell dumb-bell
l=2 d- subshell (complicated shape)
The relationship between principal and azimuthal quantum numbers is as follows.
n = l K-shell {(l = 0 {s-subshell should be called as 1s
n = 2 L-shell l=0 s-subshell 2s
l=1 p-subshell 2p
n = 3 M-shell l =0 s- subshell 3s
l =1 p- subshell 3p
l =2 d- subshell 3d
n = 4 N-shell, l =0 s-subshell 4s
l =1 p- subshell 4p
l =2 d- subshell 4d
l =3 f- subshell 4f
In Is, 2s, ……. etc, the digit represents the value of principal quantum number.'l' values also enable us to
calculate the total number of electrons in a given subshell. The formula for calculating electrons is 2 (2l + 1).
When l=0 s-subshell total electrons = 2
l=1 p- subshell total electrons = 6
l=2 d-subshell total electrons = 10
l=3 f-subshell total electrons = 14
Magnetic Quantum Number (m) (GUJ-2003, Mirpure -2004, LHR-2015)
In the defects of Bohr's model, it has been mentioned that strong magnetic field splits the spectral lines
further. In order to explain this splitting, a third quantum number called the magnetic quantum number (m) has
been proposed. Its values are
m = 0, ±1, ±2, ±3, …………
The value of'm' depends upon values of 'l '
Professor CHEMISTRY - XI (Subjective) 219
When l = 0 s- subshell m=0
l = 1 p- subshell m = 0, ±1 (p-subshell has three degenerate orbitals)
l = 2 d-subshell m = 0,±1, ±2 (d-subshell has five degenerate orbitals)
l = 2 f- subshell m = 0, ±1, ±2, ±3 (f-subshell has seven degenerate orbitals)
This above description shows that for a given value of l the total values of 'm' are (2l +1). Actually, the
value of m gives us the information of degeneracy of orbitals in space. It tells us the number of different ways in
which a given s, p, d or f-subshell can be arranged along x, y and z-axes in the presence of a magnetic field.
Thus, different values of'm' for a given value off, represent the total number of different space orientations for a
subshell.
In case of s-subshell l = 0, so, m = 0. It implies that s-subshell of any energy level has only one space
orientation and can be arranged in space only in one way along x, y and z-axes. So s-subshell is not sub-divided
into any other orbital. The shape of 's' orbital is such that the probability of finding the electron in all the
directions from the nucleus is the same. It is a spherical and symmetrical orbital. Fig (5.20).
For p-subshell, l = 1 and m = 0, ±1. These values of 'm' imply that p-subshell of any energy level has
three space orientations and can be arranged in space along x, y, and z axes Fig. (5.21). These three orbitals are
perpendicular to each other and named as p x, py, and pz. They have egg shaped lobes which touch each other at
the origin. They are disposed symmetrically along one of the three axes called orbital axis.
In the absence of the magnetic field, all the three p-orbitals have the same energy and are called
degenerate orbitals. Since, they are three in number, so these orbitals are said to be 3-fold degenerate or triply
degenerate.
For d-subshell l = 2 m = 0, ±1, ±2. It implies that it has five space orientations and are designated as
dxy (m = –2), dyz (m = –1), dxz (m = +1), dx2 z2 (m = +2) and d2(m = 0) Fig. (5.22).
All these five d-orbitals are not identical in shape. In the
absence of a magnetic field, all five d-orbitals have the same energy
and they are said to be five fold degenerate orbitals.
For f-subshell, l = 3 and m = 0, ±1, +2, ±3. They have
complicated shapes.
The whole discussion shows that magnetic quantum number
determines the orientation of orbitals, so it is also called orbital
orientation quantum number.
Spin Quantum Number (s) (LHR-2015, MLT-2004)
Alkali metals have one electron in their outermost shell. We can record their emission spectra, when
the outermost electron jumps from an excited state to a ground state. When the spectra are observed by means
of high resolving power spectrometer, each line in the spectrum is found to consist of pair of lines, this is called
doublet line structure. We should keep it in mind, that doublet line structure is different from the fine
spectrum of hydrogen (as we have discussed in azimuthal quantum number). It should be made clear that lines
of doublet line structure are widely separated from each other, while those of fine structure are closely spaced
together.
In 1925, Goudsmit and Uhlenbech suggested that an electron while moving in an orbital around the
nucleus also rotates or spins about its own axis either in a clockwise or anti-clockwise direction. This is also
called self-rotation. This spinning electron is associated with a magnetic field and hence a magnetic moment.
Hence, opposite magnetic fields are generated by the clockwise and anti-clockwise spins of electrons. This spin
motion is responsible for doublet line structure in the spectrum.
The four quantum numbers of all the electrons in the first four shells are summarized in Table (5.3).
Notice, that each electron has its own set of quantum numbers and this set is different for each electron.
Table (5.3) Quantum Numbers of Electrons
Principal Azimuthal Magnetic Spin Number of
Quantum Quantum Quantum electrons
220 Chapter # 5 (Atomic Structure)

number 'n' number V Quantum number's' accommodated

number m'
1 K 0 s 0 +,– 2
0 s 0 +,–
2 L +,–
0 P +1,0,-1
0 s 0 +,–
3 M 1 P + 1,0,-1 +,– 18
2 d +2+1, 0, -1, -2 +,–

0 s
0 +,–
1 p
+ 1,0,-1 +,–
3 N 2 d +,–
32
+2+1,0, -1, -2
3 f +,–
+3, +2+1,0,-1, -2, -3

