PART 24

INTRODUCTION TO
SPECTROCHEMICAL METHODS

1
• The interaction of rays with matter is the subject of a branch of science
called spectroscopy.

• Spectroscopy is the measurement and interpretation of electromagnetic

radiation absorbed or emitted by atoms, molecules or ions in a sample as
they transition from one energy level to another.

• Spectrochemical methods are widely used in the qualitative or quantitative

determination of inorganic or organic compounds.

2
A. PROPERTIES OF ELECTROMAGNETIC RADIATION

• Electromagnetic beam is a type of energy that can be transmitted in space

at very high speeds.

• The visible part of it is called light and the other parts are called rays.

• The radiation can be represented as a wave, determined by its

wavelength, frequency, velocity, and amplitude properties.

• However, the wave model is insufficient to explain the absorption and

propagation of radiation energy by matter.

• Therefore, it is more convenient to think of rays as discrete packets of

energy, namely particles called photons or quanta.

3
A.1. Wave Properties

• The wave of electromagnetic radiation; Amplitude, period, frequency,

wavelength and wave number are important wave properties.

• When examining phenomena such as reflection, refraction, interference

and diffraction, it is more appropriate to think of rays as waves.

• Diffraction occurs when the size of the gap through which the wave will
pass is close to or smaller than the wavelength (water, sound, light).

• A wave of electromagnetic radiation consists of electric and magnetic

fields vibrating perpendicular to each other (Maxwell model).

• It is best to accept that the ray has a peculiar behavior and this is called
'quantum mechanical behavior'.

4
 As the beam travels
through the medium,
its electromagnetic
field is affected by the
atoms or molecules in
the medium.

1-Wavelength
2-amplitude
3-Period
4-Frequency
5-Wave speed

Wave nature of a beam of single frequency electromagnetic radiation

5
a) Wave properties

• The amplitude characteristic of a sinusoidal wave is the length of the

electric field vector (A) at a maximum of the wave.

• The time taken for the passage of two consecutive maximum points (one
full wave) from a fixed point is called the period (p).

• The distance between two similar points is called the wavelength (l).

• The number of waves passing through a point in unit time, that is, the
number of vibrations in 1 s, is called frequency (n).

• Unit of frequency : wave/s = s-1 = 1 Hertz

6
• The frequency of a light or ray wave is determined by the source emitting
it, and the frequency does not change when the wave passes into another
medium.

• That is, as rays pass from space or air to a denser medium, their speed
and wavelength change, but their frequency does not.

• In contrast, the wave velocity (v) in a medium depends on both the

medium (air, water) and the wave frequency (ν).

• The product of frequency and wavelength gives the speed of the wave
(the path traveled per unit time). The speed and wavelength depend on
the medium.

(velocity) v = ν . λ (ν constant)

• The wavelengths of the rays used for the spectral regions are as
follows. 7
b) Speed of Light

• The radiations reach the maximum speed in vacuum and this speed,
indicated by the symbol c, is 2.99792x108 m/s for each frequency.

c = ν . λ = 3.00x108 m/s = 3.00x1010 cm/s

• The radiation slows down because the electromagnetic field of the beam
interacts with the electrons of atoms or molecules in a material medium.

8
• Since the frequency of the radiations is constant, the wavelength
decreases as they enter a medium through a vacuum and vice versa.

c=ν.λ

Change of wavelength as rays pass from air to dense glass medium and
back to air

9
• In electromagnetic rays, the amount of waves in 1 cm is defined as the
wave number ( ). Its unit is cm-1 (infrared !).

• The refractive index (ɳ) of a medium is a measure of the interaction of

electromagnetic radiations with that medium as they pass through it.

• Refractive index, ɳmedium = vvacuum/vmedium = c/v

• For example; If the refractive index for water is given as 1.33, then the
speed of the radiations in the water v = c/1.33 = 2.26x1010 cm dir.

Example: What is the wave number of infrared light with a wavelength of

5.00 μm?

