Atomic Structure Notes

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ATOMIC
STRUCTURE
By
PREPKNIGHT
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Table of Contents
Properties of Cathode Rays: ................................................................................................................................................. 3
Measurement of Charge to Mass Ratio: .................................................................................................................................4
Millikan's oil drop experiment ...............................................................................................................................................4
Canal rays ...............................................................................................................................................................................4
Bohr’s Atomic Model: ............................................................................................................................................................. 5
Rydberg Formula and Spectral Lines In The Hydrogen Specutrum ...................................................................................... 6
Plank’s Quantum Theory :..................................................................................................................................................... 8
Moseley's Law and his work on X-rays: ................................................................................................................................. 8
Importance of Moseley’s Law: ................................................................................................................................................9
Dual Nature of Electron: ......................................................................................................................................................10
Heisenberg’s Uncertainty Principle:....................................................................................................................................10
The Quantum Numbers and Orbitals ................................................................................................................................... 11
Shapes of Orbitals: ............................................................................................................................................................... 11
Electronic Configuration: ....................................................................................................................................................12
ATOMIC
STRUCTURE
The discharge tube experiment was a series of
Properties of Cathode Rays:
experiments conducted in the late 19th and early
• Cathode rays are streams of negatively
20th centuries which eventually lead to the
charged particles called electrons.
discovery of electron. A discharge tube is a sealed
• Cathode rays can ionize gases by
glass tube that is evacuated to a very low
knocking off electrons from gas atoms
pressure and filled with a gas. The tube has two
or molecules.
electrodes at opposite ends, and when a high
• Cathode rays can be deflected by electric
voltage is applied to the electrodes, a glow or
and magnetic fields, indicating that they
discharge can be seen within the tube.
are charged particles.
• Cathode rays behave as a stream of
particles with a fixed charge-to-mass
ratio, indicating that the particles have a
constant mass and negative charge.
• They can drive a small paddle wheel if
Important values: placed in their path. This verifies that
they are material particles and have
• At low pressure around 0.1 torr and high
certain momentum
potential 5000-10 000 Volts the gas
• Cathode rays can produce light when they
becomes conductor and gas starts to
collide with a surface, a phenomenon
emit light.
known as fluorescence.
• When pressure is reduced further to
• Cathode rays have a high velocity and can
around 0.01 torr cathode rays are given
travel in straight lines unless deflected
out.
by external fields.
James Chadwick's experiment in 1932 involved

Measurement of Charge to Mass
bombarding beryllium atoms with alpha particles,
Ratio: which resulted in the emission of neutral radiation
To determine the charge-to-mass ratio, Thomson that could penetrate through thick layers of matter.
used a cathode ray tube that had two parallel metal From this experiment, Chadwick concluded that this
plates, one above and one below the tube. He applied a radiation was composed of particles with no charge
voltage to the plates to create an electric field that and nearly the same mass as a proton, which he
could deflect the cathode rays as they passed through identified as the neutron.
the tube. By measuring the angle of deflection and the
strength of the electric field, Thomson was able to Ernest Rutherford's famous experiment in 1911
calculate the charge-to-mass ratio of the cathode ray involved firing alpha particles at a thin sheet of gold
particles. foil and observing their behavior as they passed
through it. From this experiment, Rutherford drew
Value of e/m determined by Thomson → 1.7588 x 1011 several conclusions:
Coulombs kg-1
1. Most of the alpha particles passed straight
Millikan's oil drop experiment through the gold foil without being deflected,
It provided the first accurate measurement of the indicating that most of the space in an atom
charge of an electron in 1909. It helped to establish is empty.
the concept of the electron as a fundamental particle. 2. A few alpha particles were deflected at small
The experiment also helped to confirm that the angles, suggesting that they had come close
charge of an electron is quantized, meaning it exists to positively charged particles in the atom.
only in discrete amounts. 3. A very small number of alpha particles were
deflected back towards the source, indicating
that they had encountered a dense, positively
charged nucleus at the center of the atom.
Canal rays
Are streams of positively charged particles that were From these observations, Rutherford concluded that
discovered by Eugen Goldstein in 1886. They are atoms consist of a small, dense, positively charged
produced when a high voltage is applied to a gas in a nucleus at the center, surrounded by negatively
discharge tube, causing the gas atoms to ionize and charged electrons in orbit around it. This model of the
form positive ions. These ions are then attracted atom became known as the "planetary model" and
towards a negatively charged electrode, creating a replaced the previously accepted "plum pudding"
beam of positively charged particles. model.
the electron falls back down to a lower