S.Q100 What will be the position of electron in an atom when (n + l) value is same for two sub shells?
Ans. According to Wiswesser’s (n + 1) rule. Subshells are arranged in the increasing order of (n +1) values
and if any two sub-shell have the same (n + 1) values, then electrons are placed first in that sub-shell
whose n value is smaller.
S.Q101 When azimuthal quantum number has value = 2, what will be the possible values of magnetic
quantum number?
Ans. The values of magnetic quantum number 'm' for l = 2 (d-sub-shell) = +2, +l, 0, –l, –2
These are five values, which means d-subshell has five orbitals.
S.Q102 What is the Significance or function of azimuthal quantum number? (SRG-2008)
Ans. Azimuthal quantum number is used to represent the subshells. The values of azimuthal quantum number
(l) are 0, 1,2,3 (n – 1). Its value depends upon 'n'. These values represent different subshells, which are
designated by small letters, s, p, d, f. The values of azimuthal quantum number always start from zero. A
sub-shell may have different shapes depending upon the value of 'l'. It may be spherical, dumb-bell, or
some other complicated shapes.
S.Q103 Find the values of magnetic quantum number, m, when Azimuthal quantum number, l is 3.
(SRG2014
Ans. When l = 3
m = 0, ±1, ±2, ±3.
S.Q104 Define degenerate orbitals. How degeneracy of orbitals can be lifted? (D.G. Khan-16, LHR-2017)
Ans. The orbitals having equal energy are called degenerate orbitals. The degeneracy of the orbital in space is
given by magnetic quantum number which is calculated by the formula
m = –l ... 0 ... + l or m = 0 , ±l, ...
Example: when t = 1. it is p-subshell, so m = – 1, 0, +1
It means that p-orbitals have three possible orientations in space having equal energy. Thus, p-subshell
is three-fold degenerate or triply degenerate.
S.Q105 Define quantum numbers. What is the significance of Azimuthal quantum number. (D.G.K-2012)
OR Define Azimuthal quantum Number and give its importance. (SRG- 2011: SHW-2016. AJK-2017)
Ans. The quantum number which gives information about Sub-shells is called azimuthal quantum number. It
is denoted by 'l'.
A spectrometer of high resolving power shows that an individual line in a line spectrum of an atom is
actually further divided into several fine lines. It means than an individual shell is further divided into
Professor CHEMISTRY - XI (Subjective) 221
several sub-shells. These sub-shells are explained in terms of azimuthal quantum number.
S.Q106 State spin quantum number(s) briefly. (LHR-2013: GRW-2015)
Ans. It describes the spin of electron is an atom. It is denoted by s.
In 1925. Goudsmit and Uhlenbeck suggested, that an electron also revolve about its axis. This is called
self-rotation. It may be clockwise or anticlockwise. So an electron generates two opposite magnetic
fields due to two opposite spins. This spin motion produces doublet line structure in the emission
spectrum of an atom. It can be explained by spin quantum number. The spin quantum number of an
electron may be + ½ or – ½
S.Q107 Define quantum number. Write names of four types of quantum numbers. (LHR-2014)
Ans. The behavior of electrons in space around the nucleus is described by a set of four numbers called
quantum numbers. These are
(i) Principle quantum number (ii) Azimuthal quantum number
(iii) Magnetic quantum number (iv) Spin quantum number
MCQs
1. Quantum number values for 2p orbitals are: (FSD-2008,13,15, SRG-2016, RWP-2016, LHR-2016,
SHW-2017, SR-2017)
(a)  n = 2, l = 1 (b) n = 1, l = 2 (c) n = 1, l = 0 (d) n = 2 , l = 0

2. Orbital having same energy are called: (FSD-2013, 18, SRG-2012, RWP-2014, LHR-2015, SRG-
2015, FSD-2016, LHR-2017)
(a) Hybrid orbitals (b) Valence orbitals (c) Degenerate orbitals (d) D-orbitals

3. Which 6d orbital is complete, the entering electron goes into: (RWP-12, GRW-2012, FSD-2012,
GRW-2014, GRW-2015, RWP-2015, SHW-2016, RWp-2017, LHR-2017, FSD-2017)
(a) 7f (b) 7s (c) 7p (d) 7d

4. How many unpaired electrons are present in an atom of configuration 1s2, 2s2, 2p4? (GUJ-2008)
(a) 1 (b) 2 (c) 3 (d) 4

5. When 4s orbital is complete, the next coming electron will go into (SRG-2010)
(a) 4s (b) 4p (c) 3d (d) 4f
6. Maximum number of electron is a sub-shell is given by (LHR-2005).
(a) 2l + 1 (b) 2l – 1 (c) 2(2l + 1) (d) 2(2l – 1)
39
7. The number of electrons present in 19K is (MLT-2007)
(a) 18 (b) 19 (c) 20 (d) 39
5.8.2 Shapes of Orbitals (BHR-2006)
In section 5.8.1, we were introduced to the four types of orbitals
depending upon the values of azimuthal quantum number. These
orbitals are s, p, d and f having azimuthal quantum number values as l
= 0, 1, 2, 3, respectively. Let us, discuss the shapes of these, orbitals.
Shapes of s-Orbitals (SRG-2007, 2014, BHR-2009)
s-orbital has a spherical shape and is usually represented by a
circle, which in turn, represents a cut of sphere, Fig. (5.20). With the
increase of value of principal quantum number (n), the size of s-orbital
increases. 2s-orbital is larger in size than ls-orbital. 2s-orbital is also
further away form the nucleus Fig. (5.20). The probability for finding the electron is zero between two
orbitals. This place is called nodal plane or nodal surface.
Shapes of p-Orbitals (BHR-2009, SRG-2007, 2014)
222 Chapter # 5 (Atomic Structure)
There are three values of magnetic quantum number for p-subshell. So, p-subshell has three orientations in
space i.e. along x, y and z-axes. All the three p-orbitals namely, px, py and pz have dumb-bell shapes, Fig.
(5.21). So,p-orbitals have

directional character which determines the geometry' of molecules. All the p- orbitals of all the energy levels
have similar shapes, but with the increase of principal quantum number of the shell their sizes are increased.
Shapes of d-Orbitals
For d subshell there are five values of magnetic quantum number. So, there are five space orientations
along x, yand z-axes. Fig (5.22). They are designated as d xy, dyz, dxz, dx2 – z2, dz2. The lobes of first three d-
orbitals lie between the axis. The other lie on the axis.

