CHAPTER 1: INTRODUCTION TO PERIOD (p) is the time required for one

SPECTROSCOPY METHOD OF ANALYSIS cycle to pass a fixed point in space.

SPECTROSCOPY is the study of the FREQUENCY (ν/f) is the number of cycles

interaction between electromagnetic (EM) which pass a fixed point in space per
radiation and matter. The sample solution second (Unit in Hz or s-1)
absorbs EM from an appropriate source,
AMPLITUDE (A) is the maximum length of
and the amount absorbed is related to the
the electric vector in the wave (maximum
concentration of the analyte in the
height of a wave)
solution.
WAVENUMBER (ṽ) is the number of waves
SPECTROPHOTOMETER/SPECTROMETER
per cm (Unit in cm-1)
is the instrument that determines the
absorption spectrum and spreads out light RADIANT POWER (P) is the amount of
making a spectra. energy reaching a given area per second
(Unit in watts, W)
SPECTRA is the range of electromagnetic
energy separated by wavelength. VELOCITY OF PROPAGATION is the rate at
which a wave front moves through a
ELECTROMAGNETIC RADIATION is the
propagating medium in meters per second
energy that is propagated through free
(ms-1)
space or through a material medium in the
form of electromagnetic waves, such as PROPERTIES OF ELECTROMAGNETIC
radio waves, visible light, and gamma rays. RADIATION
It is a form of energy that has both wave
1. WAVE PROPERTIES
and particle properties.
• EM radiation is conveniently modeled as
RADIATION is the emission of energy as
waves consisting of perpendicularly
electromagnetic waves or as moving
oscillating electric and magnetic fields.
subatomic particles, especially high-energy
particles which cause ionization. • At 90° to the direction of propagation is
an oscillation in the ELECTRIC FIELD.
WAVELENGTH (λ) is the distance between
two identical adjacent points in a wave • At 90° to the direction of propagation and
(usually maxima or minima) 90° from the electric field oscillation
(orthagonal) is the MAGNETIC FIELD
INTENSITY (I) is the radiant power per unit
oscillation.
solid angle (Unit in Watts per Steradian,
• Does not require a material medium and
Wsr-1)
can travel through a vacuum
SOLID ANGLE (Ω) is the size of area divided
by the square of the radius (r2) of the
sphere (Unit in steradian, sr)
 SPECTRUM REGION

WAVELENGTH UNITS

FORMULA

𝐜 = 𝐯𝛌
c = speed of light (3.00 x 108 m/s or 3.00 x COLOR OF DIFFERENT WAVELENGTH
1010 cm/s) REGIONS

ν = frequency of the waves (Hz or s-1)

 = wavelength of the waves (nm or m)

2. PARTICLE PROPERTIES

• EMR is viewed as a stream of discrete

particles of energy called photons

FORMULA

𝒉𝒄 ELECTROMAGNETIC SPECTRUM
𝐄 = 𝐡𝐯 = = 𝐡𝐜ṽ
𝝀
h = Planck’s constant (6.63  10-34 Js)

ṽ = wavenumber (cm-1)

𝟏 𝐯
ṽ= =
𝛌 𝐜
• When λ increase, energy, frequency,
wavenumber will decrease.
SPECTROSCOPIC MEASUREMENTS
• How Does Matter Absorb Radiation?
→ The absorption of radiation can be
obtained by considering the absorption of
light in the visible.
→ The color of an object we see is due to
the wavelengths transmitted or reflected.
The other wavelengths are absorbed.
→ Polychromatic light (white light) is
visible light that contains all the colors of
the rainbow.
→ If white light is passed through an
object, the object will absorb certain of the
wavelengths, leaving the unabsorbed
wavelengths to be transmitted.
ABSORPTION METHODS
• Absorption is the measure of the
decrease in radiant power
• Requires 2 power measurements which
is incident radiant power, Po and
transmitted radiant power, P
1. TRANSMITTANCE
• The fraction of incident radiation
transmitted through the sample medium.
𝐏𝐨 𝐏𝐨
𝐓= , %𝐓 = × 𝟏𝟎𝟎
𝐏 𝐏
2. ABSORBANCE
• A measurement of the amount of radiant
power absorbed by the sample defined as
the negative log of transmittance.
𝐏𝐨
𝐀 = − 𝐥𝐨𝐠 𝐓 = 𝐥𝐨𝐠
𝐏
BEER’S LAW
• Absorbance is directly proportional to
the path length (b) through the medium
and the concentration (c) of the absorbing
species.
𝐀 = 𝐚𝐛𝐜
a = absorptivity (L g-1 cm-1)
b = path length (cm-1)
c = concentration (g/L)
𝐀 = 𝐛𝐜
 = molar absorptivity (L mol-1 cm-1)
c = concentration (mol/L)
PARAMETERS THAT AFFECT ABSORBANCE
1. CONCENTRATION, c
2. WIDTH OF CUVETTE, b
• Wider cuvette consist of more absorbing
species present in the path of the light,
hence absorbance is greater.
3. INHERENT ABILITY FOR ABSORBING
SPECIES TO ABSORB LIGHT
• Chemical species vary with respect to this
inherent ability since absorption depends
on individual electronic and vibrational
transitions available in a given species.
LIMITATIONS TO THE APPLICABILITY OF
BEER’S LAW
• Deviations are frequently observed from
the direct proportionality between
absorbance, A and concentration, c when
path length, b is constant.
1. FUNDAMENTAL DEVIATIONS b) Due to presence of stray radiation