1
Answer: ν= -4 = 2000 cm-1
5,00 μm x 10 cm/μm

10
c) Radiant Power and Intensity

• The radiant power (P) in watts (W) is the energy of the beam that
reaches a certain area in 1 second. Intensity is the energy emitted per
unit solid angle.

• Both magnitudes are proportional to the square of the electric field

amplitude.

• Although not entirely accurate, the terms radiant power (P) and intensity
(I) are often used synonymously.

• On the other hand, the wave number ( ) in cm-1 is used to describe

infrared rays.

• The most useful (λ = 2.5 - 15 μm) wave number region of these rays,
which is used in the diagnosis and determination of organic species, is the
range of 4000 - 667 cm-1.
11
A. 2. The Particle Nature of Light: Photons

• To understand some of the interactions between radition and matter, it is

assumed that the beam consists of energy packets called photons.

• A photon is an electromagnetic ray particle with zero mass and energy

hѵ.
hc
E=hn= =hcv
l (joule) ( : wave number)

• Here, h is Planck's constant and it is 6.63x10-34 J s.

• The beam power of a beam of light is directly proportional to the number of

photons per second.

12
Example: Calculate the energy, in joules, of one photon and one mole of
photon of infrared light with a wavelength of 5.00 μm.

Answer:

hc
E = hn = =hcv
l

E = h c v = 6.63x10-34 J s x 3.00x1010 cm/s x 2000 cm-1

E = 3.98x10-20 J (1 foton)

E = 3.98x10-20 J/foton x 6.022x1023 foton/mol foton

E = 24.0x103 J/mol foton = 24.0 kJ/mol foton

13
B. RADIATION – MATTER INTERACTION

• Important radiation-matter interactions of spectroscopy are related to

transitions between different energy levels of chemical species (atom,
molecule).

• Other interactions such as reflection, refraction, elastic scattering,

interference and diffraction are related to the bulk properties of matter.

B.1. Electromagnetic Spectrum

• The electromagnetic spectrum includes a very wide range of energy

(frequency) and thus wavelength.

• Visible radiations cover a very narrow region of the electromagnetic

spectrum. Below are the regions of the electromagnetic spectrum.

14
(a) Types of electromagnetic radiation. Gamma rays have the shortest wavelength and
highest frequency; radio waves have the longest wavelength and the lowest frequency.
Each type of radiation is spread over a specific range of wavelengths (and
frequencies).
(b) Visible light ranges from a wavelength of 400 nm (violet) to 700 nm (red)
15
• The order of the colors in the visible region according to the decreasing
wavelengths; Red, Orange, Yellow, Green, Blue, Navy Blue, Purple.

• Spectrochemical methods using ultraviolet, visible and infrared rays are

called optical methods.

16
RF

Regions and radiation-matter interactions in the electromagnetic

spectrum
17
B.2. Spectroscopic Measurements

• In spectroscopy, the interaction of radiations with matter is used to obtain

information about a sample.

• Often, the sample is excited first using heat, electrical energy, radiations,
subatomic particles or the energy of a chemical reaction.

• Before applying the so-called excitatory energy, almost all of the analyte is
in its lowest energy state, which is called the ground state.

• The given excitatory energy causes some of the analyte to move to a

higher energy level, which is called the excited state.

18
• Information about the analyte is obtained by measuring the radiations
emitted by the analyte as it passes from this state to the ground state or
absorbed during excitation.

• In emission spectroscopy; the analyte is excited using heat, electrical

energy or chemical reaction energy (chemiluminescence).

• In chemiluminescence spectroscopy; the analyte turns into an excited

form as a result of a chemical reaction (bioluminescence-firefly).

• In emission spectroscopy, the intensity of the emitted radiations

provides information about the identity and concentration of the analyte
(qualitative and quantitative analysis).

• Below; the processes encountered in emission or chemiluminescence

spectroscopies are represented.
19
 return to stable phase
non-radiated
excitation

energy level diagram

radiated
beam power

non-radiation
processes

spectrum

Emission – Chemiluminescence events

20
• Measurement results are often given as a graph of radiation intensity
versus frequency or wavelength, which is called the spectrum.

