Atomic Structure Chemistry

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SUBJECT CHEMISTRY TOPIC ATOMIC STRUCTURE COURSE CODE AISM-09/C/ATS Trans Web Educational Services Pvt. Ltd
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Contents:- Atomic Structure

Fundamental Particles..................................3 Discovery of Electron...................................4 Discovery of Proton.....................................8 Discovery of Neutron..................................12 Atomic Terms............................................13 Atomic Models...........................................17 Electronic Magnetic Radiation.......................24 Atomic Spectrum........................................28 Plancks Quantum Theory.............................29 Bohrs Atomic Model....................................32 Quantum Numbers......................................50 Paulis Exclusion Principle..............................54 Shapes Ans Sizes of Orbitals..........................54 Hunds rule of maximum multiplicity................59 Electronic configuration of elements................60 Dual Character............................................68 Derivation of De-Broglie Equation...................69 Heisenbergs uncertainty principle..76 Quantum mechanical model of model.80 Photoelectric Effect83 Answer to excercises..88 Miscellaneous excercises.89
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FUNDAMENTAL PARTICLES Atoms are made up-essentially, of three fundamental particles, which differ in mass and electric charge as follows:
Electron Symbol e or ep 1
Proton n 1
Neutron
Approximate relative 1/1836 mass Approximate relative charge Mass in kg Mass in amu Actual charge/C 9.109534 5.4858026 1.6021892 10
31 4 19
+1 1.6726485 10
27
0 1.6749543 10
27
10 10
1.007276471 1.6021892 10
19
1.008665012 0
The atomic mass unit (amu) is 1/12th of the mass of an individual atom of
6C 12
, i.e. 1.660565
10
27
kg. The neutron and proton have approximately
equal masses of 1 amu and the electron is about 1836 times lighter; its mass can sometimes be neglected as an approximation. The electron and proton have equal, but opposite, electric charges; the neutron is not charged. The existence of electrons in atoms was first suggested, by J.J. Thomson, as a result of experimental work on the conduction of electricity through gases at low pressures, which produces cathode rays and x-rays, and a study of radioactivity by Becquerel, the Curies and Rutherford. Trans Web Educational Services Pvt. Ltd
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An atom is electrically neutral, and if it contains negatively charged electrons it must also contain some positively charged particles, and the supposition that they existed within atoms came about as a result of Rutherford's experiments in which he bombarded elements with the - rays and -rays were given off by radioactive elements. The neutron was discovered in 1932 by James Chadwick by bombarding beryllium with rays.
DISCOVERY OF ELECTRON: CATHODE RAYS During the latter half of the nineteenth century, it was found that while normally dry gases do not conduct an electric current, they do so under very low pressure and then patches of light are seen. The passage of electricity through gases as studied by a number of physicists, particularly by Faraday, Davy, Crookes and J.J. Thomson. When a current of high voltage (10,000 volts) is passed through a gas of air kept at a very low pressure (0.01 0.03 mm) blue rays are seen emerging from the case. These rays are called Cathode Rays.

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Cathode Rays
Cathode
Fluorescence Glass Tube
To Vacuum Pump
+ (Anode)
CATHODE RAY EXPERIMENT (DISCHARGE TUBE)
Some of the important properties of the cathode rays studied by Sir J.J. Thomson and others are given below:
Cathode rays come out at right angles to the surface of the cathode and move in straight lines. Their path is independent on the position of the anode. They produce phosphorescence on certain salts like ZnS and
fluorescence on glass. They blacken photographic plates. The rays pass through thin sheet of metals. If the metal sheet is too thick to be penetrated the rays cast a shadow. They produce X ray when they strike a metal.

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The rays ionize a gas through which they pass. They heat a substance on which they fall. They rotate a light wheel placed in their paths. This shows that cathode rays contain material particles having both mass and velocity. The mass of a particle present in cathode rays is found to be 1/1837 of H atom. This shows that the particle is of sub atomic nature. Cathode rays are deflected by a magnetic or an electric field showing the particle to be electrically charged, the direction of deflection shows that they are negatively charged. Cathode rays contain the smallest unit of negative charge. No cathode ray was produced when the tube was completely evacuated. Different gases produce same cathode rays as they have the same e/m (charge/mass) ratio. This indicates that the particles present in cathode rays are fundamental constituent of all matter.

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Sir J.J. Thomson named these negatively charged sub atomic particles as electron. A sub atomic particle which is a fundamental constituent of all matter having a mass 1/1837th of a H atom and which carries the smallest unit of negative charge is called an electron. Determination of Velocity and Charge/mass (e/m) ratio of Electrons: Sir J.J. Thomson (1897) extended the cathode ray experiment for the determination of velocity of electrons and their charge/mass ratio, The value of e/m for an electron = 1.76 e/m = 96500/1.008 C/g. Millikans Oil Drop Method: Determination of Charge on an Electron: In 1909, Millikan measured the charge on an electron by his oil drop method. In this method a spray of oil droplets is produced by an atomizer, some of which pass through an opening into a viewing chamber, where we can observe them with a microscope. Often these droplets have an electric charge, which is picked up from the friction forming the oil droplets. A droplet may have one or more additional electrons in it, giving it a negative charge. 108 C/g. For the H+ ion (proton),

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As the droplet falls to the bottom of the chamber, it passes between two electrically charged plates. The droplet can be suspended between them; we adjust the voltage in the plates so that the electrical attraction upward just balances the force of gravity downward. We then use the voltage needed to establish this balance to calculate the mass - to charge ratio for the droplet. Because we already know the mass of the droplet we can find the charge on it. Millikan's found that the charge on all droplets could be expressed as whole number multiples of e, where the value of e is 1.602 10-19 C. By combining e/m. ratio and 'e' we calculate mass of the electron
Me
e e/m
1.6022 10 19 1.76 108
= 9.104 10-31 kg This very small value shows that the electron is a subatomic particle. Thus charge on an electron = 1.602 DISCOVERY OF PROTON: POSITIVE RAYS OR CANAL RAYS Atoms are electrically neutral. Hence after the discovery of the negatively charged constituent (electron) of an atom, attempts were made to discover the positively charged counterpart of electrons. By using a discharge tube Trans Web Educational Services Pvt. Ltd
1019C.
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containing a perforated cathode. Goldstein (1886) found that some rays passed through these holes in a direction opposite to that of the cathode rays.
Cathode Rays
Positive Rays Anode
Cathode To Vacuum Pump

POSITIVE RAYS
These are called the positive rays or canal rays. J.J. Thomson (1910) measured their charge by mass ratio from which he was able to deduce that these contain positive ions. Their properties are: They are positively charged. The positive charge is either equal to or whole number multiple of the charge on an electron. When hydrogen gas was filled in the discharge tube the positive charge on the positive rays was equal to the negative charge on an electron, and the mass was less than the hydrogen atom.

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Unlike cathode rays the properties of positive rays are characteristics of the gas in the tube. The deflection of positive rays under the influence of an electric or magnetic field is smaller than that of the cathode rays for the same strength of field. This shows that the positive rays have a greater mass than that of electrons. The mass of the positive rays depends on the atomic weights or molecular weights of the gases in the discharge tube. The charge/mass ratio also varies because the change in positive charge on the rays. It may be either equal to or integral multiple of the charge on an electron. The lightest of all particles identified in positive rays from different elements was one with a mass very slightly less than that of hydrogen atom (or nearly equal to H atom). The lightest positively charged particle is called a proton (P or P+). Positive rays are atomic or molecular resides from which some electrons have been removed. The removed electrons constitute the cathode rays and the positive residues form the positive or canal rays. Positive Rays H O H+ O+ Cathode Rays e e

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O2 O2
O2+ O22+
e 2e
The mass of a proton is very slightly less than that of a H atom. This shows that protons are sub atomic particles. Protons are fundamental constituent of matter because positive rays are produced by all substances. A sub atomic particle, which is a fundamental constituent of all matter having a mass slightly less than that of H atom and which carries a positive charge equal in magnitude to the charge on an electron, is called a proton. A proton is denoted by p or p+ of
+1p.
Comparison of Positive (Canal) Rays and Cathode Rays: Properties Sign of Charge Mag. of Charge Mass e/m Cathode Rays Negative Always 1 Definite value Definite value Canal Rays Positive Mostly +1, but also +2, +3 Variable, depends on ions Variable, depends on ions
DISCOVERY OF NEUTRON After the discovery of electrons and protons. Rutherford (1920) had predicted the existence of a neutral fundamental particle. In 1932, Chadwick

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bombarded the element Beryllium with
particles and noticed the emission
of a radiation having the following characteristics. The radiation was highly penetrating. The radiation was unaffected by magnetic and electric fields which show that it is electrically neutral. It was found to have approximately the same mass as the protons.
The name neutron was given to this sub atomic particle. It is denoted by n or 1 n . Bombardment of beryllium by o carbon and neutrons are emitted. Be particles results in the formation of
1 0
At present there are a number of evidences which confirm that like electron, proton and neutron is also a fundamental constituent of atoms (a single exception is 1H atom which does not contain any neutron) 1 1024g or 1.6753 1027 kg)
Mass of a neutron is 1.008930 amu (1.6753
Neutron A sub atomic particle, which is a fundamental constituent of matter having mass approximately equal to the hydrogen atom and which is electrically neutral, is called a neutron. Trans Web Educational Services Pvt. Ltd
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Illustration 1: The neutron is attracted towards (A) (B) (C) (D) Solution: Neutron is an uncharged particle. Hence (C) is correct. ATOMIC TERM Nuclide: Various species of atoms in general. Nucleons: Sub-atomic particles in the nucleus of an atom, i.e., protons and neutrons. Isotopes: Trans Web Educational Services Pvt. Ltd
Positive charged particles Negative charged particles Not attracted by any charge None of these
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Atoms of an element with the same atomic number but different mass number. Mass number (A): Sum of the number of protons and neutrons, i.e., the total number of nucleons, Atomic number (Z): The number of protons in the nucleus of an atom. This, when subtracted from A, gives the number of neutrons. Isobars: Atoms, having the same mass numbers but different atomic numbers, e.g., Isotones: Atoms having the same number of neutrons but different number of protons or mass number, e.g.,
14 6
32 15P
and
32 16S .
C,
16 8
O,
15 7
N.
Isoelectronic species: Trans Web Educational Services Pvt. Ltd

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Atoms molecules or ions having the same number of electrons, e.g., N2, CO, CN-. Nuclear isomers: Atoms with the same atomic and mass numbers but different radioactive properties, e.g., uranium X (half life 1.4 min) and uranium Z (half life 6.7 hours). Atomic mass unit: Exactly equal to 1/12th of the mass of 6C12 atom. (a.m.u.): 1 a.m.u. = 1.66 Illustration 2: The ion that is isoelectronic with CO is (A) (C) Solution: Both CO and CN have 14 electrons. Hence (A) is correct CNO2(B) (D) O2+ N2+ 1024 g 931.5 MeV

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Illustration 3. Find the number of neutrons in a neutral atom having atomic mass 23 and number of electrons 11. Solution: Number of protons = number of electrons = 11 Number of neutrons = atomic mass number of protons =2311 = 12 Illustration 4:
30 How many protons, electrons and neutrons are present in 0.18 g 15 P ?
Solution: No. of neutrons in one atom = (30 15) = 15 0.18 g

30 15
P =
0.18 = 0.006 mole 30

30 15
Now, number of
P atoms in 0.006 mole = 0.006

30 15
6.02
1023
Number of electrons in 0.006 mole of mole

30 15
P =Number of protons in 0.006
P = 15
0.006 1022
6.02
1023 = 5.418
1022 and number of
neutrons = 5.418 Exercise 1:

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(i) (ii)
Find the mass number of a uninegative ion having 10 neutrons and 10 electrons in one mole of the ions. Find the total number and total mass of protons present in 34 mg of NH3.
ATOMIC MODELS We know the fundamental particles of the atom. Now let us see, how these particles are arranged in an atom to suggest a model of the atom. Thomsons Model: J.J. Thomson, in 1904, proposed that there was an equal and opposite positive charge enveloping the electrons in a matrix. This model is called the plum pudding model after a type of Victorian dessert in which bits of plums were surrounded by matrix of pudding.
electron Positive sphere
This model could not satisfactorily explain the results of scattering experiment carried out by Rutherford who worked with Thomson.