Bohr’s Atomic Model:
energy level, it emits energy in the form of
Proposed by Neil Bohr in 1913 to remove defects of
a photon.
Rutherford Atomic Model. Bohr's model of hydrogen is
• The angular momentum of an electron in a
based on the nonclassical assumption that electrons
particular energy level is quantized and can
travel in specific shells, or orbits, around the nucleus.
only take on certain values. It is an integral
According to it:
multiple of the factor h/2π.
• Electrons in an atom can only occupy certain i.e. mvr=nh/2π where n = 1,2,3, ……
energy levels, or shells, and cannot exist in
By keeping the electrons in circular, quantized orbits
between these levels.
around the positively-charged nucleus, Bohr was able
• Electrons can move from one energy level to
to calculate the energy of an electron in the nth
another by absorbing or emitting a specific
energy level of hydrogen:
amount of energy in the form of photons.
• The energy of an electron in a particular 𝟏
𝑬(𝒏) = − 𝒏𝟐 ⋅ 𝟏𝟑. 𝟔ⅇ𝑽
shell is proportional to its distance from the
nucleus. Bohr explained the hydrogen spectrum in terms of
• The ground state of an atom is the state in electrons absorbing and emitting photons to change
which all electrons are in their lowest energy energy levels, where the photon energy is:
level. 𝟏 𝟏
• When an atom absorbs energy, an electron 𝒉𝒗 = 𝜟𝑬 ( − ) ⋅ 𝟏𝟑. 𝟔ⅇ𝒗
𝒏𝟐𝒍𝒐𝒘 𝒏𝟐𝒉𝒊𝒈𝒉
can be excited to a higher energy level. When
❖ The limitation of Bohr model is that it does not work for systems with more than one electron.
Calculations of Wave Numbers of Photons of Various Spectral Series by Bohr’s Theory

The following equation gives the values of wave number of photons emitted or absorbed when the electron
jumps between n1 and n2 orbits.
1 1
𝑣̅ = 1.09678 × 107 [𝑛2 − 𝑛2 ] 𝑚−1
1 2
Where 1.09678 x 107 is the Rydberg constant.
Defects OF BOHR’s Atomic Theory:

The Bohr Model was an important step in the development of atomic theory. However, it has several limitations.
• It is in violation of the Heisenberg Uncertainty Principle. The Bohr Model considers electrons to have both a
known radius and orbit, which is impossible according to Heisenberg.
• The Bohr Model is very limited in terms of size. Poor spectral predictions are obtained when larger atoms
are in question.
• It cannot predict the relative intensities of spectral lines.
• It does not explain the Zeeman Effect, when the spectral line is split into several components in the
presence of a magnetic field.
• The Bohr Model does not account for the fact that accelerating electrons do not emit electromagnetic
radiation.
Zeeman effect: splitting of atomic energy levels in a magnetic field, causing spectral lines to split into multiple
components.
Stark effect: shifting of atomic energy levels in an electric field, causing spectral lines to shift in frequency or
wavelength.
A continuous spectrum is produced when an atom emits or absorbs radiation over a broad range of frequencies or
wavelengths. This type of spectrum is typically seen in solids, liquids, and dense gases.
A line spectrum, on the other hand, is produced when an atom emits or absorbs radiation at specific frequencies or
wavelengths, resulting in discrete lines in the spectrum. This type of spectrum is typical of gases and is often
referred to as an atomic emission or absorption spectrum.
The line spectrum observed in the Bohr model is a consequence of the discrete energy levels of the electron in the
atom.
RYDBERG FORMULA AND SPECTRAL LINES IN THE HYDROGEN

