Atomic Structure: Rutherford Atomic Model, Planck's Quantum Theory, Bohr Atomic Model, de Broglie Dual Nature, Heisenberg's Uncertainty Principle
Atomic Structure: Rutherford Atomic Model, Planck's Quantum Theory, Bohr Atomic Model, de Broglie Dual Nature, Heisenberg's Uncertainty Principle
Atomic Structure: Rutherford Atomic Model, Planck's Quantum Theory, Bohr Atomic Model, de Broglie Dual Nature, Heisenberg's Uncertainty Principle
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• Greater the magnitude of the charge on the particle, greater is the interaction with the electric or
magnetic field and thus greater is the deflection. Lighter the mass of the particle, greater the deflection
• By carrying out accurate measurements on the amount of deflections observed by the electrons on the
electric field strength or magnetic field strength, Thomson was able to determine the value of e/me as:
𝑒
= 1.758820 × 1011 C kg–1
𝑚𝑒
2. Atomic Models
The major problems before the scientists after the discovery of sub-atomic particles were:
i. To account for the stability of atom
ii. To compare the behavior of elements in terms of both physical and chemical properties
iii. To explain the formation of different kinds of molecules by the combination of different atoms
iv. To understand the origin and nature of the characteristics of electromagnetic radiation absorbed or
emitted by atoms
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Fig.3 Schematic view of Rutherford’s scattering experiment. When a beam of alpha (𝛼) particles is
“shot” at a thin gold foil, most of them pass through without much effect. Some, however, are deflected.
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• On the basis of the observations, Rutherford drew the following conclusions regarding the structure
of atom:
(i) Most of the space in the atom is empty as most of the 𝛼–particles passed through the foil
undeflected.
(ii) A few positively charged 𝛼–particles were deflected. The deflection must be due to enormous
repulsive force showing that the positive charge of the atom is not spread throughout the
atom but concentrated in a very small volume that repelled and deflected the positively
charged 𝛼–particles.
(iii) Calculations by Rutherford showed that the volume occupied by the nucleus is negligibly
small as compared to the total volume of the atom. The radius of the atom is about 10–10 m,
while that of nucleus is 10–15 m.
• On the basis of above observations and conclusions, Rutherford proposed the nuclear model of atom:
(i) The positive charge and most of the mass of the atom was densely concentrated in extremely
small region. This very small portion of the atom was called nucleus by Rutherford.
(ii) The nucleus is surrounded by electrons that move around the nucleus with a very high speed
in circular paths called orbits.
(iii) Electrons and the nucleus are held together by electrostatic forces of attraction.
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into the nucleus. But this does not happen. Thus, the Rutherford model cannot explain the stability of
an atom.
ii. Another serious drawback of the Rutherford model is that it says nothing about distribution of the
electrons around the nucleus and the energies of these electrons.
iii. Line Spectra of atom can’t be explained by this model.
• It is now well established that there are many types of electromagnetic radiations, which differ from
one another in wavelength (or frequency). These constitute what is called electromagnetic spectrum
(Fig.6). The small portion around 1015 Hz, is what is ordinarily called visible light. It is only this part
which our eyes can see (or detect). Special instruments are required to detect non-visible radiation.
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(a)
(b)
Fig.6 (a) The spectrum of electromagnetic radiation. (b) Visible spectrum. The visible
region is only a small part of the entire spectrum.
• These radiations are characterized by the properties, namely, frequency (𝜐) and wavelength (𝜆).
(i) Frequency: Frequency is defined as the number of oscillations of a wave per unit time.
The SI unit for frequency (𝜈) is hertz (Hz, s–1)
(ii) Wavelength: Wavelength can be defined as the distance between two successive crests or
troughs of a wave. Wavelength should have the units of length and the SI units of length is
meter (m).
(iii) Velocity: Wave velocity is the distance travelled by a wave per unit time. In vacuum all types
of electromagnetic radiations, regardless of wavelength, travel at the same speed, i.e., 3.0 × 108
m s–1. This is called speed of light and is given the symbol ‘c’.
(iv) Wave number: The number of waves per unit distance of radiant energy of a given
wavelength: the reciprocal of the wavelength (𝜆). Its units are reciprocal of wavelength unit,
𝟏
i.e., m–1 or cm-1 ̅=
𝝊 𝝀
• The frequency (𝜈), wavelength (𝜆) and velocity of light (c) are related by the equation:
𝝂𝝀 = 𝒄
(i) the nature of emission of radiation from hot bodies (black -body radiation)
(ii) ejection of electrons from metal surface when radiation strikes it (photoelectric effect)
(iii) variation of heat capacity of solids as a function of temperature
(iv) Line spectra of atoms with special reference to hydrogen.
(ii) The energy can take any one of the values from the following set, but cannot take on any values
between them. E = 0, h𝜈, 2h𝜈, 3h𝜈....nh𝜈.....