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Rutherfords Model: particles emitted by radioactive substance were shown to be dipositive Helium ions (He++) having a mass of 4 units and 2 units of positive charge. Rutherford allowed a narrow beam of particles to fall on a very thin gold
foil of thickness of the order of 0.0004 cm and determined the subsequent path of these particles with the help of a zinc sulphide fluorescent screen. The zinc sulphide screen gives off a visible flash of light when struck by an particle, as ZnS has the remarkable property of converting kinetic energy of particle into visible light. [For this experiment, Rutherford specifically used particles because they are relatively heavy resulting in high momentum].
Observation: Majority of the particles pass straight through the gold strip with
little or no deflection. Some particles are deflected from their path and diverge.

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Very few than 90 .
particles are deflected backwards through angles greater
Some were even scattered in the opposite direction at an angle of 180 [Rutherford was very much surprised by it and remarked that It was as incredible as if you fired a 15inch shell at a piece of tissue paper and it came back and hit you]. There is far less difference between air and bullet than there is between gold atoms and distance of nucleus from where the -particle assuming of course that density of a gold atom is evenly distributed. The - particle returns back through 180 is called distance of closet approach and is given by
r0 q1q2 1 4 0 mv 2 2
Conclusions: The fact that most of the - particles passed straight through the
metal foil indicates the most part of the atom is empty. The fact that few deflections to occur - particles are deflected at large angles indicates - particles must have come closer to or collided
the presence of a heavy positively charge body i.e., for such large with a massive positively charged body.

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The fact that one in 20,000 have deflected at 180 backwards indicates that volume occupied by this heavy positively charged body is very small in comparison to total volume of the atom.
Illustration 5: An 10
10
particle is traveling towards gold nuclei returns back through m from it. What is the velocity of the 10
27
- particle. [Given 1
amu = 1.66
kg, atomic mass of He = 4 and gold = 79 and
1 4
0
=9
109 Nm2C 2]
Solution:
We known that ro
q1q2 1 4 0 mv 2 2
v2
2q1q2 4 0mr0
Now one He atom has charge (q1) = 2e One gold atom has charge (q2) = 79e Putting these values we get
v
2
2 1.6 10
19
79 1.6 10
27
19
9 109
4 1.66 10
10
10
v = 3.311
105 m/s

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Conclusions of -Scattering Experiment: On the basis of the above observation, and having realized that the rebounding follows. All the +ve charge and nearly the total mass of an atom is present in a very small region at the centre of the atom. The atoms central core is called nucleus. The size of the nucleus is very small in comparison to the size of the atom. Diameter of the nucleus is about 10 13cm while the atom has a diameter of the order of 108 cm. So, the size of atom is 105 times more than that of nucleus. Most of the space outside the nucleus is empty. The electrons, equal in number to the net nuclear positive charge, revolve around the nucleus with fast speed just like planets around the sun. The centrifugal force arising due to the fast speed of an electron balances the coulombic force of attraction of the nucleus and the Trans Web Educational Services Pvt. Ltd
-particles had met something even more massive than
themselves inside the gold atom, Rutherford proposed an atomic model as
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electron remains stable in its path. Thus according to him atom consists of two parts (a) nucleus and (b) extra nuclear part. Defects in Rutherfords Atomic Model: Position of electrons: The exact positions of the electrons from the nucleus are not mentioned. Stability of the atom: Bohr pointed out that Rutherfords atom should be highly unstable. According to the law of electrodynamics, when a charged body moves under the influence of an attractive force, it loses energy continuously in the form of electromagnetic therefore, radiation. The emit
+
electron
should
continuously
radiation and lose energy. As a result of this a moving electron will come closer and closer to the nucleus and after passing through a spiral path, it should ultimately fall into the nucleus. It was calculated that the electron should fall into the nucleus in less than 108 sec. But it is known that electrons keep moving outside the nucleus. To solve this problem Neils Bohr proposed an improved form of Rutherfords atomic model. Trans Web Educational Services Pvt. Ltd
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Before going into the details of Neils Bohr model we would like to introduce you some important atomic terms. Illustration 6: Prove that density of the nucleus is constant. Solution: Radius of the nucleus = 1.33 number = 1.33 1011 A1/3 m
Mass Volume
kg A
1/ 3 3
1013
A1/3 cm, where A is the mass
Density of nucleus = =
A 1.66 10 4 3 (1.33 10
27 11
=
)
1.66 10 27 3 4 3.14 (1.33 10
11 3
kg/m3 = constant
Thus density of nucleus is constant, independent of the element under consideration. SOME IMPORTANT CHARACTERISTICS OF A WAVE A wave is a sort of disturbance which originates from some vibrating source and travels outward as a continuous sequence of alternating crests and

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troughs. Every wave has five important characteristics, namely, wavelength ( ), frequency ( ), velocity (c), wave number and amplitude (a).
Crest a
Crest
Trough
Trough
Electronic Magnetic Radiation: Ordinary light rays, Xrays, rays, etc. are called electromagnetic radiations because similar waves can be produced by moving a charged body in a magnetic field or a magnet in an electric field. These radiations have wave characteristics and do not require any medium for their propagation. Wavelength ( ): The distance between two neighbouring troughs or crests is known as wavelength. It is denoted by and is expressed in cm, m, nanometers (1 nm =109 m) or Angstrom (1 =1010 m). Frequency ( ): The frequency of a wave is the number of times a wave passes through a given point in a medium in one second. It is denoted by (nu) and is expressed in cycles per second (cps) or hertz (Hz) 1Hz = 1cps. The frequency of a wave is inversely proportional to its wave length ( ) Trans Web Educational Services Pvt. Ltd
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or
Velocity: The distance travelled by the wave in one second is called its velocity. It is denoted by c and is expressed in cm sec 1.
c=
or
Wave number is denoted by
: It is defined as number of wavelengths per cm. It and is expressed in cm1.
or
Amplitude: It is the height of the crest or depth of the trough of a wave and is denoted by a. It determines the intensity or brightness of the beam of light. Electromagnetic Spectrum: The arrangement of the various types of electromagnetic radiation in order of increasing or decreasing wavelengths or frequencies is known as electromagnetic spectrum.
Wavelengths of Electromagnetic Radiations:

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Electromagnetic radiations Radio waves Micro waves Infrared (IR) 1.1.1 Visible Ultra violet (UV) Xrays Gamma rays Cosmic rays
Wave length () 3 1014 to 3 107 3 109 to 3 106 6 106 to 7600 7600 to 3800 3800 to 150 150 to 0.1 0.1 to 0.01 0.01 to zero
Illustration 7: Find out the longest wavelength of absorption line for hydrogen gas containing atoms in ground state. Solution:
RZ 2
1 2 n1
1 2 n2
For longest wavelength from n = 1 to n = 2
E should be smallest, i.e. transition occurs

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n=7 n=6 n=5 n=4 n=3
n=2 n=1
i.e.
= 109673 cm1
12
1 12
1 22
= 109673
3 4
cm1
4 3 109673cm
= 1.2157
105 cm = 121.6 nm
Illustration 8: Calculate the energy in kJ per mole of electronic charge accelerated by a potential of 1 volt. Solution: Energy in joules = charge in coulombs = 1.6 1019 = 9.632 6.02 1023 1 104 J or 96.32 kJ Trans Web Educational Services Pvt. Ltd
potential difference in volt
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Exercise 2: (i) What is the ratio between energies of two radiations one with a wavelength of 6000 and other with 2000 . (ii) Find the frequency and wave number of a radiation having wavelength of 1000 . ATOMIC SPECTRUM If the atom gains energy the electron passes from a lower energy level to a higher energy level, energy is absorbed that means a specific wave length is absorbed. Consequently, a dark line will appear in the spectrum. This dark line constitutes the absorption spectrum. If the atom loses energy, the electron passes from higher to a lower energy level, energy is released and a spectral line of specific wavelength is emitted. This line constitutes the emission spectrum. Types of Emission Spectra: Continuous spectra: When white light from any source such as sun or bulb is analyzed by passing through a prism, it splits up into seven different wide bands of colour from violet to red (like rainbow). These Trans Web Educational Services Pvt. Ltd
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colour are so continuous that each of them merges into the next. Hence the spectrum is called as continuous spectrum. Line spectra: When an electric discharge is passed through a gas at low pressure light is emitted. If this light is resolved by a spectroscope, It is found that some isolated coloured lines are obtained on a photographic plate separated from each other by dark spaces. This spectrum is called line spectrum. Each line in the spectrum corresponds to a particular wavelength. Each element gives its own characteristic spectrum. PLANCKS QUANTUM THEORY When a black body is heated, it emits thermal radiations of different wavelengths or frequency. To explain these radiations, Max Planck put forward a theory known as Plancks quantum theory. The main points of quantum theory are Substances radiate or absorb energy discontinuously in the form of small packets or bundles of energy. The smallest packet of energy is called quantum. In case of light the quantum is known as photon.

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The energy of a quantum is directly proportional to the frequency of the radiation. E 6.626 1034 Jsec. (or) E = h where is the frequency of radiation 1027 erg sec or and h is Plancks constant having the value 6.626
A body can radiate or absorb energy in whole number multiples of a quantum h , 2h ,3h ..nh . where n' is the positive integer. Neils Bohr used this theory to explain the structure of atom.
Illustration 9. The wave number of a radiation is 400 cm 1. Find out its (a) (c) (e) Solution: Wavelength J per photon kJ per mol of photons (b) Frequency (d) kcal per mol of photons
(a) (b) (c)
or
c
1 400 cm
= 2.5
103 cm 400 cm1 = 1.2 10 7 s 1
= c
=3
hc
1010 cm/s = h c 1034 Js 3
Ephoton = h =
= 6.626
108 cm/s
400 cm1

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= 7.95 (d) Ephoton = 7.95
1021J 1021J 1021J 6.022 1023 mol1 103 J mol1) (1 kcal/4184 J)
For 1 mol of photon energy = 7.95 = (4.7875 (e) E = (4.7875 = 1.14 kcal mol 1
103 J mol1) (1 kJ/1000J)
= 4.7875 kJ mol 1 Illustration 10: A near ultraviolet photon of 300 nm is absorbed by a gas and then re emitted as two photons. One photon is red with wavelength 760 nm. What would be the wavelength of the second photon? Solution:
E=
hc
Wavelength of the 1st photon = E1 =

hc
1
And that of second photon = E2 =

hc
2
ETotal = E1 + E2= emitted energy

hc hc
1
hc
2

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1 300 1
2
1 760 1 300
1
2
1 760
1
2
760 300 760 300
= wavelength of the second photon = 496 nm
BOHRS ATOMIC MODEL Bohr developed a model for hydrogen atom and hydrogen like oneelectron species (hydrogenic species). He applied quantum theory in considering the energy of an electron bound to the nucleus. Important Postulates: An atom consists of a dense nucleus situated at the centre with the electron revolving around it in circular orbits without emitting any energy. The force of attraction between the nucleus and an electron is equal to the centrifugal force of the moving electron. Of the finite number of circular orbits around the nucleus, an electron can revolve only in those orbits whose angular momentum (mvr) is an integral multiple of factor h 2 mvr =
nh 2
where, m = mass of the electron Trans Web Educational Services Pvt. Ltd
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v = velocity of the electron n = orbit number in which electron is present r = radius of the orbit As long as an electron is revolving in an orbit it neither loses nor gains energy. Hence these orbits are called stationary states. Each stationary state is associated with a definite amount of energy and it is also known as energy levels. The greater the distance of the energy level from the nucleus, the more is the energy associated with it. The different energy levels are numbered as 1,2,3,4, (from nucleus onwards) or K, L, M, N etc. Ordinarily an electron continues to move in a particular stationary state without losing energy. Such a stable state of the atom is called as ground state or normal state. If energy is supplied to an electron, it may jump (excite)
instantaneously from lower energy (say 1) to higher energy level (say 2, 3, 4, etc.) by absorbing one or more quanta of energy. This new state of electron is called as excited state. The quantum of energy absorbed is equal to the difference in energies of the two concerned levels. Since the excited state is less stable, atom will lose its energy and come back to the ground state. Trans Web Educational Services Pvt. Ltd
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Energy absorbed or released in an electron jump, ( E) is given by E = E 2 E1 = h where E1 and E2 are the energies of the electron in the first and second energy levels, and Note: If the energy supplied to hydrogen atom is less than 13.6 eV, it will accept or absorb only those quanta which can take it to a certain higher energy level i.e., all those photons having energy less than or more than a particular energy level will not be absorbed by hydrogen atom. But if energy supplied to hydrogen atom is more than 13.6 eV then all photons are absorbed and excess energy appears as kinetic energy of emitted photo electron. Radius and Energy Levels of Hydrogen Atom: Consider an electron of mass m and charge e revolving around a nucleus of charge Ze (where, Z = atomic number and e is the charge of the proton) with a tangential velocity v. r is the radius of the orbit in which electron is revolving. is the frequency of radiation absorbed or emitted.

