Christopher Mwanza

INTRODUCTION TO
SPECTROCHEMICAL METHODS

LAB TECHNIQUES
Christopher Mwanza

BACKGROUND

• Many instrumental methods of analysis

involve the refraction,
refraction absorption,
absorption or emission
of light.

These can be referred to as spectrochemical

methods.

•
Christopher Mwanza

BACKGROUND

• science that deals with the refraction

of light is called refractometry
• & instrument used is called the
refractometer.
Christopher Mwanza

BACKGROUND

• The science that deals with the absorption & emission of

light is called spectroscopy or spectrometry.

• The broad term for the instruments used is spectrometer.

• a slightly more specific term is spectrophotometer- when

a light sensor known as a phototube is used.
BACKGROUND

• A phototube or photoelectric cell is a type of gas-filled or

vacuum tube that is sensitive to light.
light
• Hence can be used as photodetectors.

Christopher Mwanza
Christopher Mwanza

BACKGROUND

• Spectroscopy-interactions of radiation & matter.

• Spectroscopic methods are based on measuring

the amount of electromagnetic radiation, emr,
produced or absorbed by the molecular or atomic
species of interest (analyte)!
analyte
Christopher Mwanza

BACKGROUND
Christopher Mwanza

PROPERTIES OF
ELECTROMAGNETIC RADIATION
• The modern characterization of light is that it has a dual
nature.
i. we describe light as consisting of moving particles, often
called photons or quanta -particle theory of light.

ii.describe light as consisting of moving electromagnetic

disturbances called as electromagnetic
waves -wave theory of light.
 PROPERTIES OF
ELECTROMAGNETIC RADIATION
exhibits wavelike characteristics, travels through
space at the speed of light in a vacuum.
A wave consists of repeating units called cycles or
crests

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 ELECTROMAGNETIC
RADIATION
• Main wave characteristics:
i. Wavelength () – the distance between two successive
crests/peaks (or bottom of two troughs).
 length of an electromagnetic wave.

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 MAIN WAVE
CHARACTERISTICS:
• ii. Frequency (,nu) – # of crests or troughs
that pass through a given point per second.

• has units of time−1, usually per second

(s−1) or Hertz.

• 1Hz=1/s or 1Hz=1 s-1

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 ELECTROMAGNETIC RADIATION

• iii. Wave number: If the wavelength is expressed in centimeters, waves of light

are sometimes characterized by the
reciprocal of this wavelength.

expressed as cm–1

used especially in conjunction with infrared light

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 ELECTROMAGNETIC RADIATION

• iv. Velocity:
Velocity it is defined as the linear distance travelled by the
wave in 1 sec.
Velocity in m/s can be obtained by multiplying frequency in
Hertz (s–1) with wavelength in meters.

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 ELECTROMAGNETIC RADIATION

The velocity of a radiation depends on the medium.

In a vacuum the velocity is equal to 2.998 X 10 8 m s-1.

• The constant ‘c’ is the speed of light with the value

2.997925 x 108 m s−1.

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 ELECTROMAGNETIC RADIATION

• Properties of waves
 Wave with shortest  has the highest frequency

• Wave with longest  has the lowest frequency

• Hence  is inversely proportional to frequency
()

 All types of electromagnetic radiation travel at the same speed, 2.998 X 10 8

m/s which often referred to as speed of light (c).

•
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 ELECTROMAGNETIC RADIATION
EMR also show the characteristics of particles.
These are called as quanta.
These quanta are actually bundles of energy.
A quantum of visible light is called a photon!

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 ELECTROMAGNETIC RADIATION

Possible to determine that the E of each quantum..

equal to the frequency of the radiation multiplied by a
universal constant known as Planck's constant.

E = h
• h is Planck’s constant = 6.626 x 1034 J s photon 1
(measures the energy of an individual quantum)

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 ELECTROMAGNETIC RADIATION

E of EMR is proportional to the frequency

of the radiation
– the higher the frequency, the greater the
radiation

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 EMR-THE PARTICULATE NATURE

 The E of the quantum can also be related to the wavelength or wave number as:

 Hence, E of photon can be readily calculated from these equations if we know

the frequency, wavelength or wave number.

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EXAMPLE 1
EXAMPLE 2
PROPERTIES OF ELECTROMAGNETIC
RADIATION

• Light is a form of energy (E) & has specific each

wavelength or frequency has a certain amount of E
associated with it.
• This E is considered to be the energy associated with a
single photon of the light.

