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01 Atomic Structure Theory Final E
01 Atomic Structure Theory Final E
Chapter
2
Structure of atom
John Dalton 1808, believed that matter is made up of extremely (vi) Cathode rays heat the object on which they fall due to transfer
minute indivisible particles, called atom which can takes part in chemical of kinetic energy to the object.
reactions. These can neither be created nor be destroyed. However, modern
researches have conclusively proved that atom is no longer an indivisible (vii) When cathode rays fall on solids such as Cu, X rays are
particle. Modern structure of atom is based on Rutherford’s scattering produced.
experiment on atoms and on the concepts of quantization of energy. (viii) Cathode rays possess ionizing power i.e., they ionize the gas
through which they pass.
Composition of atom
(ix) The cathode rays produce scintillation on the photographic
The works of J.J. Thomson and Ernst Rutherford actually laid the plates.
foundation of the modern picture of the atom. It is now believed that the atom (x) They can penetrate through thin metallic sheets.
consists of several sub-atomic particles like electron, proton, neutron, positron, (xi) The nature of these rays does not depend upon the nature of gas
neutrino, meson etc. Out of these particles, the electron, proton and the neutron or the cathode material used in discharge tube.
are called fundamental subatomic particles and others are non- (xii) The e/m (charge to mass ratio) for cathode rays was found to
fundamental
particles.
be the same as that for an e (1.76 108 coloumb per
Electron ( e )––11
oo
gm). Thus, the cathode rays are a stream of electrons.
(1) It was discovered by J.J. Thomson (1897) and is (xiii) According to Einstein’s theory of relativity, mass of electron
negatively charged particle. Electron is a component particle of cathode Rest mass of electron(m)
rays. in motion is, m [1 (u / c)2 ]
(2) Cathode rays were discovered by William Crooke's & J.J.
Thomson (1880) using a cylindrical hard glass tube fitted with two metallic Where u = velocity of electron, c= velocity of light.
electrodes. The tube has a side tube with a stop cock. This tube was known When u=c than mass of moving electron =.
as discharge tube. They passed electricity (10,000V) through a discharge
tube at very low pressure ( 10 2 to 10 3 mm Hg) . Blue rays were
Proton (H , H , P)
emerged from the cathode. These rays were termed as Cathode rays.
11 ++
11
Relative 1/1837 1 1
The atomic mass unit (amu) is 1/12 of the mass of an individual atom of 6 C12 , i.e. 1.660 10 27 kg .
Table : 2.2 Other non fundamental particles
Particle Symbol Nature Charge esu Mass Discovered by
(amu)
10 –10
(N – Z) or (A – 2Z) neutrons.
39 19
Isodiaphers (ii) Physical and chemical properties. (ii) 19 K , 9F
(iii) 29 Cu
65
, 24 Cr 55
(i) No. of electrons At. No., mass No. (i) N 2O, CO2 , CNO (22e )
(ii) Electronic configuration
(ii) CO, CN , N 2(14e )
Isoelectronic species
(iii) H , He, Li, Be 2(2e )
(iv) P 3 , S 2 , Cl , Ar, K and Ca 2 (18e
)
(i) No. of atoms (i) N 2 and CO
(ii) No. of electrons
(ii) CO 2 and N 2O
(iii) Physical and chemical properties.
Isosters (iii) HCl and F2
(v) C6 H6 and B3 N 3 H6
Electromagnetic radiations
(1) Light and other forms of radiant energy propagate without any measured is terms of centimeter(cm), angstrom(Å), micron( ) or
medium in the space in the form of waves are known as electromagnetic
radiations. These waves can be produced by a charged body moving in a nanometre (nm).
magnetic field or a magnet in a electric field. e.g. rays, rays,
cosmic rays, ordinary light rays etc.
(2) Characteristics
(i) All electromagnetic radiations travel with the velocity of light. Crest Wavelength
(ii) These consist of electric and magnetic fields components
Vibrating
that oscillate in directions perpendicular to each other and source
perpendicular to the direction in which the wave is travelling.
(3) A wave is always characterized by the following five Energy
characteristics,
(i) Wavelength : The distance between two nearest crests or nearest
troughs is called the wavelength. It is denoted by (lambda) and is Trough
Fig. 2.2
Structure of atom
incandescent object resolved through prism or spectroscope, it also gives
continuous spectrum of colours.
(ii) Line spectrum : If the radiation’s obtained by the excitation of a
substance are analysed with help of a spectroscope a series of thin bright
lines of specific colours are obtained. There is dark space in between two
1Å 10 8 cm 10 10 m ; 1 10 4 cm 10 6 m consecutive lines. This type of spectrum is called line spectrum or atomic
;
1nm 107 cm 109 m ; 1cm 108 Å 104 107 nm spectrum..