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By Coulombs Law, the electrostatic force of attraction between the moving electron and nucleus is Coulombic force =
KZe2 r2
K=
1 4
o
(where
is permittivity of free space)
K = 9 109 Nm2 C2 In C.G.S. units, value of K = 1 dyne cm2 (esu)2
The centrifugal force acting on the electron is
mv 2 r
Since the electrostatic force balances the centrifugal force, for the stable electron orbit.
mv 2 KZe2 = 2 r r
(1)
or
v2 =
KZe2 mr
(2)
According to Bohrs postulate of angular momentum quantization, we have
mvr =
nh 2

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v=
nh 2 mr
2 2 v2 = n2 h 2
4 m r2
(3)
Equating (2) and (3)
KZe2 mr
n2h2 4 2m2r 2
Solving for r we get r =
n2h2 4 me2
2
Where n = 1, 2, 3 - - - - Hence only certain orbits whose radii are given by the above equation are available for the electron. The greater the value of n, i.e., farther the energy level from the nucleus the greater is the radius. The radius of the smallest orbit (n=1) for hydrogen atom (Z=1) is ro.
ro
n2h2 = 2 2 = 4 me K 4
12 3.14
2
6.626 10
31
34
9 10
1.6 10
19
9 10
=5.29
1011 m=0.529
Radius of nth orbit for an atom with atomic number Z is simply written as Trans Web Educational Services Pvt. Ltd
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rn = 0.529
n2 Z
Calculation of Energy of an Electron: The total energy, E of the electron is the sum of kinetic energy and potential energy. Kinetic energy of the electron = mv 2
Potential energy =
KZe2 r
Total energy = 1/2 mv2
KZe2 r
(4)
From equation (1) we know that
mv 2 KZe2 = r r2
mv2 =
KZe2 2r
Substituting this in equation (4)
Total energy (E) =
KZe2 KZe2 = 2r r
KZe2 2r

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Substituting for r, gives us
E=
22mZ2e4K 2 n2h2
where n = 1, 2, 3.
This expression shows that only certain energies are allowed to the electron. Since this energy expression consist of so many fundamental constant, we are giving you the following simplified expressions.
E = 21.8 1012
Z2 erg per atom n2
= 21.8 1019
Z2 J per atom n2
= 13.6
Z2 eV per atom n2
(1eV = 3.83 1023 kcal 1eV = 1.602 1012 erg 1eV = 1.602 1019J)
E = 313.6
Z2 kcal / mole (1 cal = 4.18 J) n2

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The energies are negative since the energy of the electron in the atom is less than the energy of a free electron (i.e., the electron is at infinite distance from the nucleus) which is taken as zero. The lowest energy level of the atom corresponds to n=1, and as the quantum number increases, E becomes less negative. When n = , E = 0, which corresponds to an ionized atom i.e., the electron
and nucleus are infinitely separated. H H++ e (ionization).
Calculation of Velocity: We know that
mvr =
nh nh ;v = 2 mr 2
By substituting for r we get
v=
2 KZe2 nh
Where except n and Z all are constants

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v = 2.18 108
Z n
cm/sec.
Further application of Bohrs work was made, to other one electron species (Hydrogenic ion) such as He+ and Li2+. In each case of this kind, Bohrs prediction of the spectrum was correct. Illustration 11: The velocity of electron in the second orbit of He will be (A) (C) Solution:
2.18 106 m / s
(B) (D)
1.09 106 m / s
4.36 106 m / s
None of these
vn
v0 Z n
. Hence (A) is correct.
Illustration 12: Calculate the velocity of an electron in Bohrs first orbit of hydrogen atom (Given r = 0.53 1010 m)
Solution:

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According to Bohrs theory mvr =

nh 2 or v nh 2 mr
r = 0.53
1010m 1034kg m2 s1, m = 9.1

34
n = 1, h = 6.62 v=
22 2 (9.1 10 7
31
1031 kg 106 m/s
1 (6.62 10
kgm2 s 1 )
10
= 2.18
m)
kg) (0.53 10
Illustration 13: The velocity of e in first Bohrs orbit is 2.17 velocity in 3rd orbit of He2+ ion. Solution: 106 m/s. Calculate the
vn = v 0
Z n
6 Hence v = 2.19 10 2 = 1.45
106 m/s
HYDROGEN ATOM If an electric discharge is passed through hydrogen gas taken in a discharge tube under low pressure, and the emitted radiation is analyzed with the help of spectrograph, it is found to consist of a series of sharp lines in the UV, visible and IR regions. This series of lines is known as line or atomic Trans Web Educational Services Pvt. Ltd
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spectrum of hydrogen. The lines in the visible region can be directly seen on the photographic film. Each line of the spectrum corresponds to a light of definite wavelength. The entire spectrum consists of six series of lines, each series, known after their discoverer as the Balmer, Paschen, Lyman, Brackett, Pfund and Humphrey series. The wavelength of all these series can be expressed by a single formula.
=R
1 2 n1
1 n2 2
Where,
= wave number = wave length
R = Rydberg constant (109678 cm1) n1 and n2 have integral values as follows Series Lyman Balmer Paschen Brackett Pfund n1 1 2 3 4 5 n2 2, 3, 4, etc 3, 4, 5 etc 4, 5, 6 etc 5, 6, 7 etc 6, 7, etc Main spectral lines Ultra violet Visible Infra red Infra red Infra red

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Note: All lines in the visible region are of Balmer series but reverse is not true. i.e., all Balmer lines will not fall in visible region] The pattern of lines in atomic spectrum is characteristic of hydrogen. Illustration 14: Find the wavelength of a spectral line produced when an electron in the H-atoms jumps from 4th level to 2nd level. Solution:
RH
1 2 n1
1 n2 2
109678
1 22
0
1 cm 42
16 cm 3 109678
= 4863 A Merits of Bohrs Theory: The experimental value of radii and energies in hydrogen atom are in good agreement with that calculated on the basis of Bohrs theory.

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Bohrs concept of stationary state of electron explains the emission and absorption spectra of hydrogen like atoms. The experimental values of the spectral lines of the hydrogen spectrum are in close agreement with that calculated by Bohrs theory.
Limitations of Bohrs Theory It does not explain the spectra of atoms having more than one electron. Bohrs atomic model failed to account for the effect of magnetic field (Zeeman effect) or electric field (Stark effect) on the spectra of atoms or ions. It was observed that when the source of a spectrum is placed in a strong magnetic or electric field, each spectral line further splits into a number of lines. This observation could not be explained on the basis of Bohrs model. De Broglie suggested that electrons like light have dual character. It has particle and wave character. Bohr treated the electron only as particle. Another objection to Bohrs theory came from Heisenbergs
Uncertainty Principle. According to this principle It is impossible to determine simultaneously the exact position and momentum of a small Trans Web Educational Services Pvt. Ltd
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moving particle like an electron. The postulate of Bohr, that electrons revolve in well defined orbits around the nucleus with well defined velocities is thus not tenable. Illustration 15: The radii of two of the first four Bohr orbits of the hydrogen atom are in the ratio 1 : 4. The energy difference between them may be (A) (C) Solution: 0.85 eV 3.40 eV (B) (D) 2.55 eV 8.20 eV
rn
r0n2 and En Z
E0 Z2 . Hence (B) is correct. n2
Illustration 16: An electron in a hydrogen atom in its ground state absorbs 1.50 times as much energy as the minimum required for its escape from the atom. What is the wavelength of the emitted electron? (me = 9.11 1031 kg) (A) (C) Solution: Trans Web Educational Services Pvt. Ltd
4.7 9.4
(B) (D)
4.7 nm 9.40 nm
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Since 13.6 eV is need for ionization Total energy absorbed = 1.5 13.6eV 20.4eV 6.8 eV is converted into K.E.
h 2m KE 6.625 10 2 9.11 10
31 34 19
= 4.7 10 10 m 4.7
6.8 1.6 10
Hence (A) is correct. Illustration 17: The observation that electrons can be diffracted is an evidence that electrons (A) (C) Solution: Diffraction prove wave character of electron. Hence (B) is correct. have particle properties (B) are emitted by atoms (D) have wave properties are absorbed by ions

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Illustration 18: A series of lines in the spectrum of atomic hydrogen lies at wavelengths 656.46, 482.7, 434.17, 410.29 wavelength of next line in this series? Solution: The given series of lines are in the visible region and thus appears to be Balmer series Therefore n1 = 2 and n2=? for next line If = 410.29 107 cm and n1 = 2 n2 may be calculated for the last line
1
nm.
What
is
the
=R
1 2 n1
1 2 n2
1 410.29 10
= 109673
1 22
1 n2 2
n2 = 6 Thus next line will be obtained during the jump of electron from 7 th to 2nd shell i.e,
1
=R
1 22
1 72
= 109673
1 4
1 49
= 397.2 107 cm = 397.2 nm Illustration 19:

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Find the energy released in (ergs) when 2.0 gm atom of hydrogen undergo transition giving spectral line of lowest energy in visible region of its atomic spectrum. Solution:
E = 2.178
1018 (Z2)
1 2 n1
1 J / atom n2 2
For visible photon, n1 = 2 For lowest energy transition n2 = 3 E = 2.178 For 2.0g atom E = (2 6.023 1023) 2.178 1018
5 36
1018
12
1 22
1 32
J/atom
joules
= 3.63 Illustration 20:
105J = 3.63
1012 ergs
Which hydrogen like ionic species has wavelength difference between the first line of Balmer and first line of Lyman series equal to 59.3 109 m? Neglect the reduced mass effect. Solution:

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Wave number of first Balmer line of an species with atomic number Z is given by
RZ2
5RZ2 36
1 22
1 32
; Similarly wave number of v of first Lyman line is given by

1 1 22
= RZ2 12
= RZ 2 ;
36 5RZ2
3 4
and
4 3
4 = 1 2 36 2 RZ 5 3RZ
88 15RZ2
Z2 = or
59.3 10
88 15 1.097 107
=9
Z=3
ionic species is Li 2+ Exercise 3: (i) Calculate of of the radiations when the electron jumps from III to II atoms are 5.42 1012 and 2.41 1012 erg
orbit of hydrogen atom. The electronic energy in II and III Bohr orbit hydrogen respectively. (ii) In a hydrogen atom, the energy of an electron in first Bohrs orbit is 13.12 105 J mol1. What is the energy required for its excitation to Bohrs second orbit.