They are not identical in shape. Four d-orbitals out of these five contain four lobes each, while the fifth
orbital dz2 consists of only two lobes, Fig (5.22).
In the absence of magnetic field, all the five d-orbitals are degenerate. The shape of f-orbital is very
complicated.
S.Q108 Write down the-names of ‘p’ and ‘d’ orbitals (FSD-2008/s)
Ans. The names of p-orbitals are px, py and pz
The names of d-orbitals are dxy, dyz, dzx, dx2y2 and dz2
S.Q109 What is (n + l) rule?
Ans. This rule says that sub-shells are arranged according to the increasing order of n + l value. The sub-
shell, which has lower value of n + l will be filled first. If any two sub-shells have equal values of n+l,
then that sub-shell is filled first which has less value of ‘n’.
MCQs
1. The relative energies of 4s, 4p and 3d orbitals are in the order (MCAT-2012)
(a) 3d < 4p <4s (b) 4s < 3d < 4p (c) 4p < 4s < 3d (d) 4p < 3d < 4s
2. n = l value of 6d orbital is (BHR-2017, D.G. Khan -2017, LHR-2017).
(a) 8 (b) 9 (c) 10 (d) 11
3. Maximum number of electrons in an orbital isLHR-2014).
(a) 6 (b) 10 (c) 14 (d) 2
Professor CHEMISTRY - XI (Subjective) 223
4. After filling of 4f, the entering electron goes into: (MTN-2013)
(a) 5d (b) 6p (c) 6s (d) 4d
5. Electronic configuration of Manganese (Mn) is (MCAT-2014)
(a) [Ar] 3d2 4s2 (b) [Ar] 3d4 4s2 (c)  [Ar] 3d6 4s2 (d) [Ar] 3d6 4s2
6. When 4s orbital is complete, the electron goes into(SRG-2010: LHR-2014).
(a) 4p orbital (b) 3d (c) 4d (d) 4f
7. Which one of the following pairs has the same electronic configuration as possessed by Neon (Ne-
10)? (MDCAT-2015)
(a) Na+, Cl– (b) K+, Cl– (c) Na+, Mg2+ (d) Na+, F–

5.9 ELECTRONIC DISTRIBUTION

In order to understand the distribution of electrons in an atom, we should know the following facts.
Table (5 > 4) Arrangement of orbitals
n 1 n+1
1s 1 0 1+0=1
2s 2 0 2+0=2
2p 2 1 2 +1=3
3s 3 0 3+0=3
3p 3 1 3+1=4
3d 3 2 3+2=5
4s 4 0 4+0=4
4p 4 1 4+1=5
4d 4 2 4+2=6
4f 4 3 4+3=7
5s 5 0 5+0=5
5p 5 1 5+1=6
5d 5 2 5+2=7
5f 5 3 5+3=8
6s 6 0 6+0=6
6p 6 1 6+1=7
6d 6 2 6+2=8
6f 6 3 6+3=9
7s 7 0 7+0=7
1. An orbital like s, px, py, pz and dxy etc. according to (n+1) rule can have at the most two electrons.
2. The maximum number of electrons that can be accommodated in a shell is given by 2n2 formula where n
is principal quantum number and it cannot have zero value.
Moreover, following rules have been adopted to distribute the electrons in subshells or orbitals.
1. Aufbau principle 2. Pauli's exclusion principle 3. Hund's rule
But, before we use these rules, the subshells should be arranged according to (n + l ) rule, Table(5.4).
This rule says that subshells are arranged in the increasing order of (n + l) values and if any two subshells have
the same (n + t) values, then that subshell is placed first whose n value is smaller.
The arrangement of subshells in ascending order of their energy may be as follows: Is, 2s, 2p, 3s, 3p, 4s,
3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s and so no.
Aufbau Principle (S.Q) (BHR-08,15,17, MLT-2012, FSD-2016, FSD-2017, SRG-2014, LHR-2010)
The electrons should be filled in energy subshells in order of increasing energy values. The electrons are
first placed in Is, 2s, 2p and so on.
Pauli's Exclusion Principle
224 Chapter # 5 (Atomic Structure)
(S.Q) (FSD-2006, 17, SRG-2017, BHR-2015,16, DGK-2006, 16,17, GUJ-2016, MLT-2015, LHR-2007, 10, 2011, 14, 12)
This principle can be stated as follows:
It is impossible for two electrons residing in the same orbital of a poly-electron atom to have the same
values of four quantum numbers, or Two electrons in the same orbital should have opposite spins ().
Hund's Rule (S.Q) BHR-2007, RWP-2015, DGKJ-2010, 2016, SRG-2010,16, FSD-2004, SHW-
2015, MLT-2013, 17, FSD-2013, 2015, 2017)
If, degenerate orbitals are available and more than one electrons are to be placed in them, they should be
placed in separate orbitals with the same spin rather than putting them in the same orbital with opposite spins.
According to the rule, the two electrons in 2p subshell of carbon will be distributed as follows.