(ii) Frequency : It is defined as the number of waves which pass (2) Absorption spectrum : Spectrum produced by the absorbed
through a point in one second. It is denoted by the symbol (nu) and is radiations is called absorption spectrum.
expressed in terms of cycles (or waves) per second (cps) or hertz (Hz). Hydrogen spectrum
distance travelled in one second = velocity =c (1) Hydrogen spectrum is an example of line emission spectrum or
c atomic emission spectrum.
(2) When an electric discharge is passed through hydrogen gas at
low pressure, a bluish light is emitted.
(iii) Velocity : It is defined as the distance covered in one second by
the wave. It is denoted by the letter ‘c’. All electromagnetic waves travel (3) This light shows discontinuous line spectrum of several isolated
sharp lines through prism.
with the same velocity, i.e., 3 1010 cm / sec .
(4) All these lines of H-spectrum have Lyman, Balmer, Paschen,
c 3 1010 cm / sec Barckett, Pfund and Humphrey series. These spectral series were named by
(iv) Wave number : This is the reciprocal of wavelength, i.e., the the name of scientist discovered them.
number of wavelengths per centimetre. It is denoted by the symbol (nu (5) To evaluate wavelength of various H-lines Ritz introduced the
following expression,
bar). It is expressed in cm 1 or m 1 .
1 1 1
1 c R n 2 n 2
2
1
(v) Amplitude : It is defined as the height of the crest or depth of Where R is universal constant known as Rydberg’s constant its value
the trough of a wave. It is denoted by the letter ‘A’. It determines the is 109, 678 cm 1 .
intensity of the radiation.
The arrangement of various types of electromagnetic radiations in Plum pudding model of Thomson
the order of their increasing or decreasing wavelengths or frequencies is
(1) He suggected that atom is a positively charged sphere having
known as electromagnetic spectrum.
electrons embedded uniformly giving an overall picture of plum pudding.
Table: 2.4
Positively charged
– sphere
Name Wavelength (Å) Frequency (Hz) + +
Radio wave –
3 1014 3 107 1 105 1 109 – + – + +
Electron unifromly
Microwave 3 107 6 106 1 109 5 1011 + – embedded
Infrared (IR) – +
6 106 7600 5 1011 3.95 1016
Positive charge spreaded throughout the sphere
Visible 7600 3800 3.95 1016 7.9 1014
(2) This model failed tFoige. x2p.3lain the line spectrum of an
Ultraviolet (UV) 3800 150 7.9 1014 2 1016 element and the scattering experiment of Rutherford.
X-Rays 150 0.1 2 1016 3 1019
Rays 0.1 0.01 3 1019 3 10 20 Rutherford's nuclear model
Cosmic Rays 0.01- zero 3 10 20 infinity
(1) Rutherford carried out experiment on the bombardment of thin
(10 mm) Au foil with high speed positively charged particles
–4
ch3 1n2 n2
one electron, viz. hydrogen atom, He, Li2 etc.
1 2 1 1
(ii) Calculation of radius of Bohr’s orbit : According to Bohr, radius This can be represented as RZ n n2
of n orbit in which electron moves is
th
1 2
rn 2 2k 2me
2h
2
2 . n2 Where, 4 ; R is known as Rydberg constant. Its
R ch3
4 me k Z
value to be used is 109678cm1.
Where, n Orbit number, m Mass number
9.1 10 31
kg , e Charge on the electron 1.6 10 19
Z Atomic
The negative sign in the above equations shows that the electron
and nucleus form a bound system, i.e., the electron is attracted towards the
number of element, k = Coulombic constant 9 10 Nm c
9 2 2 nucleus. Thus, if electron is to be taken away from the nucleus, energy has
to be supplied. The energy of the electron in n 1 orbit is called the
After putting the values of m,e,k,h, we get. ground state energy; that in the n 2 orbit is called the first excited state
energy, etc. When n then E 0 which corresponds to ionized atom
n2
rn 0.529 Å i.e., the electron and nucleus are infinitely separated H H e
Z
(ionization).