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(iii)
What is the wavelength of the light emitted when the electron in a hydrogen atom undergoes transition from an energy level with n = 4 to an energy level with n =? What is the colour corresponding to this wavelength? (Rydberg constant = 109,677 cm 1)
QUANTUM NUMBERS An atom contains large number of shells and subshells. These are distinguished from one another on the basis of their size, shape and orientation (direction) in space. The parameters are expressed in terms of different numbers called quantum numbers. Quantum numbers may be defined as a set of four numbers with the help of which we can get complete information about all the electrons in an atom. It tells us the address of the electron i.e., location, energy, the type of orbital occupied and orientation of that orbital. Principal quantum number (n): It tells the main shell in which the electron resides, the approximate distance of the electron from the nucleus and energy of that particular electron. It also tells the maximum number of electrons that a shell can accommodate is 2n 2, where n is the principal quantum number. Shell K L Principal quantum number (n) 1 2 Trans Web Educational Services Pvt. Ltd
M 3
N 4
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Maximum number of electrons
18
32
Azimuthal or angular momentum quantum number : This represents the number of subshells present in the main shell. These subsidiary orbits within a shell will be denoted as 0, 1, 2, 3, 4, or s, p, d, f This tells the shape of the subshells. The orbital angular momentum of the electron is given as particular value of n where possible
or
1 for a
h 2
. For a given value of n values of
vary from 0 to n 1.
The magnetic quantum number (m): An electron due to its angular motion around the nucleus generates an electric field. This electric field is expected to produce a magnetic field. Under the influence of external magnetic field, the electrons of a subshell can orient themselves in certain preferred regions of space around the nucleus called orbitals. The magnetic quantum number determines the number of preferred orientations of the electron present in a subshell. The values allowed depends on the value of l, the angular momentum quantum number, m can assume all integral values between to + including zero. Thus m can be 1, 0, +1 for associated with a particular value of

= 1. Total values of m
is given by 2 + 1.
The spin quantum number (s): Just like earth which not only revolves around the sun but also spins about its own axis, an electron in an atom not only revolves around the nucleus but also spins about Trans Web Educational Services Pvt. Ltd
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its own axis. Since an electron can spin either in clockwise direction or in anticlockwise direction, therefore, for any particular value of magnetic quantum number, spin quantum number can have two values, i.e., +1/2 and 1/2 or these are represented by two arrows pointing in the opposite directions, i.e., and . When an electron goes to a vacant orbital, it can have a clockwise or anti clockwise spin i.e., +1/2 or 1/2. This quantum number helps to explain the magnetic properties of the substances. Illustration 21: If the principal quantum number n has a value of 3, what are permitted values of the quantum numbers and m? Solution: If principal quantum number (n) has the value of 3, subsidary quantum number () will also have three values i.e. 0, 1 and 2 and magnetic quantum number (m) will have n 2, i.e. 32 i.e. 9 values in all and they are designated as under: n=3 = 0 m = 0 (s) = 1 m = 1 (p) m=0 m=+1 = 2 m = 2 (d) Trans Web Educational Services Pvt. Ltd
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m=1 m=0 m = +1 m = +2 Illustration 22: In which orbital the electron will reside if it has the following values of quantum numbers. (i) (ii) n = 3, 1, m 0 n = 4, 0, m 0
Solution: (i) (ii)

1 for p subshell and m = 0 for pz orbital.
Hence electron will residue in 3pz orbital.

0 for s subshell. Hence electron will residue in 4s orbital.
Illustration 23: Write all the quantum numbers for the following orbitals. (i) 3 d z
2
(ii) 3s
(iii) 4px
Solution:

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(i) (ii) (iii)
n
n n
3,
3, 4,
2, m
0, m 1 m ,
0, s
0, s 1 or
1/ 2
1/ 2 1s , 1/ 2
Paulis Exclusion Principle: According to this principle, an orbital can contain a maximum number of two electrons and these two electrons must be of opposite spin. Two electrons in an orbital can be represented by
or
SHAPES AND SIZE OF ORBITALS An orbital is the region of space around the nucleus within which the probability of finding an electron of given energy is maximum (9095%). The shape of this region (electron cloud) gives the shape of the orbital. It is basically determined by the azimuthal quantum number , while the orientation of orbital depends on the magnetic quantum number (m). Let us now see the shapes of orbitals in the various subshells.

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sorbitals: These orbitals are spherical and symmetrical probability of about the nucleus. electron The is
y
finding
the
maximum near the nucleus and keep on decreasing as the distance from the nucleus increases. There is vacant space between two successive sorbitals known as radial node. But there is no radial node for 1s orbital since it is starting from the nucleus. The size of the orbital depends upon the value of principal quantum number (n). Greater the value of n, larger is the size of the orbital. Therefore, 2sorbital is larger than 1s orbital but both of them are non-directional and spherically symmetrical in shape. porbitals ( =1): The probability of finding the pelectron is maximum in two lobes on the opposite sides of the nucleus. This gives rise to a dumbbell shape for the porbital. For porbital
1s nucleus x 2s
radial node
= 1. Hence, m = 1, 0, +1. Thus, porbital have
three different orientations. These are designated as p x, py & pz depending upon whether the density of electron is maximum along the x y and z axis respectively. As they are not spherically symmetrical, they have directional character. The two lobes of porbitals are separated by a nodal plane, where the probability of finding electron is zero. Trans Web Educational Services Pvt. Ltd
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Y py Z
X px
pz
The three p-orbitals belonging to a particular energy shell have equal energies and are called degenerate orbitals. dorbitals ( = 2): For dorbitals, l = 2. Hence m = 2,1, 0, +1, +2. Thus there are 5d orbitals. They have relatively complex geometry. Out of the five orbitals, the three (dxy, dyz,dzx) project in between the axis and the other two dz
dx2
y2
2
and
lie along the axis.

Z X
Y
dz 2 dx 2
y2
Doughnut shape or Baby soother shape

X X
Clover leaf shape
Y dxy dxz
Z dyz

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Illustration 24:
An electron has a spin quantum number number 1. It cannot occupy a/an (A) (C) Solution: For s orbital m = 0. Hence (D) is correct. Illustration 25: d orbital p orbital (B) (D) f orbital s orbital
1 2
and a magnetic quantum
Which d-orbital has electron density in all the planes? Solution: orbital has lobe along Z-axis and a belt of electrons in xy plane.
dz 2
Hence it has electron density in all xy, xz and yz plane. RULES FOR FILLING OF ELECTRONS IN VARIOUS ORBITALS The atom is built up by filling electrons in various orbitals according to the following rules. Trans Web Educational Services Pvt. Ltd
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Aufbau Principle: This principle states that the electrons are added one by one to the various orbitals in order of their increasing energy starting with the orbital of lowest energy. The increasing order of energy of various orbital is 1s,2s,2p,3s,3p,4s,3d,4p,5s,4d,5p,6s,4f,5d,6p,5f,6d,7p How to remember such a big sequence? To make it simple we are giving you the method to write the increasing order of the orbitals. Starting from the top, the direction of the arrow gives the order of filling of orbitals.
1s 2s 3s 4s 5s 6s 7s 2p 3p 4p 5p 6p 3d 4d 5d 4f
Alternatively, the order of increasing energies of the various orbitals can be calculated on the basis of (n + ) rule.

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The energy of an orbital depends upon the sum of values of the principal quantum number (n) and the azimuthal quantum number ( ). This is called (n + ) rule. According to this rule, In neutral isolated atom, the lower the value of (n + ) for an orbital, lower is its energy. However, if the two different types of orbitals have the same value of (n + ), the orbitals with lower value of n has lower energy. Illustration of (n + ) Rule:
Type of Value Values Values of orbitals of n 1s 2s 2p 3s 1 2 2 3 of
(n+ ) 1+0=1 2+0=2 2+1=3 3+1=4
Relative energy Lowest energy Higher energy than 1s orbital 2p orbital (n=2) have lower energy than 3s orbital (n=3)
0 0 1 0
Hunds Rule of Maximum Multiplicity: This rule deals with the filling of electrons in the equal energy (degenerate) orbitals of the same sub shell (p, d and f). According to this rule, Electron pairing in p,d and f orbitals cannot occur until each orbital of a given subshell contains one electron each or is singly occupied.

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This is due to the fact that electrons being identical in charge, repel each other when present in the same orbital. This repulsion can, however, be minimized if two electrons move as far apart as possible by occupying different degenerate orbitals. All the electrons in a degenerate set of orbitals will have same spin. Electronic Configuration of Elements: Electronic configuration is the distribution of electrons into different shells, subshells and orbitals of an atom. Keeping in view the above mentioned rules, electronic configuration of any orbital can be simply represented by the notation]
Number of electrons in the subshell
x
n
Principal quantum number
Symbol of subshell or orbitals (s,p,d,f)
Alternatively: Orbital can be represented by a box and an electron with its direction of spin by arrow. To write the electronic configuration, just we need to know (i) the atomic number (ii) the order in which orbitals are to be filled (iii) maximum number of electrons in a shell, subshell or orbital. Each orbital can accommodate two electrons Trans Web Educational Services Pvt. Ltd
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The number of electrons to be accomodated in a subshell is 2 numbers of degenerate orbitals. Subshell s p d f Maximum number of electrons 2 6 10 14
The maximum number of electrons in each shell (K, L, M, N) is given by 2n2 where n is the principal quantum number. The maximum number of orbitals in a shell is given by n 2 where n is the principal quantum number.
Importance of Knowing the Electronic Configuration: The chemical properties of an element are dependent on the relative arrangement of its electrons. Illustration 26: Write the electronic configuration of nitrogen (atomic number = 7)

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Solution:
1s
2s
2p
Illustration 27: Write the electronic configuration of following: (i)

S2 z 16 (ii) Fe2 z 26
Solution: (i) (ii)
1s2 2s2 2p6 3s2 3p6

1s2 2s2 2p6 3s2 3p6 3d6
Exceptional Configurations: Stability of Half Filled and Completely Filled Orbitals: Cu has 29 electrons. Its expected electronic configuration is 1s22s22p63s23p64s23d9 But a shift of one electron from lower energy 4s orbital to higher energy 3d Trans Web Educational Services Pvt. Ltd
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orbital will make the distribution of electron symmetrical and hence will impart more stability. Thus the electronic configuration of Cu is 1s2 2s22p63s23p64s13d10 Fully filled and half filled orbitals are more stable. Illustration 28: Which of the following metals has the highest value of exchange energy required for exchange stabilization? (A) (C) Solution: Cu has full filled d-subshell. Hence (C) is correct. Illustration 29: The total spin resulting from a d7 configuration is (A) (C) 1
5 2
Mn Cu
(B) (D)
Cr Zn
(B) (D)
2
3 2

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Solution: S = n/2, where n = number of unpaired electrons = 3. Hence (D) is correct. Illustration 30: The electronic configuration of an element is 1s 22s22p63s23p63d54s1. This represents its (A) (C) Solution: It is ground state electronic configuration of Cr. Hence (B) is correct. Illustration 31: Write the electronic configuration of the following ions: (A) (C) Solution: H+ O2 (B) (D) Na+ F excited state cationic form (B) (D) ground state anionic form

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(A) (B) (C) (D)
1s0 1s22s22p6 1s22s22p6 1s22s22p6
Illustration 32: We know the Hunds rule. Explain how to arrange three electrons in p orbitals. Solution: The important point to be remembered is, all the singly occupied orbitals should have parallel spins, i.e in the same direction eitherclockwise or anticlockwise. 2px 2py 2pz
= 1 The maximum multiplicity means that the total spin of unpaired electrons is maximum.

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Illustration 33: We know that fully filled and half filled orbitals are more stable. Can you write the electronic configuration of Cr(Z = 24)?. Solution: Cr (Z = 24) 1s2, 2s2,2p6,3s2,3p6,4s1,3d5. Since half filled orbital is more stable one 4s electron is shifted to 3d orbital. Illustration 34: The configuration of potassium (19) is 1s22s22p63s24s1 and not 1s22s22p63s23p63d1. Why? Solution: According to Aufbau Principles electron first fill in a sub-level of lower energy level (lower n+). The energy of 4s(4 + 0 = 4) is lower than that of 3d (3 + 2 = 5), so the electronic configuration of K is 1s22s22p63s23p64s1.