6C = 1s 2s 2px 2py 2pz

The three orbitals of 2p subshell are degenerate.
5.9.1 Electronic Configuration of Elements
Keeping in view the rules mentioned above, the electronic configurations of first thirtv six elements are
given in Table (5.5). Table (5.5) Electron configurations of elements
Element Atomic number Electron Configuration Notation
Hydrogen 1 11
Helium 2 Is2
Lithium 3 ls22s
Beryllium 4 ls22s2
Boron 5 ls22s22px 2py 2pz'
Carbon 6 ls22s22px 2py 2pz
Nitrogen 7 ls22s22px 2p 2pz
Oxygen 8 ls22s22p2x 2py2pz
Fluorine 9 ls22s22p2x 2p2y2pz
Neon 10 ls22s22p2x 2p2y2p2z
Sodium 11 [Ne] 3s
Magnesium 12 [Ne] 3s
Professor CHEMISTRY - XI (Subjective) 225

S.Q110 How many electrons can be filled in shells, sub-shells and orbital
Ans. The electrons are filled in orbits or shells according to formula. 2n 2. Where, n = 1, 2, 3, 4,.. The electrons
in sub-shells are filled according to "2 (2l +1)" formula i.e. l = 0 for s-sub-shell = 2 electrons. The
maximum of two electrons can be filled in an oribtal.
S.Q111 Distribute the electron in 29Cu and 35Br. (FSD-2008)
Ans. (i) The electronic configuration of Cu is [Ar]4s1, 3d10
(v) The electronic configuration of Br35 is [Ar], 4s2,3d10, 4p5.
S.Q112 Give the electronic configuration of Ca29 and Br35. (FSD-2009)
Ans. The electronic configuration of Ca29 is [Ar]4s2
The electronic configuration of Br35 is [Ar], 4s2, 3d10, 4p5.
S.Q113 Define atomic number? Write the electronic configuration of oxygen (LHR-2005)
Ans. Atomic number is the number of electrons and protons in an atom. Oxygen has eight electrons and has
the electronic configuration as follows:

O = 1s 2s 2px 2py 2pz

8

S.Q114 Write electronic configuration of elements: (i) Cu (ii) K? (LHR-2008, FSD-2009, 2011, Rwp-2011)
226 Chapter # 5 (Atomic Structure)
Ans. Cu = 1 s2 2s2 2p6 3s2 3p6 4s 3d 3d 3d 3d 3d
29

K = 1s2 2s2 2p6 3s2 3p6 4s

19

S.Q115 What will be the position of electron in an atom when (n + I) value is same for two sub-shells?
(RWP-2008)
Ans. The electron will be accommodated in that orbital whose 'n' value is smaller.
S.Q116 Write the electronic configuration of 26Ca and 35Br. (D.G. Khan -2011)
2 2 6 2 6 2
Ans. 20Ca = 1s 2s 2p 3s 3p 4s
2 2 6 2 6 2 10 5
35Br = 1s 2s 2p 3s 3p 4s 3d 4p .
________________

KEY POINTS
 Matter is made up of extremely small particles called atoms.
 Cathode rays and positive rays were discovered during discharge tube experiments. The properties of
cathode rays showed them to be negatively charged
 Atomic Structure
 particles called electrons, whereas, the positive rays were found to contain positively charged particles
called protons.
 Neutron was discovered through artificial radioactivity.
 Electrons, protons and neutrons are regarded as the fundamental particles of an atom.
 Rutherford discovered the nucleus and successfully explained the presence of moving electrons
around the nucleus.
 In 1905, Planck put forward his famous Planck's quantum theory.
 Neil Bohr explained the structure of hydrogen atom by using Planck's quantum theory. He also
calculated the radius and energy of electron in the nth shell of hydrogen atom.
 Bohr's atomic model successfully explained the origin of line spectrum and the lines present in the
spectrum of hydrogen atom in the visible and invisible regions.
 X-rays are produced when rapidly moving electrons collide with heavy metal anode in the discharge
tube.
 Moseley discovered a simple relationship between the frequency of X-rays and the atomic number of
the target element.
 de-Broglie discovered wave particle duality of material particles. According to him, all material
particles in motion have a dual character. Davisson and Germer experimentally verified the wave
concept of an electron.
 Heisenberg pointed out that it is not possible for us, to measure the exact position and the exact
momentum of electron simultaneously.
 After the failure of Bohr's atomic model, Schrodinger developed the wave- mechanical model of
hydrogen atom. According to him, although the position of an electron cannot be found exactly, the
probability of finding an electron at a certain position at any time can be calculated.
 An electron in an atom is completely described by its four quantum numbers. Three out of these four
quantum numbers, have been derived from Schrodinger wave equation, when it is solved for hydrogen
atom.