• Many different processes such as scattering, refraction and reflection

can occur when the sample is excited by an external light source.

• The important thing in spectroscopy is that some of the radiations are

absorbed, resulting in the excited state of analyte species.

• In absorption spectroscopy, the amount of absorbed radiation is

measured as a function of wavelength.

• Emission or absorption spectroscopy measurement results can give

qualitative and quantitative information about the sample.

21
 absorblanan enerjiler

Absorption spectrum
Absorbans

Absorption phenomena (method)

22
• On the other hand, photons emitted in all directions after absorption are
measured in photoluminescence spectroscopy

• The most important forms of photoluminescence for analytical purposes

are fluorescence spectroscopy and phosphorescence spectroscopy.

photon release
(dashed arrows non-radiant)

Photoluminescence methods

23
• In photoluminescence spectroscopy, the wavelength of the emitted
radiations also corresponds to the differences in energy levels.

• The main difference between fluorescence and phosphorescence;

fluorescence is fast and phosphorescence is slower.

• The processes shown so far can be possible in any region of the

electromagnetic spectrum.

• The excited different energy levels of matter can be nuclear levels,

electronic energy levels, vibrational levels, or spin levels.

• In this section, the priority will be absorption spectroscopy in the UV/visible

region of the spectrum (common use).

24
Absorption and emission of electromagnetic rays

25
C. RADIATION ABSORPTION

• If the substance is excited by an external source of radiation, each

chemical species absorbs specific frequencies from electromagnetic
radiations.

• Thus, the intensity of the radition used in the processes in which energy is
transferred to the species is reduced. That is, the radiation becomes
weaker.

C.1. Absorption Process

• The Beer-Lambert absorption law shows quantitatively how the amount

of attenuation depends on the concentration of the absorbing molecules
and the path length over which absorption occurs.

• At constant analyte concentration, the longer the beam path, the greater
the attenuation of the beam, which encounters more absorbing species.
26
• Likewise, while the beam path is constant, the intensity of the beam
decreases as the analyte concentration increases.

Transmittance

Absorbance

Radition path

Reduction of beam intensity by an absorbing solution

27
• Parallel beam of monochromatic radiation passing through b cm thick
medium with absorber at c concentration is shown above.

• The transmittance of the solution (T) is the the fraction of incident

radiation transmitted by the solution.

Transmittance : T = P/P0

• Often, the transmittance is given in percent and is called the percent

transmittance.

28
a) Absorbans

• There is a logarithmic relationship between absorbance (A) and

transmittance of a solution.

b) Measurement of transmittance and absorbance

• Transmittance and absorbance as described above cannot be measured

directly in the laboratory.

• Because, even if the solution to be analyzed is in a transparent container,

reflection and scattering may occur on the container walls that reduce the
beam intensity.

• For example, the loss is 8.5% when there is only water.

29
• In addition, some large molecules can cause scattering of the radiations,
reducing the radiation intensity even though they do not absorb.

• Sometimes even the cell wall can absorb.

Reflection and scattering losses in solution in a typical glass cell

30
• In order to eliminate all these effects, the way is always followed.

• The intensity of the radiation passing through the analyte solution is

compared with the intensity of the radiation passing through an identical
cell containing only solvent.

• That is, the symbols P0 and P are the intensities of the radiations after they
leave the solvent and solution, respectively.

c) Beer’s Law

• According to Beer's law; The absorbance is directly proportional to the

path (b) traveled by the radiation in the absorbing medium and the
concentration (c) of the absorber species.

31
 [a : L/g.cm]

• Here; a is a constant called absorbtivity. The numerical value and units of

absorptivity depend on the units of b (cm) and c (g/L).

• If the concentration unit is mol/L and the optical path is taken in cm, the
molar absorbtivity (ε) is used instead of absorptivity (a) term.

[ε : L/mol.cm]

• The molar absorptivity of each species at its absorption maximum is a

species-specific value.

• In quantitative analysis, a large molar absorptivity is desired. Because, in

this case, the sensitivity increases.