• At high concentration (> 0.01M) the → Due to instrument imperfections.

extent of solute-solvent interactions,
→ Stray radiation or scattered radiation is
solute-solute interactions, or hydrogen
defined as radiation from the instrument
bonding can affect the analyte
that is outside the nominal wavelength
environment and its absorptivity.
band selected.
• At high concentration, the average
→ Usually the wavelength of the stray
distances between molecules or ion are
radiation is very different from the
diminished where each particle affects the
wavelength band selected. It is known that
charge distribution of its neighbours and
radiation exiting from a monochromator is
thus the extent of absorption of its
often contaminated with minute
neighbours.
quantities of scattered or stray radiation.
• Therefore, this interaction alters the
→ This stray radiation is due to reflection
ability of analyte species to absorb a given
and scattering by the surfaces of lenses,
wavelength of radiation which causes
mirrors, gratings, filters and windows.
deviation from the linear relationship
between absorbance and concentration. → The wavelength of stray radiation differs
greatly from the principal radiation and
2. INSTRUMENTAL DEVIATIONS
may not have passed through the sample.
a) Due to polychromatic radiation
→ If the analyte absorbs at the wavelength
→ Polychromatic: describe light that of the stray radiation, a deviation from
exhibits more than one color, which also Beer’s law is observed similar to the
means that it contains radiation of more deviation due to polychromatic radiation.
than one wavelength.
𝐥𝐨𝐠 𝑷𝒐 + 𝐥𝐨𝐠 𝑷𝒔
𝐀 =
→ Beer’s Law strictly applies when 𝑷 + 𝑷𝒔
measurements are made with Ps = power of non-absorbed stray radiation
monochromatic source radiation.
𝐏𝐬
→ In practice, however, it is common to % 𝐒𝐭𝐫𝐚𝐲 𝐫𝐚𝐝𝐢𝐚𝐭𝐢𝐨𝐧 = × 𝟏𝟎𝟎
𝐏𝐨
use a polychromatic source of radiation
c) Due to mismatched cells
with continuous distribution of
wavelengths along with a filter or a grating → If the cells holding the analyte and the
unit (monochromators) to create a blank solutions are having different path-
monochromatic beam from this source. lengths, or unequal optical characteristics,
it is obvious that there would be a
→ Deviations occur if the radiation is
deviation observed in Beer’s law.
polychromatic since the relationship
between A and c is no longer linear when 
is differ.
→ In such cases when a plot of absorbance
versus concentration is made, the curve
will have an intercept k and the equation
will be defined as:
𝐀 = 𝛆𝐛𝐜 + 𝐤
3. CHEMICAL DEVIATIONS
• Occur when the analyte undergoes
dissociation, association or reaction with
the solvent to give products that absorb
differently than the analyte.
• Analyte undergoes dissociation as
absorbance is recorded.
• Example: the ionisation of acidic or basic
indicator
TYPE OF EM INTERACTIONS
• The interaction of radiation with matter
can cause redirection of the radiation
and/or transitions between the energy
levels of the atoms or molecules.
1. Absorption: EMR energy transferred to
absorbing molecule (transition from low
energy to high energy state)
2. Emission: EMR energy transferred from
emitting molecule to space (transition
from high energy to low energy state)
3. Scattering: Redirection of light with no
energy transfer
• When a species (atoms/molecules)
changes its state, it absorbs or emits an
amount of energy exactly equal to the
energy difference between the states.
• When atoms/molecules absorb or emit
radiation in making the transition from one
energy state to a second, the frequency (ʋ)
or the wavelength (λ) of the radiation is
related to the energy difference between
the states.
𝐡𝐜
𝐄 − 𝐄𝐨 = 𝐡𝐯 =
𝛌
ABSORPTION RADIATION
• Atoms are the basic blocks of matter
which consist of heavy particles (called
protons and neutrons) in the nucleus,
surrounded by lighter particles called
electrons.
• An electron will interact with a photon.
• An electron that absorbs a photon will
gain energy.
• An electron that loses energy must emit
a photon.
• For absorption to occur, the energy of the
photon must exactly match an energy level
in the atom (or molecule) it contacts.
E =E
ENERGY LEVEL DIAGRAM FOR
MOLECULAR ABSORPTION
1. ATOMIC ABSORPTION
• Electrons bound to atoms have discrete
energies (i.e. not all energies are allowed).
• Thus, only photons of certain energy can
interact with the electrons in a given atom.
• Transitions between electronic levels of
the electrons produce line spectra.
• The energy of photon that can promote
electrons to excite/jump to a higher energy
level depends on the energy difference
between the electronic levels.
• Each atom has a specific set of energy
levels, and thus a unique set of photon
wavelengths with which it can interact.
EXAMPLE: ABSORPTION SPECTRUM OF Na
• Sodium vapor exhibits two closely
spaced, sharp absorption peaks in yellow
region of the visible spectrum (589.0 and
589.6 nm). Reason: Excitation of the 3s
electron to two 3p states that differ only
slightly in energy.
2. MOLECULAR ABSORPTION
• Eelectronic = energy associated with the
electrons in the various outer orbitals of
the molecules
• Evibrational = energy of the molecules as a
whole due to interatomic vibrations
• Erotational = energy associated with
rotation of the molecule about its center
of gravity
• A molecule may absorb energy in 3 ways:
1. By raising an electron (or electrons) to a
higher energy level (ELECTRONIC)
2. By increasing the vibration of the
constituent nuclei (VIBRATIONAL)
• Atoms or group of atoms within the
molecules vibrate relative to each other.
Therefore, the molecule absorb radiation
and be raised to a higher vibrational energy
level.
• Note that the differences in energy
among the vibrational states are
significantly smaller than among energy
levels of the electronic state.
3. By increasing the rotation of the
molecule about the axis (ROTATIONAL)