EXERCISE
Professor CHEMISTRY - XI (Subjective) 227

Q.1 Fill in the blanks

(i) -particles are nothing but ______ moving with a very high speed.
(ii) The charge on one mole of electrons is ______coulombs.
(iii) The mass of hydrogen atom is______ grams.
(iv) The mass of one mole of electron is ______.
(v) Energy is______when electron j umps from higher to a lower orbit.
(vi) The ionization energy of hydrogen atom can be calculated from______model of atom.
(vii) For d-subshell, the azimuthal quantum number has value of ______.
(viii) The number of electrons in a given subshell is given by formula______.
(ix) The electronic configuration of H is ______.
ANSWERS
(i) electron (ii) 96500 (iii) 1.67 10–24 g (iv) 0.55 mg (v) emitted (vi) Bohr (vii) 2 (viii) 2(2l+1) (ic) 1s2
Q.2 Indicate True or False.
i. A neutron is slightly lighter particle than a proton.
ii. A photon is the massless bundle of energy but has momentum.
iii. The unit of Rydberg constant is the reciprocal of unit of length.
iv. The actual isotopic mass is a whole number.
v. Heisenberg's uncertainty principle is applicable to macroscopic bodies.
vi. The nodal plane in an orbital is the plane of zero electron density.
vii. The number of orbitals present in a sublevel is given by the formula (2^ + 1).
viii. The magnetic quantum number was introduced to explain Zeeman and Stark effect.
ix. Spin quantum number tells us the direction of spin of electron around the nucleus.
ANSWERS
(i) False (ii) True (iii) True (iv) True (v) False (vi) True (vii) True
(viii) True (ix) True
Q. 3. Multiple choice questions. Encircle the correct answer.
(i) The nature of the positive rays depend on
(a) the nature of the electrode (b) the nature of the discharge tube
(c) the nature of the residual gas (d) all of the above
(ii) The velocity of photon is
(a) independent of its wavelength (b) depends on its wavelength
(c) equal to square of its amplitude (d) depends on its source
(iii) The wave number of the light emitted by a certain source is 2  106 m–1. The wavelength of this
light (BHR-2014, MLT-2014, SRG-2015, LHR, SHW-2016, FSD-2014, 17)
(a) 500 nm (b) 500 m (c) 200nm (d) 5l07m
(iv) Rutherford's model of atom failed because
(a) the atom did not have a nucleus and electrons
(b) it did not account for the attraction between protons and neutrons
(c) it did not account for the stability of the atom
(d) there is actually no space between the nucleus and the electrons
(v) Bohr model of atom is contradicted by
(a) Planck's quantum theory (b) dual nature of matter
228 Chapter # 5 (Atomic Structure)
(c) Heisenberg's uncertainty principle (d) all of the above
(vi) Splitting of spectral lines when atoms are subjected to strong electric field is called,
(a) Zeeman effect (b) Stark effect (c) Photoelectric effect (d) Compton effect
(vii) In the ground state of an atom, the electron is present
(a) in the nucleus (b) in the second shell
(c) nearest to the nucleus (d) farthest from the nucleus
(viii) Quantum number values for 2p orbitals are
(a) n = 2, t = 1 (b) n = 1, t = 2 (c) n = 1, l = 0 (d) n = 2, l = 0
(ix) Orbitals having same energy are called (RWP-2009, SRG-, BHR- LHR-2015, FSD-2011,13,16)
(a) hybrid orbitals (b) valence orbitals (c) degenerate orbitals (d) d-orbitals
(x) When 6d orbital is complete, the entering electron goes into (LHR-MLT-2007, RWP-2010, DGK-
2014, RWP, GUJ, LHR-2015, SHW-2016, FSD-2012, 17)
(a)  7f (b) 7s (c) 7p (d) 7d
SHORT QUESTIONS
Q.4 Keeping in mind the discharge tube experiment, answer the following questions.
(a) Why is it necessary to decrease the pressure in the discharge tube to get the cathode rays?
Ans. At ordinary pressure, gases are nonconductor of electricity. The pressure of discharged tube is decreased
to reduce the number of gas molecules, so that the hindrance for the movement of electrons (cathode
rays) reduces and cathode rays can move easily from the cathode to the anode.
(b) Whichever gas is used in the discharge tube, the nature of the cathode rays remains the same.
Why?
Ans. Cathode rays are ejected from the cathode plate at high voltage and low pressure and not from the gas
used in the discharge tube. Therefore, the nature of cathode rays remain the same whichever gas is used
in the discharge tube.
(c) Why e/m value of tue cathode rays is just equal to that of electron?
Ans. Since cathode rays are electrons, so their e/m values Eire just equal to that of electrons.