2.3.4 Evidence for the quantized Electronic Energy Levels: Atomic spectra
a. Continuous Spectra: Ordinary white light consists of waves with all the wavelengths in the
visible range, a ray of white light is spread out into a series of colored bands called spectrum. Such
a spectrum is called continuous spectrum. Continuous because violet merges into blue, blue into
green and so on. A similar spectrum is produced when a rainbow forms in the sky.
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(a)
(b)
Fig.8 (a) Atomic emission. The light emitted by a sample of excited hydrogen atoms (or any other element) can be
passed through a prism and separated into certain discrete wavelengths. Thus, an emission spectrum, which is a
photographic recording of the separated wavelengths is called as line spectrum. Any sample of reasonable size contains
an enormous number of atoms. Although a single atom can be in only one excited state at a time, the collection of
atoms contains all possible excited states. The light emitted as these atoms fall to lower energy states is responsible for
the spectrum. (b) Atomic absorption. When white light is passed through unexcited atomic hydrogen and then through
a slit and prism, the transmitted light is lacking in intensity at the same wavelengths as are emitted in (a) The recorded
absorption spectrum is also a line spectrum and the photographic negative of the emission spectrum.
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Where me is the mass of electron, v is the velocity and r is the radius of the orbit in which electron
is moving.
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2.3.7 Radius, Velocity and Energy of nth orbital from Bohr’s Theory
𝒏𝟐 𝒉𝟐 𝒏𝟐 𝒏𝟐
i. Radius: 𝒓𝒏 = ⟹ 𝒓𝒏 ∝ ⟹ 𝒓𝒏 = 𝒓𝟏
𝟒𝝅𝟐 𝒎𝒁𝒆 𝟐 𝒁 𝒁
𝟐𝝅𝒁𝒆𝟐 𝒁 𝒁
ii. Velocity: 𝒗𝒏 = ⟹ 𝒗𝒏 ∝ ⟹ 𝒗𝒏 = 𝒗𝟏
𝒏𝒉 𝒏 𝒏
𝟐𝝅𝒆𝟐
For electron revolving in the 1st Bohr orbital of Hydrogen, Z=1 and n=1 𝒗𝒏 = = 𝒗𝟏
𝒉
𝟐𝝅𝟐 𝒎𝒁𝟐 𝒆𝟒 𝒁𝟐 𝒁𝟐
iii. Energy: 𝑬𝒏 = − ⟹ 𝑬𝒏 ∝ ⟹ 𝑬𝒏 = 𝑬𝟏
𝒏𝟐 𝒉𝟐 𝒏𝟐 𝒏𝟐
• What does the negative electronic energy (En) for hydrogen atom mean?
This negative sign means that the energy of the electron in the atom is lower than the energy of a free
electron at rest. A free electron at rest is an electron that is infinitely far away from the nucleus and is
assigned the energy value of zero. Mathematically, this corresponds to setting n equal to infinity in
the equation. so that 𝐸∞ = 0. As the electron gets closer to the nucleus (as n decreases), En becomes
larger in absolute value and more and more negative. The most negative energy value is given by
n=1 which corresponds to the most stable orbit. We call this the ground state.
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𝟔.𝟔𝟐𝟔 𝑿 𝟏𝟎−𝟑𝟒 𝑱𝒔
= = 𝟏𝟎−𝟐𝟖 𝒎−𝟐 𝒔−𝟏
𝟒 𝑿 𝟑.𝟏𝟒𝟏𝟔 𝑿 𝟏𝟎−𝟔 𝒌𝒈
The value of ∆𝑣. ∆𝑥 obtained is extremely small and is insignificant. Therefore, one may say that in
dealing with milligram-sized or heavier objects, the associated uncertainties are hardly of any real
consequence.
ii. In the case of a microscopic object like an electron on the other hand, ∆𝑣. ∆𝑥 obtained is much
larger and such uncertainties are of real consequence. For example, for an electron
whose mass is 9.11×10-31 kg., according to Heisenberg uncertainty principle
𝒉
∆𝒗. ∆𝒙 =
𝟒𝝅𝒎
𝟔.𝟔𝟐𝟔 𝑿 𝟏𝟎−𝟑𝟒 𝑱𝒔
= = 𝟏𝟎−𝟒 𝒎−𝟐 𝒔−𝟏
𝟒 𝑿 𝟑.𝟏𝟒𝟏𝟔 𝑿 𝟗.𝟏𝟏 𝑿 𝟏𝟎−𝟑𝟏 𝒌𝒈
➢ Numerical
Q1. The wavelength range of the visible spectrum extends from violet (400 nm) to red (750 nm).