32
d) Terms used in absorption spectrometry

• In addition to the terms used to describe the absorption of radiant energy,

old terms related to the subject should also be known.

33
e) Using of Beer's law

• Beer's law can be used for a variety of purposes. For example, absorbtivity
can be calculated when the concentration is known.

• If the molar absorbance and radiant path are known, the analyte
concentration can be found by measuring the absorbance. A = ε b c

• However, the absorptivity values change as the solvent, solution

composition and temperature change.

• Therefore, standard solutions of the analyte should be prepared in the

same solvent and at the same temperature, and absorbtivity should be
found first.

• Usually, a calibration curve is prepared first in this way.

34
Example: The transmittance of a 7.25x10-5 M solution of potassium
permanganate measured in a cell with a wavelength of 525 nm and a light
path of 2.10 cm was found to be 44.1% (T%).

(a) Find the absorbance of this solution.

(b) Calculate the molar absorptivity for KMnO4.

Answer: The absorbance (A) is found as:

(a) A = - log T = - log 0.441 = - (- 0.3556) = 0.3556

(b) A = ε b c

ε = A / b c = 0.3556 / (2.10 cm x 7.25x10-5 mol.L-1)

= 2.34x103 L.mol-1cm-1

35
f) Applying of Beer's law to mixtures

• Beer's law can also be applied to solutions containing more than one
absorber that absorbs the same radiation.

• Provided that there is no interaction between the various species in

solution, the total absorbance of the system can be calculated as follows.

Atotal = A1 + A2 + ….+ An = ε1bc1 + ε2bc2 + …+ εnbcn

• Here, the numbers 1, 2, 3, ….., n represent the components.

• As a result, absorbances can add up if the absorbing species do not

interact.

36
C.2. Absorption Spectra

• The absorption spectrum is a graph of wavelength (λ) versus

absorbance (A) and an example spectrum is given below.

A = log (P0/P) = a b c
Absorption
a : constant
spectra of
Path lenght 1.00 cm potassium
permanganate
solutions at five
different
concentrations
(ppm).

37
• Absorbance can also be plotted against wavenumber or frequency.

• Absorption spectra can be obtained directly in most scanning

spectrophotometers.

• On older devices, transmittance is read and plotted against wavelength,

T or T%.

• The plot of molar absorbtivity (ε) as a function of wavelength is

concentration independent, that is, it is constant (ε : L/mol. cm).

• Such a graph is characteristic for a particular molecule and is sometimes

used for qualitative analysis.

• The color of a solution is related to the absorption spectrum of that

solution.

38
Example: Why is the color of an aqueous solution that appears red, such as
Fe(SCN)2+ ?

Answer: It is due to the fact that the complex transmits red, which absorbs
the green radiation in the incoming white light beam.

Here, the green ray is called the absorbed radiation, while the red
radiation that passes is called the complementary color (the radiation
used in colorimetry).

A solution color

39
a) Atomic absorption

• A spectrum can be obtained by passing a beam of polychromatic

radiation in the UV or visible region through a medium containing gaseous
atoms.

• At this time, the radiations with a certain frequency in the beam are
attenuated due to absorption and absorption lines appear in the spectrum.

• For example, the transitions belonging to the formation of the three

absorption lines seen in the sodium atom spectrum given below are
explained as follows.

• The single outer electron of the Na atom in its ground state is excited from
the 3s to the 3p, 4p or 5p orbitals as a result of radiation absorption.

40
• Each transition occurs with the complete
absorption of the beam (hѵ) photon, which
has an energy exactly matching the energy
difference between the orbital in which the
electron will be excited and the 3s.

• Transitions between two different orbitals are

called electronic transitions.

• However, atomic absorption is measured

using a very narrow and almost
monochromatic light source, that is, at a
single wavelength.

41
• The electron volt (eV) is a unit of energy. q = 1.60x10-19 coulombs is the
energy consumed or released when an electron with a charge is moved
under a potential difference of 1 volt (1 joule/coulomb).