• Thus, the particle theory and the wave theory are linked
via the energy .
Christopher Mwanza

PROPERTIES OF
ELECTROMAGNETIC RADIATION

• the electromagnetic spectrum is arbitrarily broken down

into different regions according to wavelength.
ELECTROMAGNETIC SPECTRUM
Christopher Mwanza

PROPERTIES OF
ELECTROMAGNETIC RADIATION

• The wavelength of electromagnetic radiation varies from a

few angstroms to several meters.

• The units used to describe the wavelength are as follows:

•
Christopher Mwanza

PROPERTIES OF
ELECTROMAGNETIC RADIATION

• The wavelength unit preferred for the ultraviolet and

visible regions of the spectrum is
nanometer,
• The unit micrometer is preferred for the infrared (IR)
region.
• In IR, wavenumbers are often used in place of
wavelength, and the unit is cm .
-1
PROPERTIES OF ELECTROMAGNETIC
RADIATION
• gamma-ray & X-ray will not be discussed here; although these
high-energy radiations can be used in principle
in the same manner as lower-energy radiations.

• The UV region extends from about 10 to 380 nm, but the most
analytically useful region is from 190 to 380 nm, called the near-
ultraviolet or quartz UV region
 PROPERTIES OF ELECTROMAGNETIC
RADIATION
• Below 190 nm, O2 absorbs appreciably & so the instruments
are operated under a vacuum.
• hence, this wavelength region is called the vacuum-
ultraviolet region.
• The visible (Vis) region is actually a very small region, & it
is the region of wavelengths that can be seen by the human
eye.
• In Vis region light appears as different colors, depending on
the wavelength.
 PROPERTIES OF ELECTROMAGNETIC
RADIATION

• The Vis region extends from the near-ultraviolet region (380 nm,
deep violet) to about 780 nm (far red).
• The infrared (IR) region extends from about 0.78 μm (780 nm) to
300 μm, but the range from 2.5 to 15 μm is the most frequently
used for analysis,…
• This range corresponds to a wavenumber range of 4000 to 667 cm . -1
 PROPERTIES OF ELECTROMAGNETIC
RADIATION
• The 0.8- to 2.5-μm range is known as
the near-infrared region.
• the 2.5- to 16-μm region as the mid- or NaCl-infrared
regio & longer wavelengths as the far-infrared region.
Christopher Mwanza

PROPERTIES OF
ELECTROMAGNETIC RADIATION

• Radio waves are on the long end of the electromagnetic

spectrum
• Their wavelengths are on the order of kilometers long.
• These are very low energy waves (long wavelength =
low energy) that do no harm as far as
our health & safety are concerned.
Christopher Mwanza

PROPERTIES OF
ELECTROMAGNETIC RADIATION

• Microwaves have wavelengths on the order of a

centimeter & are also of low energy.
energy
• can be dangerous because their absorption causes the
generation of much internal heat
• Microwave ovens are used in our kitchens & used in
labs for heating samples.
 Christopher Mwanza

INTERACTION OF RADIATION & MATTER

spectrochemical methods of analysis also involve the

absorption & emission of light.
Consider the Vis region to understand the process of light
absorption.
There is visual evidence of light absorption based on the ability
to see the colors that are the visible wavelengths.
Objects display a color because some visible light wavelengths
are absorbed.
 Christopher Mwanza

INTERACTION OF RADIATION & MATTER

Why does a red sheet of paper appear red?

All the wavelengths of visible light from the sun & the light bulbs on in
the room are absorbed except for the red wavelengths, and these are
reflected to our eye
 Christopher Mwanza

INTERACTION OF RADIATION &

MATTER
 Why does a solution of KMnO4 appear to be a deep
purple color?
 The wavelengths of Vis light that are incident on the
solution from the light in the room are all absorbed
except for those in the violet & red ends of the visible
region.
 The result is an intense purple color.

 Thus, those wavelengths of light that are not absorbed

 Christopher Mwanza

INTERACTION OF RADIATION & MATTER

The Big Question……

 What is the nature of the interaction between light & matter
that causes certain wavelengths of light to be absorbed?
The answer lies in the structure of the atoms & molecules of
which matter is composed.
First, consider atoms.
 Christopher Mwanza

INTERACTION OF RADIATION &

MATTER

In atoms, electrons exist in energy

levels around the nucleus.