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Illustration 35: How many maximum number of electrons can be present in 3rd shell of an atom? Solution: Total number of electrons in a shell = 2n 2 =2 Illustration 36: How many maximum number of electrons a d-orbital can have? Solution: Any orbital can have maximum of 2 electrons. Illustration 37: Calculate the total number of d-electrons in molybdenum (atomic number = 42). Solution: 32 = 18

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Electronic configuration of Mo is
1s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d4
Hence, total number of d-electrons = 10 + 4 = 14 Exercise 4: (i) Write the electronic configuration of the following: (a) Cr3+ (b) Mn2+ (c) Cu (ii) Write the orbital rotation for the following quantum numbers. (a) (b) (c)
n = 4, = 2
n = 2, = 1
n = 3, = 0
DUAL CHARACTER (PARTICLE AND WAVE CHARACTER OF MATTER AND RADIATION) In case of light some phenomenon like diffraction and interference can be explained on the basis of its wave character. However, the certain other phenomenon such as black body radiation and photoelectric effect can be

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explained only on the basis of its particle nature. Thus, light is said to have a dual character. Such studies on light were made by Einstein in 1905. Louis de Broglie, in 1924 extended the idea of photons to material particles such as electron and he proposed that matter also has a dual character-as wave and as particle. Derivation of de-Broglie Equation: The wavelength of the wave associated with any material particle was calculated by analogy with photon. In case of photon, if it is assumed to have wave character, its energy is given by E=h (i)
(according to the Plancks quantum theory) where is the frequency of the wave and h is Plancks constant
If the photon is supposed to have particle character, its energy is given by E = mc2 (ii)

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(according to Einsteins equation) where m is the mass of photon, c is the velocity of light. By equating (i) and (ii) h But = mc2 = c/
= mc2
(or)
= h /mc
The above equation is applicable to material particle if the mass and velocity of photon is replaced by the mass and velocity of material particle. Thus for any material particle like electron.
= h/mv
or
h p
where mv = p is the momentum of the particle.
Relation Between Kinetic Energy and Wavelength: K.E (E)=1/2 mv2

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v=
2E m
h mv
h 2E.m
Derivation of Angular Momentum from de Broglie Equation: According to Bohrs model, the electron revolves around the nucleus in circular orbits. According to de Broglie concept, the electron is not only a particle but has a wave character also. If the wave is completely in phase, the circumference of the orbit must be equal to an integral multiple of wave length ( ) Therefore 2 r = n
where n is an integer and r is the radius of the orbit But = h/mv or mvr = n h/2
2 r = nh /mv
which is Bohrs postulate of angular momentum, where n is the principal quantum number. Trans Web Educational Services Pvt. Ltd
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Thus, the number of waves an electron makes in a particular Bohr orbit in one complete revolution is equal to the principal quantum number of the orbit. Alternatively:
Number of waves n
2 r
2 mvr 2 r = h h mv
Where v and r are the velocity of electron and radius of that particular Bohr orbit in which number of waves are to be calculated, respectively. The electron is revolving around the nucleus in a circular orbit. How many revolutions it can make in one second? Let the velocity of electron be v m/sec. The distance it has to travel for one revolution 2 r, (i.e., the circumference of the circle).
Thus, the number of revolutions per second is =
v 2 r
Common unit of energy is electron volt which is amount of energy given when an electron is accelerated by a potential of exactly 1 volt. This energy equals the product of voltage and charge. Since in SI units

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coulombs
volts = joules, 1 eV numerically equals the electronic charge
except that joule replaces coulombs. Illustration 38: An e-, a proton and an alpha particle have K.E of 16 E, 4 E and E respectively. Whats the qualitative order of their Broglie wavelengths? (A) (C) Solution:
e P
> <
P e
> <
a a
(B) (D)
e a
> <
p e
= =
a P
h 2mK.E
. Hence (B) is correct.
Illustration 39: Calculate the de Broglie wavelength of a ball of mass 0.1 kg moving with a speed of 60 ms1. Solution:
h mv
6.6 10 34 0.1 60
= 1.1
1034 m.

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This is apparent that this wavelength is too small for ordinary observation. Although the de Broglie equation is applicable to all material objects but it has significance only in case of microscopic particles. Since, we come across macroscopic objects in our everyday life, de Broglie relationship has no significance in everyday life. [Distinction between the wave- particle nature of a photon and the particle- wave nature of a sub atomic particle]: Photon 1. 2. Energy = h Wavelength =
c
Sub Atomic Particle Energy =

1 mv2 2 h mv
Wavelength =
Note: We should never interchange any of the above Illustration 40: Calculate the number of waves made by electron in 4th Bohrs orbit. Solution: Trans Web Educational Services Pvt. Ltd
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Number of waves made by electron in n th orbit = n Hence the number of waves in 4rd orbit = 4 Illustration 41: What is the de-Broglie wavelength of electron having K.E. of 5 eV? Solution:
K.E. =
v
1 mv 2 2
2K.E. m
h mv
Now,
= =
h 2K.E. m
6.62 10 2 5 1.6 10
19 34
9.1 10
31
= 5.486 Illustration 42:
10
10
Through what potential difference an electron must be accelerated to have a de-Broglie wavelength of 1 A .
o

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Solution: = 10
10
m
1 mv 2 2 eV
We know K.E. = v= Now Hence v

2eV m
h mv h
2eVm
h2 2 2 em
6.62 10 2 10
10
34
1.6 10
19
9.1 10
31
= 1.5
106 volt
HEISENBERGS UNCERTAINTY PRINCIPLE All moving objects that we see around us e.g., a car, a ball thrown in the air etc., move along definite paths. Hence their position and velocity can be measured accurately at any instant of time. Is it possible for subatomic particle also? As a consequence of dual nature of matter, Heisenberg, in 1927 gave a principle about the uncertainties in simultaneous measurement of position and momentum (mass This Principle States: Trans Web Educational Services Pvt. Ltd
velocity) of small particles.
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It is impossible to measure simultaneously the position and momentum of a small microscopic moving particle with absolute accuracy or certainty i.e., if an attempt is made to measure any one of these two quantities with higher accuracy, the other becomes less accurate. The product of the uncertainty in position ( x) and the uncertainty in the momentum ( p = m. v where m is the mass of the particle and uncertainty in velocity) is equal to or greater than h/4 Plancks constant. Thus, the mathematical expression for the Heisenbergs uncertainty principle is simply written as x. p h/4 v is the where h is the
Explanation of Heisenbergs uncertainty principle Suppose we attempt to measure both the position and momentum of an electron, to pinpoint the position of the electron we have to use light so that the photon of light strikes the electron and the reflected photon is seen in the microscope. As a result of the hitting, the position as well as the velocity of the electron are disturbed. The accuracy with which the position of the particle can be measured depends upon the wavelength of the light used. The uncertainty in position is . The shorter the wavelength, the greater is the accuracy. But shorter wavelength means higher frequency and hence Trans Web Educational Services Pvt. Ltd
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higher energy. This high energy photon on striking the electron changes its speed as well as direction. But this is not true for macroscopic moving particle. Hence Heisenbergs uncertainty principle is not applicable to macroscopic particles. Illustration 43: Why electron cannot exist inside the nucleus according to Heisenbergs uncertainty principle? Solution: Diameter of the atomic nucleus is of the order of 10 15m The maximum uncertainty in the position of electron is 10 15 m. Mass of electron = 9.1 1031 kg. x. p = x v=
h 4
(m. v) = h/4
h 4 1 6.63 10 = 22 x.m 4 7
34
10
15
1 9.1 10
31
v = 5.80 possible. Illustration 44:
1010 ms1
This value is much higher than the velocity of light and hence not

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What is the uncertainity in the position of electron, if uncertainity in its velocity is 0.0058 m/s? Solution:
h 4 m
6.02 10 34 4 3.14 9.1 10 31 0.0058
x = 0.01 m Illustration 45: What is the uncertainity in the position of a ball of mass 10 g and which is moving with a velocity of 100 m/s with 0.002 % uncertainity? Solution:
h 4 m v 100 0.002 100 0.002 m/ s
Now
x
6.02 10 34 4 3.14 9.1 10 31 0.002
0.0289 m
Exercise 5:

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(i)
Two particles A and B are in motion. If the wavelength associated with particle A is 5 108 m, calculate the wavelength associated with particle B if its momentum is half of A.
(ii)
Calculate the de Broglie wavelength of an electron that has been accelerated from rest through a potential difference of 1 kV.
(iii)
Calculate the uncertainty in position of a particle when uncertainty in the momentum is (a) 1 102 gm cm sec1 and (b) zero.
QUANTUM MECHANICAL MODEL OF ATOM The atomic model which is based on the particle and wave nature of the electron is known as wave or quantum mechanical model of the atom. This was developed by Erwin Schrodinger in 1926. This model describes the electron as a three dimensional wave in the electronic field of positively charged nucleus. Schrodinger derived an equation which describes wave motion of an electron. The differential equation is
2 2
2 2
8 2m (E V) h2
where x, y, z are certain coordinates of the electron, m = mass of the electron E = total energy of the electron. V = potential energy of the electron; h = Plancks constant and (psi) = wave function of the electron. Trans Web Educational Services Pvt. Ltd
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Significance of
: The wave function may be regarded as the amplitude
function expressed in terms of coordinates x, y and z. The wave function may have positive or negative values depending upon the value of coordinates. The main aim of Schrodinger equation is to give solution for probability approach. When the equation is solved, it is observed that for some regions of space the value of favour of .
2
is negative. But the probability must

2
be always positive and cannot be negative, it is thus, proper to use
in
Significance of
is a probability factor. It describes the probability of
finding an electron within a small space. The space in which there is maximum probability of finding an electron is termed as orbital. The important point of the solution of the wave equation is that it provides a set of numbers called quantum numbers which describe energies of the electron in atoms, information about the shapes and orientations of the most probable distribution of electrons around nucleus. Nodal Points and Planes: The point where there is zero probability of finding the electron is called nodal point. There are two types of nodes: Radial nodes and angular nodes. The former is concerned with distance from the nucleus while latter is concerned with direction.

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No. of radial nodes = n 1
No. of angular nodes = Total number of nodes = n 1 Nodal planes are the planes of zero probability of finding the electron. The number of such planes is also equal to . Illustration 46: Calculate radial nodes and angular nodes for the following type of orbitals. (a) (c) (e) Solution: (a) (c) (e) 0, 0 1, 1 3, 0 (b) (d) (f) 0, 1 0, 2 1, 2 1s 3p 4s (b) (d) (f) 2p 3d 4d

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PHOTOELECTRIC EFFECT Sir J.J. Thomson, observed that when a light of certain frequency strikes the surface of a metal, electrons are ejected from the metal. This phenomenon is known as photoelectric effect and the ejected electrons are called photoelectrons. A few metals, which are having low ionization energy like Cesium, show this effect under the action of visible light but many more show it under the action of more energetic ultraviolet light.
Light
electrons
Evacuated quartz tube
An evacuated tube contains two electrodes connected to a source of variable voltage, with the metal plate whose surface is irradiated as the anode. Some of the photoelectrons that emerge from this surface have enough energy to reach the cathode despite its negative polarity, and they constitute the measured current. The slower photoelectrons are repelled before they get to Trans Web Educational Services Pvt. Ltd
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the cathode. When the voltage is increased to a certain value V 0, of the order of several volts, no more photoelectrons arrive, as indicated by the current dropping to zero. This extinction voltage (or also referred as stopping potential) corresponds to the maximum photoelectron kinetic energy i.e., eVo = mv2 The experimental findings are summarised as below: Electrons come out as soon as the light (of sufficient energy) strikes the metal surface. The light of any frequency will not be able to cause ejection of electrons from a metal surface. There is a minimum frequency, called the threshold (or critical) frequency, which can just cause the ejection. This frequency varies with the nature of the metal. The higher the frequency of the light, the more energy the photoelectrons have. Blue light results in faster electrons than red light. Photoelectric current is increased with increase in intensity of light of same frequency, if emission is permitted i.e., a bright light yields more photoelectrons than a dim one of the same frequency, but the electron energies remain the same. Light must have stream of energy particles or quanta of energy (h ). Suppose, the threshold frequency of light required to eject electrons from a Trans Web Educational Services Pvt. Ltd
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metal is
0,
when a photon of light of this frequency strikes a metal it
imparts its entire energy (h 0) to the electron.
E=h
E>h
K. E = 0 Metal
K.Emax = h h
This energy enables the electron to break away from the atom by overcoming the attractive influence of the nucleus. Thus each photon can eject one electron. If the frequency of light is less than ejection of electron. If the frequency of light is higher than
0 0
there is no (let it be ),
the photon of this light having higher energy (h ), will impart some energy to the electron that is needed to remove it from the atom. The excess energy would give a certain velocity (i.e, kinetic energy) to the electron. h =h h =h + K.E + mv2
mv2 = h h where,
= frequency of the incident light Trans Web Educational Services Pvt. Ltd
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0
= threshold frequency = h
is the threshold energy (or) the work function denoted by
(minimum energy of the photon to liberate electron). It is constant for particular metal and is also equal to the ionization potential of gaseous atoms. The kinetic energy of the photoelectrons increases linearly with the frequency of incident light. Thus, if the energy of the ejected electrons is plotted as a function of frequency, it result in a straight line whose slope is equal to Plancks constant h and whose intercept is h 0.
K.E of Photoelectrons
Illustration 47: Work function of sodium is 2.5 eV. Predict whether the wavelength 6500 A is suitable for a photoelectron ejection or not. Solution:
o