Example: The energy difference between the 3p and 3s orbitals in the figure
given above is 2.107 eV. What is the wavelength of the radiation to be
absorbed for excitation of the 3s electron to the 3p orbital?
(1 eV = 1.60x10-19 J).

h c 6,63 .10-34 J s x 3,00 . 1010 cm/s x 107 nm/cm

Answer: λ= =
E 2,107 eV x 1,60 .10-19 J/eV
λ = 590 nm

42
b) Molecular Absorption

• When excited by ultraviolet, visible and infrared rays, three types of

quantized transitions can occur in molecules.

• When a molecular substance absorbs the radiation; in addition to

electronic transitions, there are vibrational transitions and rotational
transitions.

• With UV and visible region rays, n electrons that are not bonded by sigma
(s) and pi (p) bonds in molecular substances are excited (mol.orbt.).

• In an electronic transition process, the hv energy of the photon

absorbed must be exactly equal to the difference between the energies of
the two orbitals.

43
 • Each molecule has a large number of
Vibration levels quantized electronic transition energy
levels (E0, E1, E2, …) in relation to the
Excited energy state interatomic bond.
Electronic transitions
• These levels are further subdivided into
Vibration levels quantized sub-energy levels. Vibration
transitions occur between these levels.
Excited
energy
state • The events during IR, VIS and UV light
Electronic
transitions
absorption of a polyatomic species are
given right side.

Vibration
levels
• The energy of infrared rays is not
sufficient for electronic transitions (λ1 -
λ4).

44
• Two of the many excited electronic energy states of a molecule relative to
the E0 ground state are shown as E1 and E2.

• In addition, some of the vibration levels available for each electronic

state are indicated by lighter horizontal lines (1, 2, 3, 4..).

• The difference between vibrational energy levels is smaller (about one-

tenth) than the energy difference of electronic transition states.

• Vibration energy levels can be explained by considering the interatomic

bond in a molecule as a spring with atoms attached to its end.

• The potential energy of such a system at any instant can take certain
values depending on the degree of tension and compression of the spring.

45
 Molecular vibration
types

The potential energy of the bond

takes certain values, which are called
vibrational energy levels.

46
• There are also many quantized rotational levels related to the rotational
motion of a molecule about its center of gravity.

• The rotational energy levels are centered around the lines in the figure
showing the vibrational energy levels.

• The difference between rotational energy levels is on the order of one-

tenth of the difference between vibrational energy levels.

• As a result, the total energy (E) of an excited molecule is given by

considering three types of transitions with the following equation.

47
1- Infrared ray absorption: The energy of infrared rays is generally too small
to provide electronic transitions.

• Transitions between the vibrational and rotational states of the molecule's

fundamental electronic state can be brought about by these rays.

2- Ultraviolet and visible light absorption: It occurs in the form of absorption

bands consisting of many lines close to each other.

• The absorbing species in the solution medium is surrounded by the

solvent molecule.

• For this reason, the clear boundaries between the absorption bands often
disappear as well.

48
• Because collisions lead to an expansion in the energies of the quantum
states. Thus, it gives smooth and continuous absorption peaks.

• For example, a typical ultraviolet absorption spectrum is given below (for

1,2,4,5-tetrazine).

• Each tetrazine molecule in the gas phase is sufficiently separated from

each other to vibrate and rotate freely (a).

• Well; Alongside the electronic transitions, sharp absorption peaks appear,

indicating transitions of various vibrational and rotational states.

• In the liquid phase and aqueous solution, the tetrazine molecules cannot
rotate freely, so fine details cannot be seen in the spectrum (b and c).

49
 Visible absorption
spectrum of 1,2,4,5-
tetrazine

(a) Electronic, vibration and

rotational transitions

(b) Electronic transitions

(vibration and rotational
transitions are lost in the
apolar solvent)

(c) The combination of

electronic transitions (in
polar solvent)

50
• Collisions and interactions with water molecules also change the energies
of vibrational energy levels in an unruly manner.

• This causes the spectrum to appear as a broad peak (c).