SPECTRUM
The easiest formula used to calculate the wavelengths of the lines in the hydrogen spectrum is the Rydberg formula:
1 1 1
= 𝑅 ( 2 − 2)
𝜆 𝑛1 𝑛2
where λ is the wavelength of the spectral line, R is the Rydberg constant, and n1 and n2 are integers that correspond
to the energy levels of the electron in the hydrogen atom. The Rydberg constant for hydrogen is approximately
1.097 x 107 m-1.
Lyman series:
• Consists of spectral lines emitted or absorbed when the electron transitions from n≥2 to n=1.
• Wavelengths fall in the ultraviolet range of the electromagnetic spectrum.
Balmer series:
• Wavelengths fall in the visible range of the electromagnetic spectrum.
Paschen series:
• Wavelengths fall in the infrared range of the electromagnetic spectrum, just beyond the Brackett series.
Brackett series:
• Wavelengths fall in the infrared range of the electromagnetic spectrum, just beyond the Paschen series.
Pfund series:
• Wavelengths fall in the infrared range of the electromagnetic spectrum.
Plank’s Quantum Theory :

Max Planck introduced the concept of energy quantization to explain the behavior of electromagnetic radiation.
• Planck proposed that energy is emitted or absorbed in small, discrete packets called "quanta".
• Planck's constant (h) is a fundamental constant of nature that relates the energy of a quantum to its
frequency: E = hf
• Using c=f λ we can also write the equation as E = hc/ λ
• Wave number represents the number of wavelengths that occur in a unit distance. Mathematically, the wave
number is defined as the reciprocal of the wavelength (λ):
𝑣̅ = 1/ λ
So Energy can also be calculated as,
E = hc𝑣̅
Moseley's Law and his work on X-rays:

X-rays are produced when rapidly moving electrons collide with heavy metal anode in the discharge tube. Energy is
released in the form of electromagnetic waves when the electrons are suddenly stopped.
Production of X-Rays:
X-rays are produced through a process called X-ray radiation or X-ray emission. The production of X-rays involves
the interaction of high-energy electrons with matter, typically within a device called an X-ray tube.
Inside an X-ray tube, a high voltage is applied between two electrodes: a cathode and an anode. The cathode consists of
a filament, usually made of tungsten, which emits electrons when heated. When a current passes through the
filament, it heats up and releases a stream of electrons. These electrons are accelerated toward the anode, which is
usually made of a metal like tungsten or copper.
• The wavelength of X-rays produced depends upon the nature of the target metal. Every metal has its own
characteristic X-rays. The X-rays are passed through a slit in platinum plate and then emerged through
aluminum window. This is thrown on a crystal of K4 [Fe(CN)6 ], which analyses the X-ray beam. The rays are
diffracted from the crystal and are obtained in the form of line spectrum of X-rays. This is allowed to fall
on photographic plate. This line spectrum is the characteristic of target material used. This characteristic
X-rays spectrum has discrete spectral lines. These are grouped into K-series, L-series and M-series, etc.
Each series has various line as Kα , Kβ, Lα , Lβ , M α , Mβ etc.
• Moseley's Law states that the square root of the frequency of the characteristic X-ray emitted by an atom
is directly proportional to the atomic number (Z) of the element. This law convinces us that it is the atomic
number and not the atomic mass of the element which determines its characteristic properties, both
physical and chemical.
√𝑣 = 𝑎(𝑍 − 𝜎)
where ν is the frequency of the characteristic X-ray, Z is the atomic number of the element, a is a proportionality
constant, and σ is a screening constant that depends on the electron configuration of the atom.
• Moseley discovered that the atomic number of an element could be determined by measuring the frequency
of its characteristic X-rays. He employed thirty eight different elements from aluminum to gold, as target
in X-rays tube.
• Moseley's work on X-ray spectral lines also led to the discovery of the K and L series of X-ray emissions.
The K series refers to the X-rays emitted when an electron transitions from a higher energy level to the
first energy level (n=1), while the L series refers to X-rays emitted when an electron transitions from a
higher energy level to the second energy level (n=2).
• Uses of X-Rays include:
1. Medical Imaging: X-ray imaging is extensively used in medical diagnostics to visualize the internal
structures of the body. It helps in detecting fractures, identifying bone abnormalities, diagnosing lung
conditions, examining the digestive system, and detecting certain types of cancers.
2. Airport Security: X-ray scanners are employed in airports for security screening of luggage and personal
belongings. These scanners use X-rays to generate images of the contents of bags, allowing security
personnel to identify any prohibited or dangerous items.
3. Industrial Radiography: In industries such as oil and gas, X-ray imaging is used to inspect the integrity of
pipelines, tanks, and other equipment. It helps identify corrosion, leaks, or structural defects that may
compromise safety.
4. Archaeology and Art Conservation: X-ray imaging is employed in archaeology and art conservation to
examine artifacts and paintings non-invasively.
5. Material Analysis: X-ray diffraction and X-ray fluorescence techniques are used to analyze the composition
and structure of materials.
Importance of Moseley’s Law:

• Moseley arranged K and Ar, Ni and Co in a proper way in Mendeleev’s periodic table.
• This law has led to the discovery of many new elements like Tc(43), Pr(59), Rh(45).
• The atomic number of rare earths have been determined by this law.
Dual Nature of Electron:

The dual nature of electrons refers to the observation that electrons, along with other particles like photons, exhibit
properties of both particles and waves. This concept was proposed by Louis de Broglie, a French physicist. According to
de-Broglie, all matter particles in motion have a dual character. It means that electrons, protons, neutrons, atoms
and molecules possess the characteristics of both the material particle and a wave.
He proposed an equation, known as the de Broglie equation, which relates the wavelength (λ) of a particle to its
momentum (p):
λ=h/p
The wavelength associated with an electron is inversely proportional to its momentum. Thus, particles with larger
momentum (such as high-speed electrons) have shorter wavelengths, while particles with smaller momentum (such as
low-speed electrons) have longer wavelengths.
Heisenberg’s Uncertainty Principle:

According to Heisenberg’s Uncertainty principle Position and Momentum of an Electron cannot be determined
simultaneously with absolute accuracy. Δx is the uncertainty in the measurement of the position and Δp is the
uncertainty in the measurement of momentum of an electron
ℎ
𝛥𝑥𝛥𝑝 ≥
4𝜋
This equation shows that if Δx is small then Δp will be large and vice versa. So, if one quantity is measured accurately
then the other becomes less accurate. Hence, certainty in the determination of one quantity introduces uncertainty in
the determination of the other quantity.
An orbital in quantum mechanics is a mathematical description of the probability distribution of finding an electron
within a specific region around the nucleus of an atom. It does not provide an exact path or trajectory for the
electron but rather a probability map.
The uncertainty principle implies that we cannot simultaneously know the precise position and momentum of an
electron in an atom. Therefore, instead of describing the electron's path, orbitals give us information about the
likelihood of finding the electron in different regions of space. The shape and size of an orbital are determined by the
quantum numbers associated with the electron, such as the principal quantum number (n), the azimuthal quantum
number (l), and the magnetic quantum number (m).
The volume of space in which there is 95% chance of finding an electron is called atomic orbital. The term orbital
should not be confused with the term orbit as used in the Bohr’s theory. The orbital can be regarded as a spread of
charge surrounding the nucleus. This is often called the “electron cloud”.
The Quantum Numbers and Orbitals