• Molecule rotates about various axes

around its center of gravity. Therefore, the
molecule absorb radiation and be raised to
a higher rotational energy level.

• These rotational energy states are

superimposed on each of the vibrational
states shown in energy diagram.

• The energy differences among these

states are smaller than those among
vibrational states.

TYPES OF SPECTRA

1. ABSORPTION SPECTRUM is a plot of

the absorbance as a function of
wavelength or frequency. The spectrum is
simple due to the small number of
possible energy states for the absorbing
particles. Atomic spectrum is sharp, well
defines lines.
2. EMISSION SPECTRUM is a plot of the relative power of the emitted radiation as a function
of wavelength or frequency.

→ Source of excitation:

• Bombardment with electrons or other elementary particles. Leads to the X-radiation.

• Exposure to an electric current, an ac spark, or an intense heat source (flame, dc arc, or

furnace). Produce UV, visible or infrared radiation.

• Irradiation with a beam of electromagnetic radiation. Produces fluorescence radiation.

•An exothermic chemical reaction that produces chemiluminescence.

LINE SPECTRUM BAND SPECTRUM CONTINUUM SPECTRUM

A series of sharp, Several groups of lines so A beam of light that contains a
well-defined peaks closely spaced that they are not broad, smooth distribution of
caused by excitation completely resolved. photon wavelength.
of individual atoms.
• Atomic transitions • Encountered in spectral • Continuum radiation is
are usually very sources when gaseous radicals produced when solids are heated
discrete changes of or small molecules are to incandescence.
electrons from one present. • Thermal radiation is called
quantum state to • Molecular transition consists black body radiation.
another energy level of 3 processes: → A characteristic of the
(shells, spins) → Rotational transition temperature of the emitting
• Only electronic → Vibrational transition surface rather than the material
transition is → Electronic transition of the surface.
quantized. ∆E = ∆Eelectronic + ∆Evibrational + → Produced by the innumerable
• No vibrational or ∆Erotational atomic and molecular oscillations
rotational transition. • Band spectra is produced excited in the condensed solid by
• When an atom due to vibrational and the thermal energy.
changes energy rotational transitions
state, it absorbs or
emits energy equal
to the energy
difference, ∆E
• The wavelength or
frequency of
radiation absorbed
or emitted during a
transition
proportional to ∆E
 QUESTIONS