The energy associated with UV & Vis

light is comparable to the energy
differences between the outermost
occupied electron energy level of an
atom & the unoccupied levels
immediately above it
 Christopher Mwanza

INTERACTION OF RADIATION & MATTER

Electrons can be moved from the lower energy level to the

higher one if conditions are right.

eg, the outermost electron of a Na atom (which has electron

configuration 1s22s22p63s1) can be moved from the 3s level to
the vacant 3p level if conditions are right.
 Christopher Mwanza

INTERACTION OF RADIATION & MATTER

These conditions consist of:

i. addition of a specific amount of energy to the electron.

ii.a vacancy for the electron with this greater energy in a certain
higher energy level (in the case of Na, the 3p level is vacant)
 Christopher Mwanza

INTERACTION OF RADIATION & MATTER

In simple terms:

if an electron absorbs the E required for it to be promoted to a
higher vacant energy level then it will be promoted to that
level.
If this E is supplied in the form of light, then the electron will
gain that specific amount of energy & move to the higher
level.
 Christopher Mwanza

INTERACTION OF RADIATION & MATTER

The light then no longer exists—it has been absorbed

 Christopher Mwanza

INTERACTION OF RADIATION & MATTER

Atoms in which no electrons are in the higher vacant level are

said to be in the ground state.
This state is designated in E level diagrams as E0.
Atoms in which there is an electron in the higher level are said
to be in an excited state.
state
Excited states are designated in E level diagrams as E1, E2, E3,
etc.
Christopher Mwanza

INTERACTION OF RADIATION &

MATTER
 An E level diagram consists of
short horizontal lines representing
the levels or states with each line
labeled as E0, E1, etc.
 an E level diagram shows the
movement of electrons between
levels with longer vertical arrows.
 movement of an electron between
electron E levels is called an
electronic energy transition
 Christopher Mwanza

INTERACTION OF RADIATION &

MATTER
 light must be exactly the same E as the E
difference between the two electronic
levels; otherwise the atom will not absorb it.

 If it is not absorbed, we see it (provided it is

in Vis region).

 It becomes part of the light that is reflected

or transmitted and therefore detected by our
eyes.
 Christopher Mwanza

INTERACTION OF RADIATION &

MATTER
 The absorption of light by atoms consists of
the absorption of only a few very specific
wavelengths because the E difference
between two levels is very specific.
 It is like climbing a ladder. If there is no rung
to stand on, then we cannot stand at the level.
 If there is no E level for the electron to go to
when supplied with light energy, then that
light cannot be absorbed.
 Christopher Mwanza

INTERACTION OF RADIATION &

MATTER
Electronic energy transitions
for gaseous Na atoms.
There are two slightly
different transitions between
the two levels because of the
effect of two spin states that
differ slightly in E.
 Christopher Mwanza

IMPORTANT POINT!!

the energy associated with electronic energy transitions in

atoms is equivalent to the energy of visible & ultraviolet light
and thus atoms absorb light in these regions.
 Christopher Mwanza

INTERACTION OF RADIATION & MATTER

What about molecules and complex ions?

absorption of light by molecules & complex ions results in the

promotion of electrons to higher energy states in the same way as
atoms.

However, it is more complicated because molecules & complex

ions have energy states that atoms do not.
 Christopher Mwanza

INTERACTION OF RADIATION & MATTER

Atoms vs. Molecules & Complex ions

Molecules & complex ions exist in vibrational & rotational
energy states as well as electronic states.
Upon absorption of the right amount of energy, a molecule
can change from one vibration or rotation state to another.
The vibrational E states exist in each electronic state &
rotational energy states exist in each vibrational state.
 Christopher Mwanza

INTERACTION OF RADIATION &

MATTER
 Atoms vs. Molecules & Complex ions
 Energy level diagrams for molecules show
additional horizontal lines, or levels, within
(“superimposed” on) each electronic level to
represent these vibrational states.

 The vibrational states can be labeled V 0, V1, V2,

etc.

 The rotational states are superimposed on the

vibrational states in the same way.

