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> Chemistry
Notes
Quantum theory in terms of wavelength of radiation
>Physical Chemistry
E=
>Atomic Structure
: wavelength of radiation
By quantum theory in terms of wavelength of radiation
E=
c=
Einstein's Equation
E=
E = Total energy of substance
m = Total mass of substance
Photoelectric Effect
=
= Frequency of incident radiation
Ve = Velocity of electron
W = Work function of metal
me = Mass of electron
Vs = Stopping potential
Bohr's Theory
mVr =
Quantization of angular momentum
Bohr's Theory for K.E.
K.E. =
rn = radius of nth Bohr orbit
Bohr's Theory for Rn
=
orbit
orbits is
Bohr's Radius
=
Radius of a stationary orbit rn is
where,
(For Bohr radius)
Energy of Stationary Orbit (En)
=
Potential Energy
=
Speed of Electron in nth Bohr Orbit
=
Speed of Electron in nth Bohr Orbit
Emission Spectrum of H-atom
=
The frequency wavelengths or wave-number of a spectral line in any of the series in the emission spectrum of hydrogen atom can be calculated
using the following Rydberg's equation :
In a given stationary orbit, the number of de-Broglie wavelengths is equal to orbit number. If an electron at rest is accelerated by a potential
difference of V volt then de-Broglie wavelength is :
Here
is uncertainty in position and
The Schrodinger's Equation
=
is uncertainty in momentum.
(orbit number)
(ii) Centrifugal force of orbiting is exactly balanced by the electrostatic attraction between nucleus and electron
...(ii)
Atomic Weight (A)
Atomic weight is the relative weight of one atom of an element with respect to a standard weight.
isotope
Quantum Numbers
Quantum Numbers
To describe an electron completely inside the atom, four sets of quantum numbers are required. They are
Principal Quantum Number (n)
This specify position and energy of an electron in the atom. Possible values of 'n' are 0,1,2,3,..
Angular Momentum (Azimuthal or Subsidiary) Quantum Number (l)
This is used to specify subshell (orbital). Possible values of l are 0, 1,2, ... (n - 1). Orbitals with different values of l are denoted as:
l = 0,
s-orbital - spherical
l= 1,
p-orbital - dumb-bell shape
l = 2,
d-orbital double dump-bell shape
l = 3,
f-orbital etc
The value of l also determine shape of orbital as mentioned above.
The value of l determines orbital angular momentum (L) as:
The value of 'l' also determine the magnitude of magnetic moment as:
Where,
Magnetic Quantum Number (m)
It determines the preferred orientation of orbitals in three dimensional space. Its possible values are :
m= -l,...,0,...,+ l
eg, for l = 2, m = -2, -1, 0, +1, +2,
Total values of m for a given value of l=(2l+ 1) = number of orbitals in a given subshell.
Splitting of spectral lines occur when placed in a magnetic field (Zeeman effect) or in an electric field (Stark effect). Total lines from a single line in
the normal spectrum = (2l +1)
Total number of orbitals in nth orbit = n
are denoted as :
, s-subshell- spherical
, p-subshell - dumb-bell shape
, d-subshell - double dumb-bell shape
, f-subshell etc.
The value of
for
Total values of m possible are
s-subshell - 1 orbital
p-subshell - 3 orbitals
d-subshell - 5 orbitals
f-subshell - 7 orbitals
Spin Quantum Number (s)
Electrons spin on its own axis like a top, in clockwise and anticlockwise directions. The two directions of spinning is denoted by spin quantum
number as :
and
,
The spin quantum numbers are also denoted by up-half arrow
and down-half arrow
but neither the +1/2 and -1/2 or the 1 or
specific for any direction, they just represent the two opposite directions of spinning of electrons.
are
and
Hund's Rule of maximum multiplicity i.e. feeding one electron to each degenerate orbitals of a subshell first with parallel spins, thereafter
pairing of elctrons in orbitals of a subshell starts.
Pauli's Exclusion Principle i.e. only two electrons with antiparallel spins in each orbital.
Quantum Mechanical Model (The Schrodinger's Equation)
Probability density is
Total Radial Probability is
Radial nodes
Angular nodes
Radial Peaks
Scattering of
K.E of electron
P.E of electron
Total energy of electron
Speed of electron
fine structure constant
C is speed of light
Ionisation energy
Separation Energy
-19
Thus , a subatomic particle, i.e., a fundamental constituent of all matter having a mass 1.673 x 10-27 kg and charge +1.602 x 10-19 C is called a
proton.
Neutron
Chadwick (1932) bombarded Be or B-atoms (sheet) with high speed alpha
particles and noticed the emission of neutral particles, i.e.,
neutrons of mass nearly equal to proton. A neutron is therefore, a subatomic particle, a fundamental constituent of matter having a mass 1.675 x
10-27 kg and no net charge. (usually represented as
)
Most of the
-particles passed without any deflection or deflected through small angles of the order of 1o.