C.3. Deviations from Beer's Law

• There are frequent deviations from the direct proportion between the
measured absorbance and the concentration. These can be grouped into
three (A = ε b c).

a) Some of these deviations are true deviations and impose limitations on

the application of Beer's law (law of borders!).

• Real deviations occur in case of high concentration of analyte or presence

of foreign substances (electrolyte!) in the environment.

51
• Concentrated foreign substances in the environment cause similar results.

• As the interaction between the particles increases, the deviation from linearity
begins.

• Because each particle will affect the charge distribution in the neighboring
particle and the degree of absorption of the used beam will change.

b) Some deviations are caused by the absorbance measurement technique,

which are called device deviations.

• Using a polychromatic beam during the measurement or inability to create a

complete monochromatic beam,

• Stray beams and uncoupled cells are instrument deviations caused by the
measuring technique.

52
• If the beam is not a perfectly monochromatic beam, a deviation from
Beer's law occurs.

• This deviation will be less at a wavelength where the molar

absorptivity remains approximately constant.

• To avoid such deviations, it is necessary to choose a band close to the

wavelength at maximum absorbance (in this region ε is constant).

• Stray rays are produced by scattering on the surfaces of prisms,

lenses, filters and windows.

• Stray rays are a major source of error, especially when reading high
absorbances. For example, absorbances greater than A = 2.

53
• Stray rays pass without being absorbed and cause an error in the
measured absorbance value.

• Also, non-conjugate cells are important.

• For example, deviations from Beer's law arise when the beam
paths or optical properties are different (A = ε b c).

c) Deviations resulting from chemical interactions related to

concentration changes are called chemical deviations.

• Chemical interaction; It is the formation of different absorber

species as a result of decomposition, association or reaction of the
absorber species with the solvent.

54
Example: A 5.0 mL solution containing 5.94 ppm Fe(III) is diluted to
50.0 mL by first treating with an excess of an appropriate amount of
KSCN solution. The molar absorptivity of the FeSCN2+ complex
formed at 580 nm is 7.0x103 L . It is given as cm-1mol-1. What is the
absorbance of this solution when measured with a 2.5 cm cell?

Answer: A = ε b c c = 0.594 ppm = 0.594 mg/L

c = 0.594x10-3 g L-1 / 56 g.mol-1

c = 10.61x10-6 mol/L

A = 7x103 L . cm-1mol-1 x 2.5 cm x 10.61x10-6 mol.L-1

A = 185.7x10-3 = 0.1857 (Units ! ! !)

55
Example: 1,10-phenanthroline is added to a 10 mL portion taken from a
Cu(I) solution and diluted to 100 mL. The molar absorptivity of this
complex at 435 nm, where it has a maximum absorbance, is 7000 L. It is
given as cm-1mol-1. Since the absorbance is 0.952 measured with a 2.0 cm
cell, find the Cu+ concentration of the first solution in ppm. (C: 63.5)

Answer: A = ε b c Measurement is done in final solution !

0.952 = 7x103 L.cm-1mol-1 x 2.0 cm x c

c = 6.8 .10-5 mol/L Initial solution : c = 6.8x10-4 mol/L

c = 6.8x10-4 x 63.5 = 431.8x10-4 g/L = 43.18 mg/L (ppm)

56
D. EMISSION OF ELECTROMAGNETIC RADIATIONS
• Atoms, ions and molecules can be excited from the ground state to one or
more higher energy levels by different excitation techniques.

• Warning:

(1) Bombardment with elementary particles such as electrons,

(2) High temperature plasma, flame or electric arc heating,

(3) It is done by irradiation with electromagnetic rays.

• The lifespan of the excited species is usually very short, 10-9 - 10-6
seconds.

• It returns to the ground state or a lower excited state by giving back its
excess energy in the form of heat, electromagnetic radiation, or both.

57
D.1. Emission Spectra

Ø Emission spectra are obtained by plotting the relative intensities of rays

emitted from a source against wavelength or frequency.

Ø Below is the emission spectrum obtained by spraying salt water onto a

hydrogen/oxygen flame.

Ø The figure shows three types of spectra: line spectrum, band spectrum
and continuous spectrum.