(d) How the bending of the cathode rays in the electric and magnetic fields shows that they are
negatively charged?
Ans. Cathode rays Eire deflected towards the positive plate when electric field is applied. It shows that
cathode rays are negatively charged. When cathode rays are passed through the magnetic field, they
bend perpendicular to the line joining the two poles. This is also due to the negative charge. Anyhow,
positively charged particles will bend in opposite direction to that of electrons.
(e) Why the positive rays are also called canal rays?
Ans. Small openings, which are present in the cathode plate are called canals. The positive rays pass through
these small openings, so they are also called canal rays.
(f) The e/m values of positive rays for different gases are different, but those for cathode rays the e/m
values are same. Justify it.
Ans. Positive rays are produced by the ionization of gas present in the discharge tube. Therefore, the nature of
particles of positive rays in a discharge tube, depend upon the nature of the gas. The nucleus of every
gas has its own number of protons and neutrons and greater the number of protons and neutrons in the
nucleus of an atom or nuclei of the molecule, smaller are the e/m values. On the other hand, cathode rays
are always electrons; therefore their e/m values remain the same.
(g) The e/m value of the positive rays obtained from the hydrogen gas is 1836 times less than that of
cathode rays.
Ans. When we use hydrogen gas in the discharge tube; the positive rays are consisted of single^ protons. The
Professor CHEMISTRY - XI (Subjective) 229
proton is 1836 times heavier than that of electron, so its e/m value is 1836 times less than that of cathode
rays.
Q. 5 (a) Explain Millikan's oil drop experiment to determine the charge' on an electron. (L.Q)
Ans. Please see article 5.1.8
(b) What is J J Thomson's experiment for determining the e/m value of electron? (L.Q)
Ans. Please see article 5.1.7
(c) Evaluates the mass of electron from the above two experiments. (L.Q)
Ans. Please see article 5.1.8
Q. 6 (a) Discuss the Chadwick experiment for the discovery of neutrons. Compare the properties of
electron, proton and neutron. (L.Q)
Ans. Please see articles 5.1.2 , 5.1.4, 5.1.5 and 5.1.6
(b) Rutherford's atomic model is based on scattering of a-particles from a thin gold foil. Discuss it
and explain the conclusions. (L.Q)
Ans. Please see article 5.2.0
Q.7 (a) Give the postulates of Bohr's atomic model. Which postulate tells us that orbits are stationary
and energy is quantized? (L.Q)
Ans. Please see article 5.4.0
(b) Derive the equation for the radius of nth orbit of hydrogen atom using Bohr's model.
Ans. Please see article 5.4.1
c) How does the equation for the radius of nth Bohr's orbit of hydrogen. —tell you that
(i) Radius is directly proportional to the square of number of orbit.
(ii) Radius is inversely proportional to the number of protons in the nucleus.
Ans. (c) (i) It is clear from the formula, r = that all the quantities in the formula except n and Z are constant.
Therefore, r  n i.e radius is directly proportional to ‘n’
Ans. c (ii) It is also clear from the equation of radius that r  — i.e. radius is inversely proportional to Z,
which is the number of the protons.
Q.7 (d) How do you come to know that the velocities of electrons in higher orbits are less than those in
lower orbits of hydrogen atom?
Ans. We know from the Bohr model that,
mvr =
or v = 
According to this equation, radius and velocities are inverse to each other. Greater the velocity of the
moving electron smaller will be the radius.
Q.7(e) Justify that the distance gaps between different orbits go on increasing from the lower to the
higher orbits.
Ans. According to Bohr's model,
The radius of an orbit is r =
It is clear that r  n2, therefore there will be greater gaps for higher orbits.
Q.8 Derive the formula for calculating the energy of an electron in nth orbit using Bohr's model.
Keeping in view this formula explain the following
(a) The potential energy of the bounded electron is negative
Ans. When electron is free from the nucleus, then potential energy of the system is zero. When electron is
under the force of attraction, the system becomes stabilized and the energy of the system becomes less
than zero, which is definitely negative. This negative potential energy which is calculated is, as
230 Chapter # 5 (Atomic Structure)

