CHEMISTRY I

SCH 1110

DR. BENSON ONGARORA

JULY, 2024
 Atomic Models
Evolution of Atomic Theories

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 Atomic Models
Evolution of Atomic Theories

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 Evolution of Atomic Theories
John Dalton (solid sphere model)
 Regarded atom as the ultimate indivisible, invisible particle of
matter
 Atom as a solid sphere
 Compounds comprised of specific ratios of different atoms

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 Evolution of Atomic Theories
Thomson Model (Plum pudding model)
 Regarded atom as a sphere
 Has positive and negative charges are embedded in it

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 Evolution of Atomic Theories
Rutherford Model (Nuclear model)
 Conducted gold foil experiment
 Electrons orbit around a fixed positively charged nucleus
 Atom is made of a tiny positively charged nucleus

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 Evolution of Atomic Theories
Bohr Model (Planetary model)
 Electrons occupy concentric, specific orbits around the nucleus
 Only certain orbits can exist and each orbit corresponds to a specific
energy
 Could not explain the spectra of multi-electron atoms
 Ignored Heisenberg uncertainty principle (dual nature of matter)

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 Evolution of Atomic Theories
Bohr-Sommerfeld Model (Extended Bohr model)
 Introduced elliptical orbits; allowed for more complex electron motion
 Accounted for fine spectral lines
 Introduced azimuthal quantum numbers (angular momentum
quantum numbers)

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 Evolution of Atomic Theories
Schrodinger Model (Quantum model)
 Location of electron could be described as part of a ‘cloud’ around the
nucleus
 In line with Heisenberg uncertainty principle (dual nature of matter)
 Not possible to determine accurately both velocity and position of
an electron (or any other very small particle) simultaneously
 Gives wave function(s) (ψ)

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 Electromagnetic Spectrum
Visible light, infrared radiation, microwaves, radio waves, ultraviolet, x-
rays and gamma rays are all types of electromagnetic radiation

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 Wave nature of electron
De Broglie’s wave-particle duality
 Not only does light have the dual properties of waves and particles, but
also particles of matter have properties of waves
 Wavelength (λ) of those particle waves is given by:
λ = h/mv

where m and v are the mass and velocity of the particle

 Planck’s constant, h, is so small that the wavelengths are in an
observable range only for particles of atomic or subatomic mass

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 Basic Ideas of Quantum Mechanics
 Atoms or molecules exist in certain energy states only
 When they emit or absorb light, their energies change
 Energy change is given by:

 Allowed energy states of atoms and molecules can be described by

sets of numbers called quantum numbers

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 Wave character of light
 Distance between two waves is the wavelength, λ
 Frequency is the number of waves passing a point in space per second, ν
 Product of wavelength and frequency is equal to the velocity of light, c
c = λν
(The value of c can be rounded to c = 2.998 × 108 m/s for most calculations)

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 Particle character of light
 Energy of light is emitted, absorbed, or converted to other forms in quanta
 Particle of light is called the photon
 Energy of a photon is proportional to the frequency:
ε = hν = (6.626 × 10−34 J · s)ν
Planck’s constant, h, is the universal proportionality constant

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Atomic spectra
 Johann Balmer (1825-1898) and Johannes Rydberg (1854-1919)
showed that the wavelengths of the various lines in the hydrogen
spectrum can be related by a mathematical equation:

 Here R is 1.097 × 107 m-1 and is known as the Rydberg constant

 The n values are positive integers, and n1 is smaller than n2
 Transitions could be in three series:
a) Lyman
b) Balmer
c) Paschen
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Example:
The figure shows the line spectra and the electron transitions of the hydrogen atom
with its characteristic three spectral series, Lyman, Balmer and Paschen. Calculate the
wavelength (in nm) of spectral line associated with the n = 6 to n = 3 electron
transition in a hydrogen atom.