Principal quantum number (n): This quantum number determines the size and energy level of an electron's orbital. It
can have integer values starting from 1 and increasing in whole numbers (2, 3, 4, etc.) For example, the principal
quantum number for the first shell is 1, the second shell is 2, and so on.
n=1 → K shell
n=2 → L shell
n=3 → M shell
n=4 → N shell
Azimuthal quantum number (l): This quantum number determines the shape of the electron's orbital. It can have
values ranging from 0 to n-1. The different values of l correspond to different subshells within an energy level. For
example, l=0 corresponds to the s subshell, l=1 corresponds to the p subshell, l=2 corresponds to the d subshell, and
l=3 corresponds to the f subshell.
Magnetic quantum number (m): This quantum number determines the orientation of the electron's orbital in space. It
can have values ranging from -l to +l. For example, if l=1, then m can have values of -1, 0, or +1, which correspond to
the three p orbitals in that subshell. If l=2, it means we are dealing with a d orbital. The magnetic quantum number
(m) can range from -2 to +2, with a total of 5 possible values. Examples of magnetic quantum numbers for l=2
include -2, -1, 0, 1, and 2.
Spin quantum number (s): This quantum number describes the intrinsic angular momentum, or spin, of the electron.
It can have a value of +1/2 or -1/2, which corresponds to the two possible spin states of an electron.
Shapes of Orbitals:
• s orbitals: These are spherical in shape and have a single lobe. They are symmetrical around the nucleus and
have no nodal planes.
• p orbitals: These are dumbbell-shaped and have two lobes, separated by a nodal plane. There are three
mutually perpendicular p orbitals.
• d orbitals: These have a more complex shape with four lobes and two nodal planes. There are five d orbitals,
each with a different orientation.
• f orbitals: These have an even more complex shape with eight lobes and three nodal planes. There are seven f
orbitals, each with a different orientation.
ELECTRONIC CONFIGURATION:
Step-by-step guide to writing electronic configurations:
• Determine the atomic number of the element you want to write the electronic configuration for. This
number indicates the number of protons in the element's nucleus.
• Use the Aufbau principle to fill the orbitals in order of increasing energy. This means that you start with the
lowest energy orbital and work your way up. The order of orbital filling is: 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d,
5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, and 7p.
• Determine the maximum number of electrons each orbital can hold. The s orbital can hold a maximum of 2
electrons, the p orbital can hold a maximum of 6 electrons, the d orbital can hold a maximum of 10
electrons, and the f orbital can hold a maximum of 14 electrons.
• Place the electrons into the orbitals in accordance with the Pauli exclusion principle, which states that no
two electrons in an atom can have the same set of quantum numbers.
• If the atom has a charge, add or subtract electrons accordingly. For example, if the atom is positively
charged, subtract electrons from the highest energy orbital first.
• Write the electronic configuration using the orbital notation or the shorthand notation. In the orbital
notation, each orbital is represented by a box, and the electrons are represented by arrows. In the shorthand
notation, the energy level and the number of electrons in each subshell are indicated by a superscript next
to the chemical symbol. For example, the shorthand notation for carbon would be: 1s2 2s2 2p2.
Aufbau principle: This principle states that electrons fill atomic orbitals in order of increasing energy. For
example, when writing the electronic configuration of carbon (atomic number 6), we start with the 1s orbital,
then move to the 2s orbital, and then fill the 2p orbitals in order (2px, 2py, 2pz).
Hund's rule: This rule states that when there are multiple orbitals with the same energy
level (such as the three 2p orbitals in carbon), electrons will occupy separate orbitals with parallel spins
before pairing up. For example, in the electronic configuration of carbon (1s2 2s2 2p2), the two electrons in
the 2p subshell will occupy separate orbitals with parallel spins (one in 2px and one in 2py) before they
pair up.
Pauli's exclusion principle: This principle states that no two electrons in an atom can have the same set of
four quantum numbers. In other words, each electron must have a unique combination of principal quantum
number (n), azimuthal quantum number (l), magnetic quantum number (m l), and spin quantum number (ms).
For example, the two electrons in the 2s orbital of carbon have the same values of n, l, and ml (2, 0, 0), but
they have opposite spins (ms = +1/2 and -1/2).

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AKU & MDCAT Notes by PrepKnight.

James Chadwick's experiment in 1932 involved

the electron falls back down to a lower

Calculations of Wave Numbers of Photons of Various Spectral Series by Bohr’s Theory

Where 1.09678 x 107 is the Rydberg constant.

Defects OF BOHR’s Atomic Theory:

RYDBERG FORMULA AND SPECTRAL LINES IN THE HYDROGEN

Plank’s Quantum Theory :

So Energy can also be calculated as,

Moseley's Law and his work on X-rays:

Importance of Moseley’s Law:

Dual Nature of Electron:

Heisenberg’s Uncertainty Principle:

The Quantum Numbers and Orbitals

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