Express these wavelengths in frequencies (Hz). (1nm = 10–9 m)
𝒄 𝟑 𝑿 𝟏𝟎𝟖 𝒎𝒔−𝟏
Solution: 𝝂 = = = 𝟕. 𝟓𝟎 𝑿 𝟏𝟎𝟏𝟒 𝑯𝒛 (Violet)
𝝀 𝟒𝟎𝟎 𝑿 𝟏𝟎−𝟗 𝒎
𝒄 𝟑 𝑿 𝟏𝟎𝟖 𝒎𝒔−𝟏
𝝂= = = 𝟒 𝑿 𝟏𝟎𝟏𝟒 𝑯𝒛 (Red)
𝝀 𝟕𝟓𝟎 𝑿 𝟏𝟎−𝟗 𝒎
Q2. Calculate energy of one mole of photons of radiation whose frequency is 5 ×1014 Hz.
𝑬 = 𝒉𝝂
= (6.626 × 10−34 𝐽 𝑠) × (5 × 1014 𝑠 −1 ) = 3.313 × 10−19 𝐽
Q3. A 100 watt bulb emits monochromatic light of wavelength 400 nm. Calculate the number of
photons emitted per second by the bulb.
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Q4. What will be the wavelength of a ball of mass 0.1 kg moving with a velocity of 10 m s–1?
Q5. The mass of an electron is 9.1×10–31 kg. If its K.E. is 3.0×10–25 J, calculate its wavelength.
𝒉 6.626 𝑋 10−34 𝐽𝑠
𝝀= = = 8967 × 10−10 m = 897.6 nm
𝒎𝒗 (0.1 𝑘𝑔)(812 𝑚𝑠 −1 )
𝟏 𝟏
̅ =𝑹(
Solution: We know, 𝝂 − )𝒁𝟐
𝒏𝟐𝟏 𝒏𝟐𝟐
For Balmer series n1=2 and for the line 𝑯𝜶 , n2=3
𝟏 𝟏 𝟏
𝝂̅ = = 𝑹 ( − ) (For Hydrogen Z=1)
𝝀 𝒏𝟐𝟏 𝒏𝟐𝟐
𝟏 𝟏
= 𝟏𝟎𝟗𝟔𝟕𝟖 ( − )
𝟐𝟐 𝟑𝟐
∴ 𝝀 = 𝟔. 𝟓𝟔𝟒 × 𝟏𝟎−𝟓 𝒄𝒎
Q7. What is the value of the highest and lowest wavelength for Lyman series of hydrogen
spectra?
𝟏 𝟏 𝟏
̅ =𝑹(
Solution: 𝝂 − )𝒁𝟐 and 𝝂̅ =
𝒏𝟐𝟏 𝒏𝟐𝟐 𝝀
For Lyman series n1=1
When wavelength is maximum, wavenumber is minimum. This is satisfied when n2=2
𝟏 𝟏
𝝂̅ = 𝟏𝟎𝟗𝟔𝟕𝟖 ( − ) ⟹ 𝝀 = 𝟏𝟐𝟏𝟓. 𝟔𝟕 × 𝟏𝟎−𝟖 𝒄𝒎 = 𝟏𝟐𝟏𝟓. 𝟔𝟕Å
𝟏𝟐 𝟐𝟐
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Q8. If the energy of the 1st Bohr orbit of hydrogen is -13.6eV. What will be the energy of the 3rd
Bohr orbit?
𝒁𝟐
Solution: We know, 𝑬𝒏 = 𝑬𝟏
𝒏𝟐
𝟏𝟐
𝑬𝒏 = −𝟏𝟑. 𝟔 ( 𝟐) 𝒆𝑽 = −𝟏. 𝟓𝟏𝟏 𝒆
𝟑
Q9. Uncertainty in position of an electron moving with velocity of 𝟑 × 𝟏𝟎𝟒 𝒎/𝒔 accurate upto
0.001%. What will be the uncertainty in position?
0.001
Solution: Accuracy= 0.001%= 100
0.001
Δ𝑣 = 3 × 104 × = 0.3 𝑚/𝑠
100
𝒉 6.626 × 10−27
𝚫𝒙 = = = 1.93 𝑐𝑚
𝟒𝝅𝒎𝚫𝒗 4𝜋(9.1 × 10−28 ) × 0.3
Q10. The difference between the radii of 3rd and 4th orbitals of Li+2 is ∆𝑹𝟏 . The difference
between the radii of 3rd and 4th orbitals of He+ is ∆𝑹𝟐 . What is the ratio of ∆𝑹𝟏 and ∆𝑹𝟐 ?
𝒏𝟐
Solution: 𝒓𝒏 = 𝒓𝟏
𝒁
For Li 2+
𝒓𝟒 − 𝒓𝟑 = 𝒓𝟏 (𝟏𝟔 − 𝟗)/𝟑 = ∆𝑹𝟏
∆𝑹𝟏 𝒓𝟏 (𝟏𝟔−𝟗)/𝟑 2
Now, = =
∆𝑹𝟐 𝒓𝟏 (𝟏𝟔−𝟗)/𝟐 3
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