CH 110
ATOMIC STRUCTURE
&
PERIODICITY
2
Atomic Spectra
Another mystery in
the early twentieth
century involved the
emission spectra
observed from
energy emitted by
atoms and
molecules.
Atomic Spectra
• For atoms and
molecules, one does
not observe a
continuous spectrum,
as one gets from a
white light source.
• Only a line spectrum
of discrete
wavelengths is
observed.
© 2012 Pearson Education, Inc.
Atomic Spectra
• An atom with lowest energy is in its ground
state; principal quantum # is 1.
• Principal quantum number determines the
energy level of an electron.
• Excitation of an electron by absorbing energy
raises the atom to higher energy levels
(excited state, where n = 2,3, etc).
• A quantum of energy in the form of light is
emitted when the electron falls back to a
lower energy level.
Atomic Spectra
• The light emitted by an electron moving from a
higher to lower energy level has a frequency
directly proportional to the energy change of
the electron (Recall: E α v).
• Passing this light through a slit and then
refracting it by a prism gives a LINE
SPECTRUM (aka Atomic Emission Spectrum)
• It does not produce a continuous spectrum or
rainbow as sunlight does.
• The line spectrum has a series of fine lines
called spectral lines separated by black spaces
Atomic Spectra
• The wavelengths of the spectral lines are
characteristic of the element producing it.
• The color of the spectral lines indicates the
wavelength of the radiation producing it.
Atomic Spectra
• In the visible hydrogen spectrum, Johann
Balmer observed that there are four prominent
spectral lines.
– A red line with wavelength of 6563 Å
– A blue-green line with a wavelength of 4861 Å
– A blue line with a wavelength of 4340 Å
– A violet line with a wavelength of 4102 Å
• These four lines were named the Balmer series.
Lines in Balmer Series
Name Transition Wavelength (Å) Colour
Hα 3–2 6563 Red
Hβ 4–2 4861 Blue-Green
Hγ 5–2 4340 Blue
Hσ 6–2 4102 Violet
• Balmer found that the wavelength of lines in
the line spectrum could be given by the
equation:
• Where λ = wavelength, nf & ni are positive
integers where ni > nf; R = Rydberg constant
= 1.097 x 107m-1
• Balmer series limit occurs when n =
i.e. atom ionises.
The Nature of Energy
The energy absorbed or emitted
from the process of electron
promotion or demotion can be
calculated by the equation:
1 1
E = −hcR ( nf2
-
ni2 )
where R is the Rydberg constant,
1.097 107 m−1, and ni and nf are
the initial and final energy levels
of the electron.
• Alternatively, ∆E can be given by:
1 1
E = −RH ( nf2
- 2
ni )
• Where RH is another version of the
Rydberg constant = -2.178 x 10-18 J
Other Spectral Series
• In addition to
Spectral nf ni
Balmer series,
Region
Lines values values four other
spectral
Lyman UV 1 ≥2
series were
Balmer UV/VIS 2 ≥3 discovered in
Paschen IR 3 ≥4 the infra-red &
UV regions of
Brackett IR 4 ≥5 the hydrogen
Pfund IR 5 ≥6 spectrum.
Bohr Model for Hydrogen
• Niels Bohr adopted Planck’s
assumption and explained
these phenomena in this
way:
1. Electrons in an atom can only
occupy certain orbits
(corresponding to certain
energies).
The Nature of Energy
• Niels Bohr adopted Planck’s
assumption and explained
these phenomena in this
way:
2. Electrons in permitted orbits
have specific, “allowed”
energies; these energies will
not be radiated from the atom.
The Nature of Energy
• Niels Bohr adopted Planck’s
assumption and explained
these phenomena in this
way:
3. Energy is only absorbed or
emitted in such a way as to
move an electron from one
“allowed” energy state to
another; the energy is defined
by
E = h
The Bohr Model
• When the electron moves from one energy
level to another.
E = Efinal - Einitial
E = -2.178 x 10-18 J Z2 (1/ nf2 - 1/ ni2)
Recall: E = −hcR ( 12 - 1
)
n f ni2