(b) Total energy of the bounded electron is also negative

Ans. When the potential and kinetic energies are added up, then the overall answer is negative, because the
value of K.E is –
(c) Energy of an electron is inversely proportional to 'n2' but energies of higher orbits are always
greater than those of the lower orbits.
Ans. The formula for the energy of an electron revolving in any orbit is given by the equation
En = – 2.178  10–18
It is clear from the equation that greater the value of n' greater the value of energy because energy is
negative inverse of n. Therefore, energies of higher orbits are always greater than those of lower orbits.
(d) The energy difference between adjacent levels goes on decreasing sharply.
Ans. If we put the value of n as 1,2,3. . we get the energies of various orbits of hydrogen atom. These values
are as follows
(i) E1 = – 2.18  10–18j (ii) E2 = – 0.54  1018 (iii) E3 = – 0.24  1018 J
It is clear from these values that energy differences between adjacent levels go on decreasing from lower
to the higher level.
Q.9 (a)Derive the following equations for hydrogen atom which are related to
(i) Energy difference between two levels, m and m.
(ii) Frequency of photon emitted when the electron jumps from m to ni.
(iii) Wave number of the photon when the electron jumps from m to ni.
Ans. Please see article 5.5.6
(b) Justify that Bohr's equation for the wave number can explain the spectral lines of Lyman, Balmer
and Paschen series.
Ans. Please see article 5.5.6
Q.10 (a) What is spectrum? Differentiate between continuous spectrum and line spectrum. (L.Q)
Ans. Please see articles 5.5.1 and 5.5.2 ,
(b) Compare line emission and line absorption spectra.
Ans. Please see article 5.5.3 and 5.5.4
(c) What is the origin of line spectrum?
Ans. According to Bohr, when an element, say hydrogen is heated, its electron moves from lower orbit to
higher orbit absorbing a particular wavelength of energy. When it comes back, the same energy is
released as photons of radiation, the spectrum is the line emission spectrum.
Q.11 (a) Hydrogen atom and He+ are mono-electronic systems, but the size of He+ is much smaller than
H+. Why?
Ans. Hydrogen atom and He+ ion both have single electron each in their valance shells but He* ion has two
protons in the nucleus, so it will have greater force of attraction for the single electron. Therefore, the
size of He+ is smaller than H-atom, which has single proton in its nucleus.
rHe+ = 0.529 o = o = 0.2645o
Q.12 (a) Do you think that the size of Li+2 is even smaller than He*. Justify with calculations.
Ans. The size of Li+2 is even smaller than He+, because Li+2 has three protons in the nucleus. It has only one
electron. So,
rLi+2 = 0.529 o = o = 0.176o
Q.12 (a) What are X-rays? What is their origin? How was the idea of atomic number derived from the
discovery of the X-rays? (L.Q)
Ans. Please see article 5.6.0
(b) How does the Bohr's model justify the Moseley's equation? (L.Q)
Professor CHEMISTRY - XI (Subjective) 231
Ans. Please see article 5.6.0
Q.13 Point out the defects of Bohr's model. How these defects are partially covered by dual nature of
electron and Heidelberg's uncertainty principle? (L.Q)
Ans. Please see article 5.5.7
Q.14 (a) Briefly discuss the wave mechanical model of atom. How does it give the idea of orbital?
Compare orbit and orbital.
Ans. Please see article 5.8.0
(b) What are quantum numbers? Discuss their significance.
Ans. Please see article 5.8.1
(c) When azimuthal quantum number has a value of thi;ee, then there are seven values of magnetic
quantum number. Give reasons.
Ans. Please see article 5.8.1
Q.15 (a) Discuss rules" for the distribution of electrons in energy subshells and in orbitals.
Ans. Please see article 5.9.0
(b) What is (n + l ) rule? Arrange the orbitals according to this rule. Do you think that this rule is
applicable to degenerate orbitals?
Ans. Please see article 5.9.0
(c) Distribute the electrons in orbitals of 57La, 29CU, 79Au, 24Cr, 53I and 86Rn.
Ans. The distribution of, electrons in various orbitals of following atoms are as follows.
57La = 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d10, 4p6, 5s2, 4d10, 5p6, 6s2, 5d1
29Cu = 1s2, 2s2, 2p6, 3s2, 3p6, 4s3, 3d10
79Au = 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d10, 4p6, 5s2, 4d10, 5p6, 6s1, 4f14, 5d10
24Cr = 1s2, 2s2, 2p6, 3s2, 3p6,4s1, 3d5
53I = 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d10, 4p6, 5s2, 4d10, 5p5
86Rn = 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d10, 4p6, 5s2, 4d10, 5p6, 6s2, 4f14 5d10, 6p6
Q.16 Draw the shapes of s, p and d orbitals. Justify these by keeping in view the azimuthal and
magnetic quantum numbers. (L.Q)
Ans. Please see article 5.8.2
Q.17 (a) A photon of light with energy 1019 J is emitted by a source of light.
(a) Convert this energy into the wavelength, frequency and wave number of the photon in terms of meters,
hertz and m 1 respectively.
(b) Convert this energy of the photon into ergs and calculate the wavelength in cm. frequency in Hz and
wave number in cm 1
Ans. (a) E = 1019J , h = 6.625  10–34 Js
(i) V =
or  = = = 1.99  10–6 m
(ii) E = hv
or v = = = 1.51  1014 s–1 or Hz
(iii) – = = = 5.03.2  105 m–1
(b) E = 1019 J
1Erg = 10–7 J
Energy in erg = = 1  10–12 ergs
(i)  = = = 1.99  10–4 m
(ii) v = = = 1.509  1014 s–1 or Hz
232 Chapter # 5 (Atomic Structure)
(iii) – = = = 50302 cm–1
Q.18 (a) The formula for calculating the energy of an electron in H-atom is given by Bohr model
Eo =
Calculate the energy of the electron in first orbits of hydrogen atom.
o = 8.85  l012 c2J–1 m–1, h = 6.624  10–34Js, m = 9.108  l0–31 kg, e = 1.60210–19 c
Ans. Formula:
Eo =
Putting values of e, m, h ande0
E1 =
= –2.18  10–18 J
Q.19 Bohr’s equation for the radius of nth orbit of electron in hydrogen atom is
ro =
(a) When the electrons moves from n = 1 to n = 2, how much does the radius of the orbit increases?
(b) What is the distance traveled by electron, when it goes from n = 2 to n = 3 and n= 9 to n= 10.
0 = 8.85  1012 , c2J–l m–l , h = 6.624  10–34 Js,  = 3.14,
m = 9.108  10–3l kg, e = 1.602  10–19c
While doing calculations, take care of units of energy parameter.
[J = kg m2sr2, c = kg1/2m3/2 s–1]
Solution: (a) ro =
r1 = (1) 2
= (1)2  10–10m = 0.529 o
(b) rn = 0.529  (n)2 A
r2 = 0.529A°  (2)2 = 2.116 o
r3 = 0.529A°  (3)2 = 4. 761 o
r3 – r2 = 4.761 – 2.116 = 2. 645o (Ans.)
r9 = 0.529A°  (9)2 = 42.85 o
r10 = 0.529A°  (10)2 = 52. 9o
r10 – r9 = 42.85 – 52.9 = 10. 5o (Ans.)
Q.20 Answer the following questions, by performing the calculations. Calculate the energy of first five
orbits of hydrogen atom and determine the energy difference between them,
Ans. (a) The formula of energy of an electron H-atom is
En = – 2.18  10–18 J
Where 'n' is the number of orbit. Putting values of n , as 1 Ej = -2. 18 x 10 >8 J, n = 2. E2 = - 0.545 x 1 0
18 J, n = 3 Ea = - 0.242 x 10'8J
E4 = – 0. 14  10 18J, n = 0 E5 = – 0.08  10–18J
E2 – E1 = – 0.545  1 0–18 – (–2. 18  10–18) = 1.63  10–18 J
E3 – E2 = – 0.242  10–18 – (– 0.545  1 0–18) = 0.303  10–18 J
E4 – E3 = – 0. 14  10–18 – (– 0.242  10–18) = 1.05  10–18 J and so on
(b) Justify that the energy difference between second and third orbit is approximately five times
smaller than that between first and second.
E2 – E1 = 1.63  10–18J
E3 – E1 = 0.303 10–18J
Hence, the energy difference between second and third orbit is approximately 5 times less than that of
first and second.
(c) Calculate the energy of electron of He* in first five orbits and justify that the energy differences
Professor CHEMISTRY - XI (Subjective) 233