(6) Spectral evidence for quantisation (Explanation for hydrogen spectrum
(iii) Calculation of velocity of electron on the basisof bohr atomic model)
2e 2 ZK
1/ 2.188 108 Z (i) The light absorbed or emitted as a result of an electron changing
Ze 2
2
Vn , Vn ; Vn cm. sec 1
orbits produces characteristic absorption or emission spectra which can be
nh mr n recorded on the photographic plates as a series of lines, the optical
(iv) Calculation of energy of electron in Bohr’s orbit spectrum of hydrogen consists of several series of lines called Lyman,
Balmar, Paschen, Brackett, Pfund and Humphrey. These spectral series were
Total energy of electron = K.E. + P.E. of electron named by the name of scientist who discovered them.
kZe 2 kZe 2
kZe 2
r (ii) To evaluate wavelength of various H-lines Ritz introduced the
2r 2r
following expression,
2 2 mZ 2e 4k 2 1 1 1
Substituting of r, gives us E Where, n=1, 2, R
n2h2 c 2
n
3………. 1
n
Putting the value of m, e, k, h, we get
Where, R is 24 me
2
Rydberg's constant
= 3
E 21.8 10 12 ch
Z2
2 erg per atom It's theoritical value = 109,737 cm –1
and It's experimental value =
n 2 109,677.581cm1
Z
21.8 1019 J per atom(1J 107 erg) This remarkable agreement between the theoretical and
n2 experimental value was great achievment of the Bohr model.
2
Z
E 13.6 eV per atom(1eV 1.6 10-19 J) (iii) Although H-atom consists of only one electron yet it's
n2 spectra consist of many spectral lines.
2 (iv) Comparative study of important spectral series of Hydrogen is
13.6 Z k.cal / mole (1 cal = 4.18J)
2 shown in following table.
1312 2n (v) If an electron from n excited state comes to various energy
or Z kJmol 1
th
n(n 1)
n 2
states, the maximum spectral lines obtained will be = . n=
2
When an electron jumps from an outer orbit (higher energy) n2 to principal quantum number.
an inner orbit (lower energy) n1, then the energy emitted in form of As n=6 than total number of spectral lines =
radiation is given by 6(62 1) 30
2 2k 2me 4 Z 2 1 1 2 15.
E En2 En1 2 2 2 (vi) Thus, at least for the hydrogen atom, the Bohr theory accurately
h
n1 n2 describes the origin of atomic spectral lines.
1 1 (7) Failure of Bohr model
E 13.6 Z 2 n n eV / atom (i) Bohr theory was very successful in predicting and accounting the
2
1 2 energies of line spectra of hydrogen i.e. one electron system. It could not
1 E explain the line spectra of atoms containing more than one electron.
42 Structure of
As we know that E h , c and (ii) This theory could not explain the presence of multiple spectral
, hc lines.
Structure of atom
(iii) This theory could not explain the splitting of spectral lines in (iv) This theory was unable to explain of dual nature of matter as
magnetic field (Zeeman effect) and in electric field (Stark effect). The explained on the basis of De broglies concept.
intensity of these spectral lines was also not explained by the Bohr atomic (v) This theory could not explain uncertainty principle. (vi) No
model. conclusion was given for the concept of quantisation of energy.
Table: 2.5
2
S.No. Spectral series Lies in the Transition n n
2 2
n1
2 max n
max (n2 1 n22)R min R 2
region n2 n1 2 1 min n n
2
2
2 1
(1) Lymen series Ultraviolet n1 1 n1 1 and n2 2 n1 1 and n2
region 4
n2 2,3,4.... 4 1
max min
3
3R R
(2) Balmer series Visible region n1 2 n1 2 and n2 3 n1 2 and n2
n2 3,4,5.... 4 9
36
max min 5
5R R
(3) Paschen series Infra red n=3
1 n1 3 and n2 4 n1 3 and n2
region n2 4,5,6.... 16
9
144 7
max min
7R R
(4) Brackett series Infra red n1 4 n1 4 and n2 5 n1 4 and n2
region 25
n2 5,6,7.... 16 25 16
max min 9
9R R
(5) Pfund series Infra red n1 5 n1 5 and n2 6 n1 5 and n2
region 36
n2 6,7,8.... 25 36 25
max min 11
11R R
(6) Humphrey Far infrared n1 6 n1 6 and n2 7 n1 6 and n2
series region 49
n2 7,8. . . 36 49 36
max min 13
13R R
Bohr–Sommerfeild’s model energy of photon (on the basis of Einstein’s mass energy
It is an extension of Bohr’s model. The electrons in an atom revolve relationship), E mc 2
around the nuclei in elliptical orbit. The circular path is a special case of
hc h
ellipse. Association of elliptical orbits with circular orbit explains the fine Equating both mc 2 or which is same as de-
line spectrum of atoms. mc
4r2 dr
4r2 dr
4r2 dr
6 3 3
Now since p m v
4 2
2 1 1
So equation becomes, x. m v h or x v h 0 0 0
4 4m 2 4 6 8 2 4 6 8 2 4 6 8
0.53Å r(Å) 0.53Å 2.7Å r(Å) 2.1 Å r(Å)
In terms of uncertainty in energy, E and uncertainty in time 1s 2s 2s
t, this principle is written as,
h Fig. 2.5
E . t Quantum numbers
4
Schrödinger wave equation Each orbital in an atom is specified by a set of three quantum
numbers (n, l, m) and each electron is designated by a set of four quantum
(1) Schrodinger wave equation is given by Erwin Schrödinger in numbers (n, l, m and s).