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Energy of incident light
hc
6.62 10 34 5 108 6500 10 10
= 3.055 = 1.9 eV
10
19
Which is lower than work function. Hence no ejection will take place. Exercise 6: (i) Find the threshold wavelengths for photoelectric effect from a copper surface, a sodium surface and a caesium surface. The work function of these metal are 4.5 eV, 2.3 eV and 1.9 eV respectively. (ii) Energy required to stop the ejection of electrons from Cu plate is 0.24 eV. Calculate the work function when radiation of strikes the plate? = 253.7 nm

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ANSWER TO EXERCISES Exercise 1: (i) (ii) 19 (a) (b) Exercise 2: 1.2044 2.01 1022 105 kg
(i) (ii)
E1 E2
v
hc
1
2 1
hc
2000 6000
107 m
1
1 3
3 1015 Hz,
Exercise 3: (i) (ii) (iii) 6603 9.84 105 J mol 1 486 nm, Blue
Exercise 4: (i) (a) (b) (c)
1s2 2s2 2p6 3s2 3p6 3d3

1s2 2s2 2p6 3s2 3p6 3d5 1s2 2s2 2p6 3s2 3p6 3d10 4s1

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(ii)
(a) (b) (c)
4d 2p 3s
Exercise 5: (i) (ii) (iii) 107 m 3.87 (a) (b) Exercise 6: (i) (ii) 276 nm, 540 nm, 654 nm 4.65 eV 1011 m 5.27 1028m

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MISCELLANEOUS EXERCISES Exercise 1: Calculate the ratio of specific charge (e/m) of a proton and that of an -particle. Exercise 2: What is the fraction of volume occupied by the nucleus with respect to the total volume of an atom? Exercise 3: Calculate the minimum and maximum values of wavelength in Balmer series of a H atom. Exercise 4: The wave number of the first line of Balmer series of hydrogen is 15,200 cm 1. What is the wave number of the first line of Balmer series for the Li 2+ ion? Exercise 5:

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What possible can be the ratio of the de Broglie wavelengths for two electrons having the same initial energy and accelerated through 50 volts and 200 volts? Exercise 6: What is likely to be the principle quantum number for a circular orbit of diameter 20 nm of the hydrogen atom if we assume Bohr orbit to be the same as that represented by the principle quantum number? Exercise 7: Calculate the uncertainty in the velocity of a particle weighing 25.0 g if the uncertainty in position is 10 10
34 5
m. (given Planck constant h = 6.6
Js).
Exercise 8: Calculate the de Broglie wavelength of a tennis ball of mass 60.0 g moving with a velocity of 10 metres per second (Planck constant, h = 6.63 Exercise 9: 10
34
Js).

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Suppose 1017 J of energy is needed by the interior of human eye to see an object. How many photons of green light ( needed to generate this minimum amount of energy? Exercise 10: Ionization potential of hydrogen atom 13.6 eV. If hydrogen atom in ground state excited by monochromatic light of energy 12.1 eV, then what will be the total spectral lines emitted according to Bohrs theory? = 550 nm) are

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ANSWERS TO MISCELLANEOUS EXERCISES Exercise 1: 1:2 Exercise 2: 10

15
Exercise 3: 3647 nm and 6564 nm Exercise 4: 1,36,800 cm Exercise 5: 2:1 Exercise 6: 14 Trans Web Educational Services Pvt. Ltd
1
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Exercise 7: 2.1 10
28
Exercise 8: 10
33
Exercise 9: 28 Exercise 10: 3

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SOLVED PROBLEMS
Subjective:
Board Type Questions Problem 1: Why are Bohrs orbits are called stationary states? Solution: This is because the energies of orbits in which the electrons revolve are fixed. Problem 2: Explain why the electronic configuration of Cu is 3d 104s1 and not 3d94s2. Solution: In the 3d104s1 the d-subshell is completely filled which is more stable. Problem 3: Trans Web Educational Services Pvt. Ltd
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Fe3+ ion is more stable than Fe2+ ion. Why? Solution: In Fe3+ ion 3d subshell is half filled hence more stable configuration. Problem 4: Calculate the accelerating potential that must be applied to a proton beam to give it an effective wavelength of 0.005 nm. Solution:
v
eV
h m
1 mv 2 2
Putting the values we get V = 32.85 volt Problem 5: Give one example of isodiapheres. Solution: Trans Web Educational Services Pvt. Ltd
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Isodiapheres have same difference between the number of neutrons and protons. For example
39 19 n p 1
K &
31 15 n p 1

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IIT Level Questions Problem 6: Which electronic transition in Balmer series of hydrogen atom has same frequency as that of n = 6 to n = 4 transition in He +. [Neglect reduced mass effect]. Solution:
He
RZ2
1 42
1 62
= 4R
H
36 16 36 16
=
1
5R 36
1
=R
12 22 n2
vH
R n2
vHe
5R R = 4 36
On solving above equation n2 = 9 n=3 Or corresponding transition from 3 atom has same frequency as that of 6 Problem 7: Trans Web Educational Services Pvt. Ltd
2 in Balmer series of hydrogen 4 transition in He+.
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Calculate ionization potential in volts of (a) He + and (b) Li2+ Solution:
I.E. = =
13.6Z2 n2 13.6 Z2 [Z =2 for He+] 12
= 13.6
4 = 54.4 eV
13.6 3 2 12
Similarly for Li 2+ =
= 13.6 Problem 8:
9 = 122.4 eV
Calculate the ratio of K.E and P.E of an electron in an orbit? Solution:
K.E. = P.E. =
Ze2 2r Ze2 r
P.E. = 2K.E
K.E 1 =P.E 2
Problem 9: Trans Web Educational Services Pvt. Ltd

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How many spectral lines are emitted by atomic hydrogen excited to nth energy level? Solution:
1 1 2 3 2 3
1 4 5 6 3
n=6 n=5 n=4 n=3 n=2 n=1
1 1+2=3 1+2+3= 6
Thus the number of lines emitted from nth energy level = 1 + 2 + 3 + n 1 = n=

n n 1 2
(n 1)
(n 1) =
n 1 n 1 1 2
n 1 n 2
Number of spectral lines that appear in hydrogen spectrum when an electron jumps from nth energy level =
n n-1 2
Problem 10: Calculate (a) the de Broglie wavelength of an electron moving with a velocity of 5.0 (h = 6.63 105 ms1 and (b) relative de Broglie wavelength of an atom of hydrogen and atom of oxygen moving with the same velocity 1034 kg m2 s1) Trans Web Educational Services Pvt. Ltd
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Solution:
(a)
h mv
6.63 10 9.11 10
31
34
kgm2 s
2 5 1
kg 5.0 10 ms
Wavelength (b)
= 1.46
109m
An atom of oxygen has approximately 16 times the mass of an atom of hydrogen. In the formula
h mv
, h is constant while the
conditions of problem make v, also constant. This means that and m are variables and varies inversely with m. Therefore, for for the hydrogen atom would be 16 times greater than oxygen atom. Problem 11: A 1 MeV proton is sent against a gold leaf (Z = 79). Calculate the distance of closest approach for head on collision. Solution: K.E. = P.E.
1 mv 2 2 1 Ze2 4 0 d
Ze2 1 4 0 mv 2 2
Hence d =

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9 109 79
1.6 10
13
19
1.6 10
1.137 10
13
as 1 MeV
1.6 10
13
Problem 12: What is the wavelength associated with 150 eV electron Solution:
= =
h 2 m K.E.
6.626 10 2 9.1 10
31 34
Js
19
=
J
6.626 10 4368 10
34 50
= 1010 m = 1
kg 150 1.6 10
Problem 13: The energy of electron in the second and third Bohr orbit of the hydrogen atom is 5.42 1012 erg and 2.41 1012erg, respectively. Calculate the wavelengths of emitted radiation when the electron drops from third to second orbit. Solution:

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E3 E2 = h =
6.626 10
27
hc
2.41
1012
5.42
1012)
3 1010
27 3 1010 = 6.626 10 12
3.01 10
= 6.604 Problem 14:
105 cm = 6.604
105 108 = 6604
O2 undergoes photochemical dissociation into one normal oxygen and one excited oxygen atom, 1.967 eV more energetic than normal. The dissociation of O2 into two normal atoms of oxygen atoms requires 498kJ mole1. What is the maximum wavelength effective for photochemical dissociation of O2? Solution: O2 O2 ON + Oexcited ON + ON
E = 498 103 J / mole =

498 103 J 6.023 1023
per molecule = 8.268 1019 J
Energy required for excitation = 1.967 eV = 3.146 1019J Total energy required for photochemical dissociation of O2 = 8.268 1019 + 3.146 1019 = 11.414 1019 J
hc
= 11.414 1019J

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34 3 108 = 6.626 10 = 1.7415 107 m = 1741.5 19
11.414 10
Problem 15: Compare the wavelengths for the first three lines in the Balmer series with those which arise from similar transition in Be 3+ ion. (Neglect reduced mass effect). Solution:
vH
R 12
1 22 1 22
1 n2 1 n2
vBe
R 42
vBe vH
H Be
= 16
So we can conclude that all transitions in Be 3+ will occur at wavelengths

1 times the hydrogen wavelengths. 16

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Objective:
Problem 1: For a p-electron, orbital angular moment is (A) (C) Solution:

2
6
(B) (D)
Orbital angular momentum L = L for p electron = 1(1 1) (A) Problem 2:

2
( 1) where
h 2
For which of the following species, Bohr theory doesnt apply (A) (C) Solution: Bohr theory is not applicable to multi electron species (D) Trans Web Educational Services Pvt. Ltd
H Li2+
(B) (D)
He+ Na+
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Problem 3: If the radius of 2nd Bohr orbit of hydrogen atom is r2. The radius of third Bohr orbit will be (A) (C)
4 r2 9
9 r2 4
(B) (D)
4r2 9r2
Solution:
n2h2 4 2mZe2
r2 r3
22 32
9
r3 = 4 r2 (C) Problem 4: Number of waves made by an electron in one complete revolution in 3rd Bohr orbit is (A) (C) 2 4 (B) (D) 3 1

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Solution: Circumference of 3rd orbit = 2 r3 According to Bohrs angular momentum of electron in 3 rd orbit is mvr3 = 3
h 2
or
h mv
2 r3 3
By de-Broglie equation, =
h mv
2 r3 3
2 r3 = 3 i.e. circumference of 3rd orbit is three times the wavelength of electron or number of (B) Problem 5:
RH is 16
waves
made
by
Bohr
electron
in
one
complete
revolution in 3rd orbit is three.
The degeneracy of the level of hydrogen atom that has energy (A) (C) Solution: 16 2 (B) (D) 4 1

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En =
RH n2
RH n2
RH 16
i.e. for 4th sub-shell