Some of the them were deflected away from their path by an angle as large as 90o or more.
Only a few (one in about 10,000) were returned back to their original direction of propagation.
The number of
-particles scattered and their scattering angles are represented in Fig. 2(b).
The scattering i.e., number of scattered -particles (N) is inversely proportional to the square of the kinetic energy of the incident particle. Higher
the energy of the incident particle, the smaller will be number of scattered particle.
The scatttering of
momentum.
-particles involves perfectly elastic nuclear collisions and obey the law of conservation of energy, momentum and angular
-particles (N) is proportional to the square of the atomic number (Z) of both the incident particles ( i.e.,
The scattering (N) is also proportional to the targets thickness for thin targets.
The number of
The number of
, i.e.,
, where
These observations led Rutherford to propose the concept of nucleus in an atom. The size of the various nuclei can be calculated from the
relation,
r = (1.33 x 10-13)A1/3 )
where r is the radius of the nuclei (in cm) with mass number A.
where c is velocity of light and is wavelength of light. Thus, a body can radiate or absorb energy in whole number multiplies of a quantum. i.e.,
hv, 2hv, 3hv, ... nhv ; where n is an integer.
The energy of photon decreases with increase in wavelength. That is why a photon of red light is less energitic than a photon of the blue light.
Note : Intensity of light (no. of photons falling per unit area per sec) depends upon the number of these photons and if intensity of light is
referred as amount of energy falling per unit area per sec; then it also depends upon the wavelength of photons used.
The rest of photon is zero.
Mass of moving photon m is given by;
or
Electromagnetic radiation
Thus, wave motion represents propagation of a periodic disturbance carrying energy. A wave has five characteristics, i.e., wavelength, frequency,
velocity, wave number and amplitude.
Wavelength or
It is the distance between successive points of equal phase of a wave, i.e., the distance between two neighbouring crests or troughs. It is normally
expresses in . (also in cm, m, nm, etc.)
Frequency or (v)
It is the number of cycles or oscillations or vibrations of a wave motion in unit time.
,
expressed in Hz or sec-1
Velocity
It is the distance travelled by the wave in one second.
Velocity = wavelength x frequency; (expressed in cm sec-1 )
Wave number
It is defined as the number of waves in unit length. It is reciprocal of wavelength.
i.e.,
Amplitude
If any quantity is varying in an oscillatory manner about an equilibrium value, the maximum departure from that equilibrium is called amplitude.
Electromagnetic spectrum
The arrangement of the various types of electromagnetic radiation in order of their increasing (or decreasing) wavelengths frequencies is known
as electromagnetic spectrum.
DeBroglie Wave Equation
De Broglie used Einstein special theory of relativity together with Planck's quantum theory to establish wave properties of particles.
For photon. E = mc2 = mc. c = p.c
(where p is momentum of photon)
Also, E = hv
Thus,
or
...... (22)
This relation for photon was extended to all particles by de Broglie. Particle waves are matter waves and the wave-length expressed by Eq. (22) is
called de Broglie wavelength of particle. Thus for electron if u is velocity for electron wave and is its wavelength, then
..... (23)
or
i.e., angular momentum is quantised for closed orbit. de Broglie equation was verified experimentally by Davisson and Germer by their electron
diffraction experiment using Ni crystal. The electron microscope was constructed on the basis of de Broglie concept.
or
is uncertainty in momentum;
is uncertainty in position along one axis
is uncertainty in velocity along same axis
As the mass of particle increases the uncertainty principle and de Broglie concept loses its significance in case of larger objects.
Shapes of orbital
The electron cloud represents the shape of orbital. Electron cloud is not uniform but it is dense where the probability for finding electron is
maximum.
s-orbital do not vary with angles, i.e., they do not have directional dependence. Thus, all s-orbitals are called spherically symmetrical. Their size
increases with increase in the value of n. 1s-orbital has no nodal plane (the plane at which zero electron density is noticed.) 2s-orbital has one
nodal plane; 3s-orbital has two nodal plane. It is thus, evident that number of nodal planes increases with increasing value of principle quantum
number n.
All orbitals with
have angular dependence. Therefore, p and d and other higher angular momentum orbitals are not spherically
symmetrical. p-orbitals consist of two lobes to form dumbbell shaped structure. The three p-orbitals along x, y, z-axis named as px, py, pz orbitals
are perpendicular to each other. All the three p-orbitals of a sub-shell have the same size and shape but differ from each other in orientation. The
subscripts x, y and z indicate the axis along which orbitals are oriented and possess maximum electron density. Also the orbitals of a sub-shell
having same energy are referred as degenerated orbitals.