INTERACTION OF RADIATION & MATTER
 Christopher Mwanza

INTERACTION OF RADIATION & MATTER

Atoms vs. Molecules & Complex ions

For molecules & complex ions, an electronic transition can refer to
a transition from any vibrational level in one electronic level to any
vibrational level in another electronic level.
As with atoms, the amount of E required for such a transition is
found in either the Vis or the UV regions.
thus involves either visible or ultraviolet light.
 Christopher Mwanza

INTERACTION OF RADIATION & MATTER

A vibrational transition refers to a

transition from the lowest vibrational
level within a certain electronic
level to another vibrational level in
the same electronic level.
such a transition does not involve
another electronic level, it requires
much less E.
it involves the IR region of the
electromagnetic spectrum
 Christopher Mwanza

INTERACTION OF RADIATION & MATTER

• There are 3 basic processes by which a molecule/atom can absorb

radiation; in all cases, the molecule/atom is raised to a higher
internal energy level.

• The increase in energy being equal to the energy of the absorbed

photon (hv).

• The 3 types of internal energy are quantized; ie, they exist at

discrete levels
 Christopher Mwanza

INTERACTION OF RADIATION &

MATTER
First, the molecule rotates about various
axes.

The energy of rotation being at definite

energy levels.

So the molecule may absorb radiation &

be raised to a higher rotational energy
level, in a rotational transition.
 Christopher Mwanza

INTERACTION OF RADIATION & MATTER

Second, the atoms or groups of atoms within a molecule

vibrate relative to each other
The energy of this vibration occurs at definite quantized levels.
The molecule may then absorb a discrete amount of energy &
be raised to a higher vibrational energy level, in a vibrational
transition.
 Christopher Mwanza

INTERACTION OF RADIATION & MATTER

• Third, the outer shell electrons of a molecule, valence

electrons, may be raised to a higher electron energy,
corresponding to an electronic transition.

• With absorption of even more energetic radiation, X-

rays, inner shell electrons are generally ejected (X-ray
spectroscopy).
 Christopher Mwanza

INTERACTION OF RADIATION & MATTER

• A molecule absorbs a photon by undergoing an

energy transition exactly equal to the E of the
photon.

• The photon must have the right E for this quantitized

transition.
 Christopher Mwanza

INTERACTION OF RADIATION & MATTER

Interaction of an analyte with emr can result in many types of changes :

 Christopher Mwanza

INTERACTION OF RADIATION & MATTER

NOTE:
 changes in electron distributions occur in the UV/visible
region.

 The wavenumber, wavelength, frequency, & energy are

characteristics that describe electromagnetic radiation.
 Christopher Mwanza

SPECTROSCOPIC MEASUREMENTS

Optical methods are spectroscopic methods based on UV, Vis & IR

rradiation.

Spectroscopists use the interactions of radiation with matter to obtain

information about a sample.

Several of the chemical elements were discovered by spectroscopy

 Christopher Mwanza

SPECTROSCOPIC MEASUREMENTS

sample is stimulated in some way by applying

E.
E in the form of heat, electrical energy, light,
particles, or a chemical reaction.
Prior to applying the stimulus, the analyte is
predominately in its ground state
 Christopher Mwanza

SPECTROSCOPIC MEASUREMENTS

 The stimulus causes some of the analyte species to undergo a

transition to a excited state.
 Christopher Mwanza

SPECTROSCOPIC MEASUREMENTS

We acquire infor about the analyte by measuring:

 the electromagnetic radiation emitted as it returns to
the ground state.

or by measuring the amount of electromagnetic

radiation absorbed as a result of excitation.
 Christopher Mwanza

SPECTROSCOPIC MEASUREMENTS


 Christopher Mwanza

SPECTROSCOPIC MEASUREMENTS:
emission & chemiluminescence spectroscopy.

The analyte is stimulated by applying heat or electrical energy or by a

chemical reaction.

The term emission spectroscopy usually refers to methods in which the

stimulus is heat or electrical energy.

 while chemiluminescence spectroscopy refers to excitation of the

analyte by a chemical reaction
 Christopher Mwanza

SPECTROSCOPIC MEASUREMENTS

In both cases, measurement of the radiant power emitted as the analyte
returns to the ground state can give infor about its identity &
concentration.
The results of such a measurement are often expressed graphically by a
spectrum- plot of the emitted radiation as a function of frequency or
wavelength.
 Christopher Mwanza

SPECTROSCOPIC MEASUREMENTS