EXAMPLE 1

What is the energy of a 500 nm photon?

c 3.0 × 10 𝑚/𝑠
v= = = 6.00 × 10 𝑠
λ 500 × 10 𝑚
E = hv = (6.63  10 Js)(6.00 × 10 𝑠 ) = 3.98 × 10 J

EXAMPLE 2

A solution of 10 mg/L analyzed at 520 nm in a 1.0cm cell using Spectrum 20 instrument has
30% transmittance

a) Calculate the absorbance if the b) Determine the percent transmittance

concentration of the solution is diluted to of the diluted solution in (a)
4.0 mg/L under the same condition
A = -log10 T
a=?L• g-1 • cm-1
0.2092 = -log10 T
b = 1.0 cm
T = antilog (-0.2092)
c = 10 x 10-3 g/L
T = 0.618
T = 30%
%T = 0.618 x 100 = 61.8%
A = -log10 T
EXAMPLE 3
A = -log10 (0.3)
Calculate the frequency in Hz of an X-ray
A = 0.523 photon with a wavelength of 2.35 Å.

A = abc 1 Å = 1.0 x 10-10 m

0.523 = a(1.0 cm)( 10 x 10-3 g/L) 1.0 × 10 m

2.35 Å × = 2.35 × 10 m
0.523 1Å
a=
(1.0cm)(10 × 10 𝑔/𝐿) λ = 2.35 × 10 m

a = 52.3 L • g-1 • cm-1 c 3.0 × 10 𝑚/𝑠

v= =
λ 2.35 × 10 𝑚
A = abc
𝐯 = 𝟏. 𝟐𝟖 × 𝟏𝟎𝟏𝟖 𝐬 𝟏

A = (52.3 L • g-1 • cm-1)(1.0 cm)(4.0 x 10-3

g/L) EXAMPLE 4

A = 0.2092 A sample has 2.00 mg/L of KMnO4 has

transmittance of 43.2 % in a 1.0-cm cell.
Calculate the molar absorptivity of
KMnO4 at this wavelength. (Given:
Molecular weight KMnO4 = 158 g/mol)
T = 43.2% 4.48 × 10 g 1 mol
Molarity = ×
L 158 g
 = ? L • mol-1 • cm-1
Molarity = 2.84 mol/L
b = 1.0 cm
A = bc
c = 2.00 mg/L
0.510 = (1.0cm)(2.84 mol/L)
A = -log10 T
0.510
A = -log10 (0.432) =
(1.0𝑐𝑚)(2.84 𝑚𝑜𝑙/𝐿)
A = 0.365
 = 0.18 L • mol • cm
2.00 × 10 g 1 mol
Molarity = × EXAMPLE 6
1L 158 g
A 25.6 mg sample of a compound with a
mol
Molarity = 1.27 × 10 molecular weight of 317.17 g/mol was
L
dissolved in a 300 mL flask. The
A = bc absorbance is 0.624 in a 1.00-cm cuvette.
Calculate the molar absorptivity.
0.365 = (1.0cm)(1.27 x 10-5 mol/L)
0.365 A = 0.624
=
(1.0𝑐𝑚)(1.27 × 10 𝑚𝑜𝑙/𝐿) b = 1.00 cm
 = 2.87 × 10 L • mol • cm  = ? L • mol-1 • cm-1
EXAMPLE 5 mass (m)
Concentration, c =
A solution of 4.48 ppm KMnO4 has a volume (V)
transmittance of 0.309 in a 1.00 cm cell. 25.6 × 10 g
Calculate molar absorptivity of KMnO4 c= = 0.0853 g/L
0.3 L
T = 0.309 0.0853 g 1 mol
Molarity = ×
L 317.17 g
b = 1.00 cm
Molarity = 2.69 × 10 mol/L
 = ? L • mol-1 • cm-1
A = bc
c = 4.48 ppm
0.624 = (1.0cm)(2.69 x 10-4 mol/L)
A = -log10 T
0.624
A = -log10 (0.309) =
(1.0𝑐𝑚)(2.69 × 10 𝑚𝑜𝑙/𝐿)
A = 0.510  = 2.32 × 10 L • mol • cm
mg
4.48 ppm = 4.48
L
Molecular weight of KMnO4 = 39 + 55 + (16
x 4) = 158 g/mol