1926 and based on dual nature of electron.
(1)Principle quantum number (n)
(2) In it electron is described as a three dimensional wave in the electric
field of a positively charged nucleus. (i) It was proposed by Bohr and denoted by ‘n’.
(3) The probability of finding an electron at any point around the (ii) It determines the average distance between electron and nucleus,
nucleus can be determined by the help of Schrodinger wave equation which means it denotes the size of atom.
is, (iii) It determine the energy of the electron in an orbit where
electron is present.
2 2 2 2 8 (iv) The maximum number of an electron in an orbit
m
(E V) 0
x 2 y z h2
2 2 represented by this quantum number as 2n 2 No energy shell in
.
Where x, and z are the 3 space co-ordinates, m = mass of atoms of known elements possess more than 32 electrons.
y
electron, h = Planck’s constant, E = Total energy, V = potential energy of (v) It gives the information of orbit K, L, M, N----------.
electron, = amplitude of wave also called as wave function, = for an
(vi) Angular momentum can also be calculated using principle
infinitesimal change.
quantum number
(4) The Schrodinger wave equation can also be written as,
(2) Azimuthal quantum number (l)
2
8 (E V) 0 (i) Azimuthal quantum number is also known as angular
2
h2 quantum number. Proposed by Sommerfield and denoted by ‘ l ’.
Where = laplacian operator. (ii) It determines the number of sub shells or sublevels to which the
electron belongs.
(5) Physical significance of and 2
(iii) It tells about the shape of subshells.
(i) The wave function represents the amplitude of the
(iv) It also expresses the energies of subshells s p d f
electron wave. The amplitude is thus a function of space co-ordinates
(increasing energy).
and time i.e. (x, y, z times)
(v) The value of l (n 1) always. Where ‘n’ is the number of
(ii) For a single particle, the square of the wave function ( ) at 2 principle shell.
any point is proportional to the probability of finding the particle at that
(vi) Value of l = 0 1 2 3…..(n-1)
point.
Name of subshell = s p d f
(ii) The value of ' s' is 1/2 and - 1/2, which signifies the spin
(ix) For a given value of ‘n’ the total values of ‘l’ is always equal to or rotation or direction of electron on it’s axis during movement.
the value of ‘n’.
(iii) The spin may be clockwise or anticlockwise.
(3) Magnetic quantum number (m)
(i) It was proposed by Zeeman and denoted by ‘m’. (iv) It represents the value of spin angular momentum is equal to
h
s(s
(ii) It gives the number of permitted orientation of subshells. 1). 2
(iii) The value of m varies from –l to +l through zero. (v) Maximum spin of an atom 1 / 2 number of unpaired
(iv) It tells about the splitting of spectral lines in the magnetic field electron.
i.e. this quantum number proves the Zeeman effect.
(vi) This quantum number is not the result of solution of
(v) For a given value of ‘n’ the total value of ’m’ is equal to n 2 . schrodinger equation as solved for H-atom.
(vi) For a given value of ‘l’ the total value of ‘m’ is equal to (2l 1).
Table : 2.6 Distribution of electrons among the quantum levels
Designation of Number of Orbitals in the subshell
n l m
orbitals
1 0 0 1s 1
2 0 0 2s 1
2 1 –1, 0, +1 2p 3
3 0 0 3s 1
3 1 –1, 0, +1 3p 3
3 2 –2, –1, 0, +1, +2 3d 5
4 0 0 4s 1
4 1 –1, 0, +1 4p 3
4 2 –2, –1, 0, +1, +2 4d 5
4 3 –3, –2, –1, 0, +1, +2, +3 4f 7
Shape of orbitals
(1)Shape of ‘s’ orbital (2) Shape of ‘p’ orbitals
(i) For ‘s’ orbital l=0 & m=0 so ‘s’ orbital have only one (i) For ‘p’ orbital l=1, & m=+1,0,–1 means there are three ‘p’ orbitals,
unidirectional orientation i.e. the probability of finding the electrons is same which is symbolised as p x , py , pz .
in all directions.
(ii) The size and energy of ‘s’ orbital with increasing ‘n’ will be (ii) Shape of ‘p’ orbital is dumb bell in which the two lobes on
1s 2s 3s 4s. opposite side separated by the nodal plane.
(iii) s-orbitals known as radial node or modal surface. But there (iii) p-orbital has directional properties.
is no radial node for 1s orbital since it is starting from the nucleus. Z Z
Z
Y Y Y
X X X
Px PY Pz
Fig. 2.7
1S 2S
Fig. 2.6
46 Structure of