CHEM 121 LEC Chapter 7
OUTLINE wavelengths, incident angles, and
Spectroscopy polarization angles
INTRODUCTION
PROPERTIES OF ELECTROMAGNETIC
Spectroscopy involves the study of the interactions RADIATION
of radiation and matter.
Electromagnetic radiation is a form of
Spectroscopic analytical methods are energy that is transmitted through space at
based on measuring the amount of radiation enormous velocities.
produced or absorbed by species of The term light refers only to visible
interest. radiation but is often used to refer to
They are classified according to the region electromagnetic radiation in the ultraviolet
of the electromagnetic spectrum used or (UV), visible, and sometimes infrared
produced in the measurement. regions.
Spectrochemical methods have been
valuable in elucidating molecular structure Electromagnetic radiation
and for the quantitative and qualitative
determination of compounds. can be described as a wave with
properties of wavelength, frequency,
DEFINITION OF TERMS velocity, and amplitude.
requires no transmitting medium, can
Spectroscopy travel through empty space.
is the study of the interaction between can be considered as a wave or treated
matter and electromagnetic radiation, or as discrete packets of energy or
simply the study of how light interacts with particles called photons or quanta.
matter. The dual wave/particle nature of
electromagnetic radiation is
Spectrometry complementary and also applies to
streams of electrons, protons, and other
is the measurement of the amount of elementary particles.
radiation produced or absorbed by
molecular or atomic species in the sample WAVE PROPERTIES
Spectrometer Electromagnetic radiation can be
modeled as waves consisting of
is a scientific instrument used to separate perpendicularly oscillating electric and
and measure spectral components of a magnetic fields.
physical phenomenon
Spectrochemical Methods
analytical methods used for elucidation of
molecular structure and qualitative and
quantitative determination of inorganic or
organic compounds.
CLASSIFICATION OF METHODS The amplitude of an electromagnetic wave
is a vector quantity that provides a measure
Absorption spectrometer
of the electric or magnetic field strength at a
Instruments that uses range of maximum in the wave.
electromagnetic spectra which the The period, p, is the time in seconds for
substance will absorb successive maxima or minima to pass a
point in space.
Emission spectrometer The wavelength, λ, is the linear distance
between successive maxima or minima.
Instruments that uses range of
The wave frequency, ν, is the number of
electromagnetic spectra which the
oscillations in 1 second and equals 1/p.
substance will radiate
The unit of frequency, hertz (Hz),
Scattering spectrometer corresponds to one cycle per second
(1 Hz = 1 s-1) .
Instruments measure the amount of light Unlike velocity and wavelength, frequency
that a substance scatters at certain does not change as a wave passes through
different media.
Rañeses, Charina Mae BS MLS A.Y. 2024-2025
CHEM 121 LEC Chapter 7
Equation shows the relationship between Photon – is particle of electromagnetic
velocity, frequency, and wavelength. radiation having a zero mass and an energy
= V of hv.
Relating energy of single photon to
wavelength, frequency and wave number:
Wavelength changes as radiation passes
from air to dense glass and back to air
THE ELECTROMAGNETIC SPECTRUM
Shown below the range of energies (frequencies)
and thus wavelengths of the electromagnetic
spectrum, of which the visible region is a tiny fraction
Regions of the UV, Visible, and IR Spectrum
UV 180−380 nm
The wavenumber, v, of electromagnetic Visible 380−780 nm
radiation is the number of waves per Near-IR 0.78−2.5 μm
centimeter. Mid-IR 2.5−50 μm
It has units of 𝑐𝑚−
It equals 1/λ.
It is most often used to describe The Electromagnetic Spectrum
radiation in the infrared region of
Shorter wavelength Higher energy
the electromagnetic spectrum.
Higher frequency
The radiant power, P, in watts (W) is the Longer wavelength Lower energy
energy of a beam that reaches a given area Lower frequency
per unit time.
The intensity is the radiant power-per-unit
solid angle.
Both quantities are proportional to the
square of the amplitude of the electrical
field.
Although not strictly correct, these terms are
frequently used interchangeably.
THE WAVE AND ITS PARTS
A wave can be described as a disturbance
that travels through a medium from one
location to another location
PARTICLE NATURE OF LIGHT: PHOTON
Spectrochemical methods that use UV and
infrared radiation are often called optical
Rañeses, Charina Mae BS MLS A.Y. 2024-2025
CHEM 121 LEC Chapter 7
methods even though they are not visible THE ABSORPTION PROCESS
to the human eye.
This terminology results from similarities in The absorption law, also know as the Beer-
the instruments used and in the way we Lambert law or Beer’s law, tells
view the interactions of the three types of quantitatively how the amount of attenuation
radiation with matter. depends on:
the concentration of the absorbing
molecules.
the path length over which
absorption occurs.