1 n= 4 l = 0 m=0 one s -1 0 three p +1 -2 1 0 five d +1 +2 3 2 1 0 Seven f +1 +2 +3 2 3
i.e. 1 + 3 + 5 + 7 = 16 Degeneracy is 16 Problem 6: An electron is moving with a kinetic energy of 4.55 be de Broglie wavelength for this electron? (A) (C) Solution: 5.28 107 m 2 1010 m (B) (D) 7.28 107 m 3 105 m 1025 J. What will
KE = v2 =
1 2
mv2 = 4.55
25
1025
2 4.55 10 9.1 10 31
1 106
v = 103 m/s de Broglie wavelength =

h mv
6.626 10 34 9.1 10 31 103
= 7.28 107 m

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(B) Problem 7: Suppose 1017J of energy is needed by the interior of human eye to see an object. How many photons of green light ( needed to generate this minimum amount of energy? (A) (C) Solution: Let the number of photons required = n n
hc 10
17
= 550 nm) are
14 39
(B) (D)
28 42
17 n = 10
hc
10 17 550 10 9 6.626 10 34 3 108
= 27.6 = 28 photons
(B)
Problem 8: The two electrons present in an orbital are distinguished by (A) (C) Solution: Trans Web Educational Services Pvt. Ltd
principal quantum number magnetic quantum number
(B) (D)
azimuthal quantum number spin quantum number
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They are distinguished by their spin. (D) Problem 9: The velocity of electron in the ground state hydrogen atom is 2.18 (A) (C) Solution: We know that velocity of electron in nth Bohrs orbit is given by = 2.18 106
Z n
106 ms1. Its velocity in the second orbit would be 1.09 106 ms1 5.5 105 ms1 (B) (D) 4.38 106 ms1 8.76 106 ms1-
m/s
For H, Z = 1 v1 = v2 = (A) Problem 10:

2.18 106 m/s 1 2.18 106 m/s = 1.09 2
106 m/s

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The 2.18 (A) (C) Solution:
ionization
energy
of
the (B) (D)
ground
state
hydrogen
atom is
1018J. The energy of an electron in its second orbit would be 1.09 1018 J 4.36 1018J 2.18 1018J 5.45 1019J
Energy of electron in first Bohrs orbit of Hatom E= E2 =

2.18 10 n2
18
J ( ionization energy of H = 2.18
1018J)
2.18 10 22
18
J = 5.45 1019J
(D) True and False Problem 11: All electromagnetic radiations have same energy. Solution: False. Different electromagnetic radiation have different wavelengths, hence different energy

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Problem 12: Bohrs model is applicable for H-atom only. Solution: False. Bohrs model is applicable for species having one electron like H, He +, Li2+. Problem 13: Specific charge of cathode rays remains same irrespective of the gas used in the discharge tube. Solution: True. Cathode rays contain electrons which remains same with every gas. Problem 14: Isoelectronic species have same electronic configuration. Solution: Trans Web Educational Services Pvt. Ltd
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True. Isoelectronic species have same number of electrons. Problem 15: Atoms with same atomic number but different number of neutrons are called isotopes. Solution: True. Isotopes have same atomic number but different atomic mass.

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Fill in the Blanks Problem 16: The mass of positron is ___________ electron. Solution: Equal to Problem 17: With increasing principle quantum number, the energy difference between adjacent energy levels in H-atom _________. Solution: Decreases Problem 18: If the magnetic moment of an ion An+ is 5.9, then the number of unpaired electrons present in An+ are ____________. Solution: Trans Web Educational Services Pvt. Ltd
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Five. Applying
n n 2 , where n 5
Problem 19: s-electrons are more penetrating than p-electrons. The energy required to abstract s-electrons is ____________ than for p electrons. Solution: Greater Problem 20: The wavelength of the first spectral line in Paschen series for H-atom is____________. Solution: 16410 For Paschen series n2
4, n1 3

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ASSIGNMENT PROBLEMS
Subjective:
Level O 1. How many electrons in an atom have the following quantum numbers? (i) n = 4, ms = 1/2 (ii) n = 3, 0
2. 3. 4.
Write the number of protons, electrons and neutrons in nitride ion. Distinguish between absorption and emission spectra. Write down the electronic configuration of Mn 4+ and Cr3+. How many unpaired electrons are present in them?
5.
Write correct orbital notation for each of the following sets of quantum numbers. (i) n = 1, 0 , m = 0 (ii) n = 2, 1 , m = 1
6. 7.
What are drawbacks of Rutherfords model atom? Explain why uncertainty principle is significant only for the motion of subatomic particles but not for macroscopic objects.

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8. 9. 10.
Why we do not see a car moving in the form of a wave on a road? Why e/m ratio in case of anode rays depends upon the type of gas? Why splitting of spectral lines take place when the source giving the spectrum is placed in a magnetic field?
11.
What is the maximum number of lines obtained when the excited electrons of a hydrogen atom in n = 6 drops to the ground state.
12. 13.
Calculate the radius of the third orbit of a hydrogen atom. The wavelength of a moving body of mass 0.1 mg is 3.31 10 29 m. Calculate its kinetic energy h 6.625 10 34 J sec
14. 15.
Calculate the mass and charge of one mole of electrons. Calculate (a) wave number and (b) frequency of yellow radiations having wavelength of 5800 A .
o
16.
In one discharge tube H2 gas is taken and in other O2 gas is taken. Will the negative and positive charged particles in cathode rays and anode rays be same?
17.
Explain why half filled and full filled configurations are more stable. Trans Web Educational Services Pvt. Ltd
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18.
Some energy is absorbed by hydrogen atom due to which an electron in it jumped from ground state to the state having principle quantum number 5 and again jumped back to the original level. What type of spectrum is observed and in which region. What is the name of series?

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Level I 1. What is the mass of a photon of sodium light with a wavelength of 5890 A ? h 6.63 10 27 ergsec,c 3 10 10cmsec
o
1
2.
Calculate the kinetic energy of a moving electron which has a wavelength of 4.8 pm (Mass of electron 9.11 10 31kg,h 6.63 10 34 Js)
3.
Calculate de Broglie wavelength of an electron moving with 1% of the speed of light.
4.
Calculate the energy of an electron in the second Bohr orbit of an excited hydrogen atom
5.
Calculate the velocity of an electron revolving in the second orbit of a hydrogen atom
6.
How many photons of light having a wavelength of 4000 A are necessary to provide 1 J of energy? (h = 6.63 10-34Js, c = 3 108 m/s)
7.
How the electron in the ground state of hydrogen atom is excited by means of monochromatic radiation of wavelength 970.6 A . How many different lines are possible in the resulting emission spectrum? Find the longest wavelength among these? Trans Web Educational Services Pvt. Ltd
o
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8.
The wavelength of the first line in the Balmer series is 656 nm. Calculate the wavelength of the second line and the limiting line in Balmer series.
9.
A single electron system has ionization energy 11180 kJ / mol. Find the number of protons in the nucleus of the system.
10.
Calculate the velocity of an electron placed in the third orbit of hydrogen atom. Also calculate the number of revolutions per second that this electron makes around the nucleus.
11.
(a) (b)
What is wavelength of a particle of mass 1 g moving with a velocity of 200 m/s? A moving electron has 4.55
34
10-25 joules of kinetic energy.
Calculate its wavelength (mass = 9.1 1031 kg and h = 6.6 10 kg m2sec1) (c) Calculate the de-Broglie wavelength of electron accelerated through 100 volt. 12. Calculate the radii of the I, II and III permitted electron Bohr orbits in a hydrogen atom. What are the corresponding values in the case of a singly ionised helium atom?

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13.
Calculate energy in kcal/mole necessary to remove an electron in a hydrogen atom in fourth principal quantum number to infinity.
14.
A monochromatic source of light operating at 600 watt emits 2 photons per second. Find the wavelength of the light.
1022
15.
Calculate the uncertainty in the position of an electron if it has a speed of 500 m/s with an uncertainity of 0.02%.

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Level II 1. (a) The electron energy in hydrogen atom is given by E = 21.7 1012/n2 erg. Calculate the energy required to remove an electron completely from n = 2 orbit. What is the longest wavelength (in cm) of light that can be used to cause this transition? (b) Ionization energy of hydrogen atom is 13.6 eV. Calculate the ionization energy for Li 2+ and Be3+ in the first excited state. 2. A bulb emits light of wave length 4500 . The bulb is rated as 150 watt and 8% of the energy is emitted as light. How many photons are emitted by bulb per second? 3. (a) (b) What Amount of accelerating potential is needed to produce an electron beam with an effective wavelength of 0.09 . Calculate de-Broglie wavelength of an electron moving with a speed of nearly
1 th that of light (3 20
108 ms1)
4.
A doubly ionised lithium atom is hydrogen like with an atomic no. 3. (a) Find the wavelength of the radiation required to excite the electron in Li from the first to the third Bohr orbit (ionisation energy of the hydrogen atom is equal to 13.6 eV)

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(b)
How many spectral lines are observed in the emission spectrum of the above excited system?
5.
Calculate
of the radiations when the electron jumps from III to II
orbit of hydrogen atom. The electronic energy in II and III Bohr orbit of hydrogen atoms are 5.42 1012 and 2.41 1012erg respectively. 6. 1.8 g hydrogen atoms are excited to radiations. The study of spectra indicates that 27% of the atoms are in 3 rd energy level and 15% of atoms in 2nd energy level and the rest in ground state. IP of H is 13.6 eV. Calculate (i) No. of atoms present in III and II energy level (ii) Total energy evolved when all the atoms return to ground state. 7. The IP of H is 13.6 eV. It is exposed to electromagnetic waves of 1028 and given out induced radiations. Find the wavelength of these induced radiations. 8. What is uncertainty in velocity of an electron if uncertainty in its position is 1? 9. A single electron beam, atom has nuclear charge +Ze where Z is atomic number and e is electronic charge. It requires 16.52 eV to excite the electron from the second Bohr orbit to third Bohr orbit. Find (a) The atomic no. of element

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(b) (c) (d) 10.
The energy required for transition of electron from first to third orbit. Wavelength required to remove electron from first Bohr orbit to infinity. The kinetic energy of electron in first Bohr orbit.
A sample of hydrogen gas containing some atoms in one excited state emitted three different types of photons. When the sample was exposed with radiation of energy 2.88 eV it emitted 10 different types of photons, all having energy equal or less than 13.05 eV. Find out (a) (b) (c) The principal quantum numbers of initially excited electrons. The principal quantum numbers of electrons in final excited state. The maximum and minimum energies of initially emitted photons.

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Objective:
Level I 1. The ratio of energy of the electron in ground state of the hydrogen to electron in first excited state of He+ is (A) (C) 2. 1:4 1:8 (B) (D) 1:1 1 : 16
Bohr model can explain spectrum of (A) (B) (C) (D) the hydrogen atom only all elements any atomic or ionic species having one electron only the hydrogen molecule
3.
Which is the correct order of probability of being found close to the nucleus is (A) (C) s p p d d f f s (B) (D) f d d f p p s s
4. Ratio between longest wavelengths of H atom in Lyman series to the shortest wavelength in Balmer series of He + is (A) (C)
4 3
1 4
(B) (D)
36 5
5 9

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5.
If the radius of first Bohr orbit is a, then de-Broglie wavelength of electron in 3rd orbit is nearly. (A) (C) 2 a1 9 a1 (B) (D) 6 a1 16 a1
6.
If uncertainty in position and momentum are equal, the uncertainty in velocity would be (A) (C)
1 h 2m h
(B) (D)
h 2 h m
7.
Which of the following is a coloured ion? (A) (C) Cu+(aq) Cu2+ (aq) (B) (D) Na+(aq) K+ (aq)
8.
The number of orbitals in a sub-shell are given by (A) (C) 2 2 + 1 (B) (D) n2 2n2
9.
For a d electron, the orbital angular momentum is (A) (C)

6 h/ 2
(B) (D)
2 h/ 2
h/2
2h/ 2

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10.
Hydrogen atom consists of a single electron but so many lines appear in the spectrum of atomic hydrogen because (A) (B) (C) (D) Sample contains some impurity Experiment is done on collection of atoms. Hydrogen atom splits to form more than one different species. Some different isotope of hydrogen atom may be present.
11.
A line with wave number 1.028 10-2 nm-1 is emitted in the spectrum of atomic hydrogen. In what region of the electromagnetic spectrum does this line occur? (A) (C) far UV near IR (B) (D) near UV far IR
12.
One molecule of a substance absorbs one quantum of energy. The energy involved when 1.5 mole of the substance absorbs red light of frequency 7.5 1014 sec1 will be (A) (C) 2.99 105 J 4.48 105J (B) (D) 3.23 105J 2.99 106 J
13.
If a shell is having g sub-shell, which is correct statement about principal quantum number n of this shell. (A) (C) n 5 (B) (D) n 5 n=5 Cannot be determined