The 'd' orbitals are resolved into five shapes. Each of the d-orbital possesses same energy but differ in their orientation in space. However, during
complex formation, these splits up into different energy levels in presence of ligands. Also four of the d-orbitals presence of ligands. Also four of
the d-orbitlas (dxy, dyz, dxz and dx2 - y2 ) contain four lobes while fifth, i.e., dz2 consists of only two lobes along z-axis an a doughnut in the xy-plane.
The f-orbitals are resolved into 7 shapes, Their shape is complicated. However the seven orientations of f-orbitals are represented by the terms :
fy(x2 - y2), fy(z2 - x2), fx(z2 - y2), fx(x2 - y2), fz(x2 - y2), fz(x2 - y2). fxyz
Note : 1. The plane and point at which zero electron density exists (i.e.,
) is known as nodal plane or nodal point, e.g., the probability of
finding electron between 1s and 2s-orbitals or between two lobes of p-orbitals is zero.
2. An orbital with quantum number n and possesses :
Angular or non-spherical nodes
Radial or spherical nodes
Thus, total nodes in an orbital
3. For one electron systems (an atom or an ion) the energy of orbital depends only on the number of nodes, i.e., on n and not on and
therefore, in H-atom or He+ energy levels of orbitals in a shell are same, i.e., energy level of 3s = 3p = 3d.
. It is
4. As r approaches zero, the wave function vanishes for all orbitals except the s-orbitals, thus, only an electron in 1s-orbital can penetrate the
nucleus, i.e., have a finite probability of being found right at the nucleus.
Photoelectric Effect
According to Einstein-On exposing a metal surface to radiations, a part of photon's energy (say W) is used by the electrons to escape form the
metal, the remaining imparts the kinetic energy (1/2 mu2) to the photo-electrons, If the incident radiation has frequency v, then its photons have
energy hv, it follows form the conservation of energy principle that,
or
The equation shows that if KE is plotted against frequency of incident radiation, a straight line is obtained with a slope equal to Planck's constant
The equation expresses the fact that the metal provided the photon energy (i,e, hv) is greater than the binding energy or work function (W) of the
electron in the metal, Further the released electron will escape out with kinetic energy equal to (hv - W).
Instead of irradiating a metal, one can irradiate atoms with photons of known frequency, the above equation may be written as hv = IE + KE.
This suggests that the photon energy is partly used to knock out an electron form the atom (i.e., IE) and the remainder as the kinetic energy of the
released photo-electron,
Note : An atom or a molecule can absorb only one photon.
Thus, ratio of mth and nth line of Lyman series can be written as
Lyman series :
Balmer series :
is minimum.
4. The wavelength of line in each series is minimum for the line having
for Balmer and so on.
is maximum, i.e.,
and
and
5. For Balmer series, the first line is referred as line, the second line as line and so on.
6. The series limit of any series exists when electron jumps from infinity to n1 shell, i.e., last line represents series limit of each respective series.
7. The continuum in line spectra is noticed beyond a certain limit, i.e., after certain value of n.
8. Only Lyman series is observed in emission and absorption spectrum both. This is due to the fact that usually electrons in an atom lies in ground
state,
9. For n1 = 6 and n2 > 6, the Humphry series has also discovered,
10. The restriction of emission of line spectrum for H-atom or H-like species has been given by selection rule. The transition is allowed for H-like
species or H-atom if it has.
It is thus evident that transition from 4p to 3p will not give line spectrum.
Moseley's Work and Atomic Number
Moseley's introduced the concept of atomic number. He found that on bombarding the anti cathode with cathode rays, X-rays are emitted whose
wavelength are characteristic of the element bombarded. Moseley showed that the frequency (v) of a given line in the spectrum of X-rays was
related to that atomic no. (Z) of the element by the expression :
where a is proportionality constant and b is a constant for all the lines of a given series. A straight line graph was obtained in values. This led
Moseley to modify the periodic law - The properties of elements are in periodic function to their atomic number and not atomic weight as
proposed by Mandeleef.
Photo electric effect
When light of an appropriate frequency (or correspondingly of an appropriate wavelength) is incident on a metallic surface, electrons are
liberated from the surface. This observation is known as photoelectric effect. Photoelectric effect was first observed in 1887 by Hertz. For
photoemission to take place, energy of incident light photons should be greater than or equal to the work function of the metal.
or
......... (i)
or
Here, is the minimum frequency required for the emission of electrons. This is known as threshold frequency f0 .
Thus, (threshold frequency)
...... (ii)
Here, is the largest wavelength beyond which photoemission does not take place. This is called the threshold wavelength .
Thus,
(threshold wavelength)
...... (iii)
Hence, for the photoemission to take place either of the following conditions must be satisfied.
...... (iv)
Dipole Moment
Dipole moment = ionic charge ionic distance
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