As light traverses a medium containing an
absorbing analyte, the intensity decreases
as the analyte becomes excited.
PRINCIPLES OF ABSORPTION SPECTROSCOPY
SPECTROSCOPIC MEASUREMENTS
Lamberts Law
Prior to applying the
stimulus, the analyte “It states that when monochromatic light
is predominantly in its passes through a transparent medium, the
lowest-energy or intensity of transmitted light decreases
ground state. exponentially as the thickness of absorbing
The stimulus then material increases.”
causes some of the
analyte species to Beer’s law
undergo a transition “It states that the intensity of transmitted
to a higher-energy or monochromatic light decreases
excited state. exponentially as the concentration of the
Shows a sample absorbing substance increases.”
being excited by
applying thermal, BEER-LAMBERT LAW (BEER’S LAW)
electrical, or chemical
energy. As light traverses a medium containing an
These are called nonradiative processes absorbing analyte, the intensity decreases
because no radiant energy is used to as the analyte becomes excited.
produce excited states. For an analyte solution of a given
In absorption spectroscopy, we measure concentration, the longer the length of the
the amount of light absorbed as a function medium through which the light passes
of wavelength. through (path length of light), the more
Absorption measurements can give both absorbers are in the path length of light, and
qualitative and quantitative information the greater the attenuation
about the sample.
THE ABSORPTION PROCESS
TRANSMITTANCE
Rañeses, Charina Mae BS MLS A.Y. 2024-2025
CHEM 121 LEC Chapter 7
The transmittance T of the solution is the
fraction of incident radiation transmitted by
the solution.
T = P/P0
Transmittance is often expressed as a
percentage called the percent
transmittance.
T = P/P0 x 100
ABSORBANCE
The absorbance, A, of a solution is related
to the transmittance.
As the absorbance of a solution increases,
the transmittance decreases.
Transmittance and absorbance usually
cannot be measured as shown because the
solution to be studied must be held in a
container (cell or cuvette).
Potentially substantive reflection and
scattering losses can occur at the cell walls.
Light can also be scattered by large SAMPLE
molecules or particles in the solvent.
1. A single sheet of the colored materials
transmits 70% of the light:
2. If the second sheet transmitted 70% of the
light it receives 49% (0.70 x 70% of the
original light:
3. The third sheet transmits 70% of the light it
According to Beer’s law, absorbance is receives 34.4% (0.70 x 49%) of the original
directly proportional to the concentration of light:
the absorbing species, c, and to the path
length, b, of the absorbing medium as
expressed:
In this equation, a is a proportionality
constant called the absorptivity.
When expressing the concentration in
moles per liter and b in cm, the
proportionality constant is called the molar
absorptivity and is given the symbol ε as
shown below. ε has the units of L mol-1 cm-1
Rañeses, Charina Mae BS MLS A.Y. 2024-2025
CHEM 121 LEC Chapter 7
WHY IS A RED SOLUTION RED?
An aqueous solution of the complex Fe(SCN)2+ is not
red because the complex adds red radiation to the
solvent. Instead, it absorbs green from the incoming
visible radiation and transmits the red component.
Thus, in a colorimetric determination of iron based
on its thiocyanate complex, the maximum change in
absorbance with concentration occurs with green
radiation; the absorbance change with red radiation
is negligible. In general, then, the radiation used for
a colorimetric analysis should be the complementary
color of the analyte solution. The following table
shows this relationship for various parts of the visible
spectrum.
aqueous solution of 𝐹𝑒(𝑆𝐶𝑁)2
White light from a lamp or the sun strikes an
The fairly broad absorption spectrum shows
a maximum absorbance in the 460 to 500
nm range. The complementary red color is
transmitted.
Rañeses, Charina Mae BS MLS A.Y. 2024-2025
CHEM 121 LEC Chapter 7
SAMPLE PROBLEM 3: Calculate the energy in
joules of one photon of radiation with the wavelength
given in SAMPLE PROBLEM 2
SAMPLE PROBLEMS
SAMPLE PROBLEM 1: Calculate the frequency and
energy associated with violet light of wavelength
400nm.
SEATWORK 7.1 Extinction coefficient of NADH at
340 nm is 6440 L/mol/cm. Whereas NAD does not
absorb at 340 nm. What absorbance will be
observed when light at 340 nm passes through a
1.5cm cuvette containing 10uM NAD
SAMPLE PROBLEM 2: Calculate the wavenumber
of a beam of infrared radiation with a wavelength of
5.00 μm.
Rañeses, Charina Mae BS MLS A.Y. 2024-2025
CHEM 121 LEC Chapter 7
SEATWORK 7.2 Calculate the molar absorptivity of
a solution, which has an absorbance of 0.1736,
concentration is 5.0 𝑥 10−3 𝑀.
when the path length is 1.3 cm and the
Rañeses, Charina Mae BS MLS A.Y. 2024-2025