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14.
The wave number of a spectral line is 5 corresponding to this line will be (A) (C) 3.39 1023 kJ 3.45 1024 J (B) (D)
105 m1. The energy
9.93 1023 kJ none of these
15.
Wave length of the radiation when electron jumps from second shell to 1st shell of H atom (RH = 109679 cm1) (A) (C) 1215.6 2395.87 (B) (D) 1397.5 none of these
16.
The orbital which have lobe along the axis is/are (A) (C)
dz 2
dx 2
y2
(B) (D)
dxz dxy
17.
Anode rays (A) (B) (C) (D) contain positively charged particles have constant e/m ratio irrespective of the type of gas used may contain He+ ions are always beams of protons
18.
The spectrum of He is expected to be similar to that of (A) (C) H Be2+ (B) (D) Li+ H+
19.
The total energy of electron in an atom Trans Web Educational Services Pvt. Ltd
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(A) (B) (C) (D) 20.
is less than zero is the sum of kinetic energy and potential energy is equal to kinetic energy in magnitude is equal to potential energy in magnitude
Which of the following orbitals have no nodal plane? (A) (C) px

dz 2
(B) (D)
dxy 4s

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AssertionReason type questions The following questions consist of two statements each printed as Assertion and Reason. While answering these questions, you are required to choose any one of the following five responses. (A) (B) (C) (D) (E) 21. If both Assertion and Reason are true and the Reason is a correct explanation of the Assertion. If both Assertion and Reason are true but Reason is not a correct explanation of the Assertion. If Assertion is true but the Reason is false. If the Assertion is false but the Reason is true. If both Assertion and Reason are false. A: R: A spectral line will be observed for 2px-2py transition. The energy will be released in the form of electromagnetic radiations. 22. A: R: 23. A: R: 24. A: Cs is used in photoelectric cells. Cs is an alkali metal. The energy of an electron is largely determined by its principle quantum number. 2s subshell has higher energy than 1s. Fe3+(g) ion is more stable than Fe2+(g). Trans Web Educational Services Pvt. Ltd
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R: 25. A: R:
Fe3+(g) ion has higher magnetic moment than Fe 2+(g) ion. de-Broglies equation and uncertainity principle are applicable to moving bodies. These have significance to microscopic as well as macroscopic particles.

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Level - II 1. Which statement is wrong about Bohrs theory? (A) (B) (C) (D) 2. Orbit is a three dimensional area where probability of finding electron is maximum. Orbit is a two dimensional track on which electron moves Atom has definite boundary Energies and angular momentum of orbits are quantized.
The introduction of a neutron into the nuclear composition of an atom would lead to a change in (A) (B) (C) (D) The number of electrons also The chemical nature of the atom Its atomic number Its atomic weight
3.
Which statement is true? (A) (B) (C) (D) Spacing between energy levels n = 1 and n = 2 in hydrogen atom is greater than that of n = 2 and n = 3 Spacing between energy levels n = 1 and n = 2 in hydrogen atom is equal to that n = 2 and n = 3 Spacing between energy levels n = 1 and n = 3 in hydrogen atom is less than that of n = 2 and n = 3 None of these

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4.
If the wavelength of first line of the Balmer series of hydrogen atom is 656.1 nm, the wavelength of second line of this series would be (A) (C) 218.7 nm 86.0 nm (B) (D) 328.0 nm 640.0 nm
5.
In absence of external magnetic field f sub-shell is (A) (C) 5 fold degenerate 7 fold degenerate (B) (D) 3 fold degenerate non-degenerate
6.
Which set of quantum numbers is not possible for electron in 3 rd shell? (A) (B) (C) (D) n = 3, n = 3, n = 3, n = 3,

= 2, m = 1, s = +1/2 = 2, m = 1, s = 1/2 = 2, m = 0, s = +1/2 = 3, m = 0, s = 1/2
7.
The first four ionization energies of an element are 191, 578,872 and 5962 kcal. The number of valence electrons in the element is (A) (C) 1 3 (B) (D) 2 4
8.
The radiation is emitted when a hydrogen atom goes from a high energy state to a lower energy state. The wavelength of one line in visible region of atomic spectrum of hydrogen is 6.5 difference between the two states is (A) 3.0 1017 J (B) 1.0 1018 J 109 m. Energy

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(C) 9.
5.0
1010 J
(D)
6.5 107 J
The ratio of the energy of the electron in ground state of hydrogen to the electron in first excited state of Be 3+ is (A) (C) 1:4 1 : 16 (B) (D) 1:8 16 : 1
10.
Which one of the following species is isoelectronic with P 3? (A) (C) Kr Na+ (B) (D) Ca2+ F
11.
Which of the following sets of quantum numbers is/are not allowable? (A) (B) (C) (D) n = 3, n = 2, n = 4, n = 1,
= 2, m = 0 = 0, m = 1 = 3, m = + 1 = 0, m = 0
12.
Among V (Z = 23), Cr (Z = 24), Mn (Z = 25) which will have highest magnetic moment. (A) (B) (C) (D) V Cr Mn all of them will have equal magnetic moment

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13.
If velocity of an electron in 1st Bohr orbit of hydrogen atom is x, its velocity in 3rd orbit will be (A) (C)
x 3
(B) (D)
3x
x 9
9x
14.
Which element has a hydrogen like spectrum whose lines have wavelengths one fourth of atomic hydrogen? (A) (C) He+ Be3+ (B) (D) Li
2+
B4+
15.
Calculate the wavelength of a track star running 150 metre dash in 12.1 sec if its weight is 50 kg. (A) (C) 9.11 1.12 1034 m 1045 metre (B) (D) 8.92 1037 m none of these
16.
Which of the following sets of quantum numbers is not allowed (A) (C) n = 3, n=
=
1, m = +2 0, m = 0
(B) (D)
n = 3, n = 3,
= =
1, m = +1 2, m = 2
3,
17.
Assuming that a 25 watt bulb emits monochromatic yellow light of wavelength 0.57 . The rate of emission of quanta per sec. will be (A) (C) 5.89 5 1015 sec1 (B) (D) 7.28 7.18 1017 sec1 1019 sec1 1010 sec1

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18.
How many chlorine atoms can you ionize in the process Cl by the energy liberated from the following process? Cl + e (A) (C) 1.24 2.02
Cl
Cl
+ e,
for 6
1023 atoms (B) (D) 9.82 1020 atoms
Given electron affinity of Cl = 3.61 eV, and I P of Cl = 17.422 eV 1023 atoms 1015 atoms none of these
19.
The binding energy of an electron in the ground state of the He atom is equal to 24 eV. The energy required to remove both the electrons from the atom will be (A) (C) 59 eV 79 eV (B) (D) 81 eV None of these
20.
The wave number of the shortest wave length transition in Balmer series of atomic hydrogen will be (A) (C) 4215 3942 (B) (D) 1437 3647

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ANSWERS TO ASSIGNMENT PROBLEMS
Subjective:
Level O 1. (i) (ii) 2. Total electrons in n = 4 are 2n 2 i.e. 2 have ms = 1/2. n = 3, 0 means 3s orbitals which can have 2 electrons. 42 = 32. Half of them
Nitride ion is N3 . P = 7, e = 10, n = 7
3. 4.
Refer to theory. Mn4+ (Z = 25) = 1s22s2sp63s23p63d3. It has three unpaired electrons. Cr3+ (Z = 24) = 2s22s22p63s23p63d3. It also has three electrons.
5. 6. 8.
(i) 1s
(ii) 2px or 2py
Refer to theory. We know that = h/mv, since mass of the car is large hence
wavelength is very small.

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9.
Anode rays are beams of positive ions which are different for different gases.
10.
In the presence of magnetic field the orbitals present in a subshell take up different orientations.
11.
Number of lines
n n 1 2
6 6 1 2
15
12. 13. 14. 15.
4.77 2 10
10
3
Mass = 5.486 (a) (b)
107 kg and charge = 9.65
104 C
1.72 106 m
5.172 1014 Hz
16. 17. 18.
Cathode rays are same in both cases, but anode rays will be different. Refer to theory. Emission spectrum, Lyman series.

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Level I 1.
3.75 10
33
2. 3. 4. 5. 6. 7. 8. 9. 10.
1.047 10
14
2.4 10 10 mk
2.4A
0.545 10-11 erg 1.09 108 cm/sec
2.01 1018 = 1215.68 A 364.4 nm Z=3 V3 = 7.275 rps = 2.432 105 m/sec 1014 1033m 107m Trans Web Educational Services Pvt. Ltd
11.
(a) (b)
3.313 7.25
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(c) 12.
1.227
r1= 0.53 : r1 = 0.265 r2 = 2.12 for hydrogen : r2 = 1.06 for He+ r3 = 4.77 : r3 = 2.385
13. 14. 15.
19.5 kcal/mole 6630 nm 5.77 10

4

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Level II 1. (a) (b) 2. 3. 27.2 (a) (b) 4. (i) (ii) 5. 6. 3.67 105 cm
30.6 eV for Li 2+, 54.4 eV for Be3+ 1018 1.86 4.85 104 eV 1011m
113.7 3
6603 (i) (ii) 628.72 1021 atoms
832.50 kJ.
2=
7. 8. 9. 10.
= 1028 , 105
1216 ,
= 6558
5.79
(i) 3, (ii) 108.87 eV, (iii) 1.01 (a) 2 and 3
106cm (iv) 122.4 eV

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(b) 5 (c) 12.09 eV and 1.9 eV

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Objective:
Level I 1. 4. 7. 10. 13. 16. 19. 22. 25. Level II 1. 4. 7. 10. 13. 16. 19. A C C B A A C 2. 5. 8. 11. 14. 17. 20. D C A B A D D 3. 6. 9. 12. 15. 18. A D A B B A A A C B B A, C A, B, C B C 2. 5. 8. 11. 14. 17. 20. 23. C B C A B A, C C, D B 3. 6. 9. 12. 15. 18. 21. 24. A A A C A B, C D B

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Atomic Structure Chemistry

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Atomic Structure Chemistry

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BRINGiiT on Study Pack

Contents:- Atomic Structure

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kg. The neutron and proton have approximately

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Fluorescence Glass Tube

CATHODE RAY EXPERIMENT (DISCHARGE TUBE)

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1.6022 10 19 1.76 108

Positive Rays Anode

Cathode To Vacuum Pump

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bombarded the element Beryllium with

particles and noticed the emission

Mass of a neutron is 1.008930 amu (1.6753

Isoelectronic species: Trans Web Educational Services Pvt. Ltd

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Solution: No. of neutrons in one atom = (30 15) = 15 0.18 g

0.18 = 0.006 mole 30

P atoms in 0.006 mole = 0.006

Number of electrons in 0.006 mole of mole

P =Number of protons in 0.006

1022 and number of

neutrons = 5.418 Exercise 1:

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electron Positive sphere

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Very few than 90 .

particles are deflected backwards through angles greater

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kg, atomic mass of He = 4 and gold = 79 and

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-particles had met something even more massive than

themselves inside the gold atom, Rutherford proposed an atomic model as

A1/3 cm, where A is the mass

1.66 10 27 3 4 3.14 (1.33 10

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Wave number is denoted by

: It is defined as number of wavelengths per cm. It and is expressed in cm1.

Wavelengths of Electromagnetic Radiations:

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For longest wavelength from n = 1 to n = 2

E should be smallest, i.e. transition occurs

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potential difference in volt

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(a) (b) (c)

103 cm 400 cm1 = 1.2 10 7 s 1

1010 cm/s = h c 1034 Js 3

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= 7.95 (d) Ephoton = 7.95

1021J 1021J 1021J 6.022 1023 mol1 103 J mol1) (1 kcal/4184 J)

103 J mol1) (1 kJ/1000J)

Wavelength of the 1st photon = E1 =

And that of second photon = E2 =

ETotal = E1 + E2= emitted energy

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