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Solution:

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 Quantum Numbers
Principal quantum number, n
 Denotes energy level of electrons
 The larger the value of n, the higher the energy
 The larger the value of n, the higher the orbital
 Orbitals with the same n belong to the same shell

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 Quantum Numbers
Angular momentum quantum number, l
 Denotes the shape of orbital
 Values range from 0 to n – 1
 Angular momentum quantum numbers correspond to different subshells

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 Quantum Numbers
Magnetic quantum number, ml
 Defines the different spatial orientations of the orbitals
 Values range from -l to +l
 Three p orbitals corresponding to ml = 1, 0, and -1
 However, in chemistry, the three orbitals are oriented along the x, y, and
z axes to display the shapes and their directions

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 Quantum Numbers
Magnetic quantum number, ml
 Five d orbitals corresponding to ml = 2, 1, 0, -1 and -2

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 Quantum Numbers
Spin quantum number, ms
 Denote orientations of an electron
 Two possible spins are denoted by ms = +½ and -½
 Each atomic orbital can accommodate no more than two electrons, one
with ms = +½ and another with ms = -½

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Permissible values of Quantum Numbers

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 Filling of Orbitals
Electrons are filled in orbitals in order of increasing energy in accordance
with Pauli exclusion principle and Hund’s rule
Pauli’s Exclusion Principle
“No two electrons in an atom can have the same set of four quantum
numbers”
Hund’s Rule
“Pairing of electrons in the orbitals belonging to the same subshell
does not take place until each orbital belonging to that subshell has got
one electron each, i.e., is singly occupied”

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Hund’s Rule

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 Applications of Hund’s Rule
Examples

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 Applications of Hund’s Rule
Examples

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 Applications of Hund’s Rule
Examples
 In excited state the energies of 2s and 2p come further close and hence
the four electrons (all in 2s and 2p) divide themselves between four
orbitals
 Thus, covalency of carbon is four

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 Electron configurations by the Aufbau Principle
 No two electrons in an atom may have identical sets of four quantum
numbers (Pauli exclusion principle)
 Orbitals are filled in the order of increasing energy (Klechkowski´s rule)
 Electrons occupy all the orbitals of a given subshell singly before pairing
begins
 These unpaired electrons have parallel spins (Hund´s rule)

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 Electron configurations by the Aufbau Principle
Example
 Iron has atomic number 26. Electronic configuration according to Aufbau
principle will be: 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d6
 But empty (p0 d0), half filled (p3 d5) and completely filled (p6 d10) orbitals of
a subshell provide symmetry and are more stable as compared to other
arrangements
 Thus, the other stable configuration for iron will be: 1s2, 2s2, 2p6, 3s2, 3p6,
4s2, 3d5, 4p1

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 Deviations from Aufbau Principle
Deviations from regularity may occur due to one of the following reasons:
a) half filled and completely filled orbitals are more stable than partially
filled orbitals
b) diamagnetic nature of atom
c) to explain the observed properties of elements like lanthanides and
actinides

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 Deviations from Aufbau Principle
Deviations from regularity may occur due to one of the following reasons:
a) half filled and completely filled orbitals are more stable than partially
filled orbitals
b) diamagnetic nature of atom
c) to explain the observed properties of elements like lanthanides and
actinides

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 Degenerate orbitals
Orbitals having equal energy are called degenerate orbitals

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The Periodic Table

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The Periodic Table

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The Periodic Table

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 Periodicity of atomic properties
 As n increases, atomic orbitals become larger and less stable
 As atomic number, Z, increases, any given atomic orbital becomes
smaller and more stable

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Atomic size

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Ionization charge

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 Electron affinity
Electron affinity is the energy change associated with the addition of an
electron to a gaseous atom

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 Electronegativity
Relative tendency of an atom to attract the bonding electrons to itself

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 Atomic and Mass numbers
(Z) = number of protons in the nucleus = number of electrons in a nuetral atom
Mass number (A) = number of protons (Z) + number of neutrons (n)

Atomic mass unit (amu)

 Atomic mass unit (amu) is defined as exactly 1/12 the mass of a 12C atom
 The mass of the 12C atom is taken to be exactly 12 amu

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 Isobars and isotopes
Isobars
 Atoms with same mass number but different atomic number e.g.

 Isotopes
 Atoms with identical atomic number but different atomic mass number
 The atomic mass of an element is the weighted average of the masses of
the individual isotopes of the element

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Isotopes
Example:
Naturally occurring copper consists of 69.17% 63Cu and 30.83% 65Cu. The
mass of 63Cu is 62.939598 amu, and the mass of 65Cu is 64.927793 amu.
What is the atomic mass of copper?

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