are different from those of hydrogen atom.

Ans. The formula of energy of an electron in He+ (Z = 2) is,
E0 = –2.178  10–18
Where 'n' is the number of orbit. Putting the values of n, as
n = 1, E1 = – 8. 72  10–18 J
n = 2 E2 = – 2.18  1 0–18 J
n = 3 E3 = – 0.968  10–18 J
n = 4 E4 = – 0. 54  10–18 J
n = 5 E5 = – 0.35  10–18 J
The energy differences are greater than those of H- atom. So protons of greater energies are involved in
the electron jumping
(d) Do you think that the groups of the spectral lines of He4 are at different places than those for
hydrogen atom? Give reasons.
Ans. Since energy differences are different from those of H-atom, so the positions of spectral lines will be at
different places on the photographic plate.
Q.21 Calculate the value of principle quantum number, if an electron in H-atom revolves in an orbit of
energy –0.242  10–18 J
Ans. The formula for the energy of electron in H- atom is
E0 = – 2.178 10–18
Since E0 = – 0.242  10–18 J
So – 0.242  10–18 J = 2.18  10–18
n2 = = = 9
n2 = 9
n = 3
Q. 22 Bohr's formula for the energy levels of H-atom for any system say H, He+, Li+2 etc. is
E0 =
or En = – k
For hydrogen, Z = 1 and for He+, Z = 2
(a) Draw an energy level diagram for hydrogen atom and He+.
Ans. The energy level diagrams of H and He+ are similar in the sense that, the differences go on decreasing
from lower to the higher levels, but gaps of energies in He* are more than those of H.
(b) Thinking that k = 2.18  10–18 J, calculate the energy needed to remove the electron from
hydrogen atom and from He+.
Ans. K = 2.18  10–18 J
For H, E1 = k
= – 2.18  10–18  = –2.18  10–18 J
E = – 2.18  10–18  = 000 J
E = E – E1 = 0 – (– 2.18  10–18)
= – 2.18  10–18J
For He+, E1 = –k
234 Chapter # 5 (Atomic Structure)
= – 2.18  10–18  = –8.72  10–18 J
E = – 2.18  10–18  = 000 J
E = E – E1 = 0 – (– 8.72  10–18)
= – 8.72  10–18J
(c) How do you justify that the energies calculation in (b) are the ionization energies of H and He+?
Ans. The amount of energy needed to remove an electron from an atom is called ionization energy.
So the values 2.18  10–18 J and 8.72  10–18 J are the ionization energy values respectively for H and
He+.
(d) Use Avogadro's number to convert ionization energy values in kJ mol' for H and He+.
Ans. Ionization energy value of 'H' in kJ mol–1
E = = 1313.315 kJ mol–1 (Ans.)
Ionization energy value of 'He+' in kJ mol–1
E = = 5249.4 kJ mol–1 (Ans.)
(e) The experimental values of ionization energy of H and He + are 1331 kJ mol–1 and 5250 kJ mol–1
respectively. How do you compare your values with experimental values?
Ans. Theoretical values of l. P are close to the experimental values. Bohr's Model is applicable perfectly to
the mono-electronic systems
Q.23 Calculate the wave number of the photon, when the electron jumps from
(i) n = 5 to n = 2 (ii) n = 5 to n = 1.
In which series of spectral lines these photons will appear?
Ans. We know that.
– = 1.09678  107
Wave number when electron jumps from n = 5 to n = 2
– = 1.09678  107 m–1
– = 1.09678  107 m–1
– = 1.09678  107  m–1 = 2.3032  106 m–1
– = or  = = M–1 = 4.4  10–9m = 434 nm
The photon appears in Balmer series
Wave number when electron ji mps from n = 5 to n = 1
– = 1.09678  107 m–1
– = 1.09678  107 m–1
– = 1.09678  107 m–1
– = 1.09678  107  m–1 = 1.0525  107
– = or  = = m–1 = 9.4  10–8m = 9410–9 nm
The photon appears in Lyman series
Q.24 A photon of a wave number 102.70  105 m is emitted when the electron jumps from higher orbit
to n = 1
(a) Determine the number of that orbit from where the electron Falls.
Ans. We know that
Professor CHEMISTRY - XI (Subjective) 235
– = 1.09678 107 m–1
102.7105 = 1.09678  107 m–1
Or = m–1
or 0.93637 =
0.93637 – 1 = –
– 0.0636 =
n22 =
n2 = = 3.96 = 4
So, the electron falls from n = 4 to n =l(Ans.)
(b) Indicate the name of series to which this photon belongs.
Ans. This photon belongs to Lyman series. (Ans.)
(c) If the electron will fall from that higher orbit to n = 2, then calculate the wave number of the
photon emitted. Why this energy difference is so small as compared to part (a)?
Ans. When the electron falls from n2 = 4 to n1 = 2, the energy difference is small.
– = 1.09678 107 m–1
– = 1.09678  107 m–1
r = 1.09678  107
= 1.09678  107  = 2.05646  106 m–1
Q.25 a) What is de Broglie's wavelength of an electron traveling at half a speed of light? [m = 9.109 
1031kg, c = 3  108 m/s]
Ans. Velocity of light = 3  108 m s–1. So, velocity of electron = c/2 = 1.5  108 ms–1
Mass of electron = 9.108  10–31 kg , Planck's constant = 6.625  10–34 Js
Formula:  =
 =
= 4.848 l0–12m–1
= 0.048  10–10 m = 0.048 o
(b) Convert the mass of electron into grams and velocity of light into cm s >. Calculate the wavelength
of an electron in cm.
Ans. Data: m = 9.109  10–31 kg or 9.109  10–28g, c =1.5  108
or 1.5  1010 cm–1 h = 6.625  10 –34 J.s
Formula:  =
 = = 4.8  10–10 cm (Ans.)
(c) Convert the wavelength of electron from meters to
(i) nm (ii) A (iii) pm
Ans.  = 4.848  1012m
(i) 109 m = 1 nm
4.848  10–12 m = 0.0048 = 4.848  10–3nm (Ans.)
(ii) 1010 m = 1o
4.848  10–12 m = 4.848  10–2 o = 0.04848 o (Ans.)
236 Chapter # 5 (Atomic Structure)
(iii) 10–12 m = l pm
4.348  10–12m = 4.848 pm (Ans.)
LONG QUESTIONS
1. What are Quantum numbers? Discuss their significance? (FSD-2007)
2. How the charge on an electron was determined by Millikan's oil drop method. (FSD-2008)
3. Derive radius of revolving electron in n-th orbit of an atom. (FSD-2009)
4. How Neutrons were discovered? (RWP-2012)
5. Derive the equation for radius of nth orbit of hydrogen atom using Bohr's model.
(FSD-2011, SRG-2012)
6. Write three points of Plank's quantum theory. (FSD-2010)
7. Define frequency and wavelength. (FSD-2010)
8. What are x-rays? Give the conclusions drawn by Mosely from the study of spectral lines.
(FSD-2013)
9. Give four defects of Bohr's atomic model. (FSD-2014)
10. Write down the main postulates of Bohr's theory. (GR/14, RW/FS/15, SW/RW/FS/16)
11. Discuss magnetic and spin quantum numbers.
12. How are positive rays produced in discharge tube? Give properties of these rays.
(GRW-15, SRG-16)
13. Ruther fords atomic model is based on the scattering of -particles from a thin gold foil. Describe
it and explain the conclusion. (RWP-2014)
14. What are quantum numbers? Discuss principal and Azimuthal quantum numbers. (SRG-14)
15. How charge on electron is measured by using Millikan's oil drop method? (LHR-2016)
16. What are quantum numbers? Explain principal and magnetic quantum numbers.

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