Ø Line spectra are formed as a result of excitation of atoms.

Ø Band spectra consist of groups that come from small molecules and
contain many lines that are close to each other.

58
Emission spectrum of a brine sample

4p 3s
(radikal)

(radikal)

It arises from the emission of

incandescent solid particles in
the flame.
(atomic and molecular vibration)

59
a) Line spectra

ØIf the radiating species are distant and independent atoms, the
resulting spectra are line spectra (as in gases).

ØParticles in the gaseous medium behave independently and their

spectrum is a series of sharp lines with a line width of about 0.01 Å.

ØBecause of the electron spin, the p and d levels are each split into two
sub-energy levels (doublets) with very close energies.

ØA single electron in the 3s orbital of the ground-state sodium atom can

be excited to one of these lower energy levels (E3p or E'3p) by
absorbing thermal, electrical, or radiant energy.

60
 Energy level diagram of
sodium

ionization of sodium The wavelength of the photon

emitted when returning from
3p to the ground state is as
follows.

c
E=h
λ
splitting into two lower
hc
energy levels (doublet)
λ=
due to electron spin
E
doublet hc
λ=
ΔE
hc
ground state λ1 = = 589,6 nm
( E 3p - E0 )
61
• A few nanoseconds after excitation, the electron emits a photon as it
returns from the 3p level to the 3s ground state.

hc
The wavelength of this photon, l1 = = 589,6 nm
( E 3p - E 0 )

• Similarly, when the excited atom passes from the 3p' state to the ground
state, it emits a second light of λ2 = 589.0 nm. (Δλ = 0.6 nm)

• Eventually, conversions from two very close energies to the ground state
from two separate 3p energy levels yield two very close emission lines in
the spectrum.

• According to the rules of selectivity, some transitions are possible and

some transitions are prohibited. That is, there is no random transition
between any two states.
62
b) Band spectra

Ø Many samples can form gaseous radicals and small molecules under
conditions where they can radiate.

Ø These form band spectra as well as line spectra.

Ø In the figure above, the bands of the OH and MgOH radicals and the MgO
molecule are shown.

Ø These bands are made up of many lines that are very close to each other.

Ø These lines originate from many vibrational energy levels that overlap the
fundamental electronic energy level of the molecule.

63
c) Continuum spectrum

• When solids are heated to an incandescent state, continuous spectra with

no line characters are formed.

• These radiations, which occur at high temperatures, vary with the

temperature rather than the type of the radiant substance and are called
black body radiation.

• Blackbody radiation is generated by the many atomic and molecular

vibrations present in the solid that are excited by heat energy.

• This background radiation intensity decreases as the UV region

approaches.

• Because, in order for the rays emitted by a solid object in the ultraviolet
region to be intense, it must be heated to very high temperatures.

64
 V
i
s
i
b
l
e
r
e
g
i
o
n

Blackbody radiation curves for various beam sources.

(UV : 180-380 nm, visible : 380-780 nm, near IR : 780-2500 nm)

65
d) Effect of concentration on line and band spectra

Ø The intensity of a line or band in the emission spectrum is directly

proportional to the number of excited atoms or molecules that radiate.

Ø Therefore, it is possible to write the following expression between the

beam intensity (P) and the concentration (c).

P=kc

Here, k is a proportionality coefficient.

• The basis of quantitative (quantitative) emission spectroscopy is

based on this relation.

66
D.2. Emission by Fluorescence and Phosphorescence

• Fluorescence and phosphorescence are important emission processes

that occur after the excitation of atoms or molecules with a beam of light.

• In both processes, the excited species returns to its ground state

(photoluminescence), releasing its extra energy in the form of photons.

• Fluorescence is much faster than phosphorescence, and this process is

usually completed in a short time (10-5 s) following the excitation.

• Phosphorescence, on the other hand, can last for minutes or even hours
after excitation is over.

• Fluorescence is much more important in analytical chemistry.

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a) Atomic Fluorescence

Ø Gaseous atoms can fluoresce if exposed to a beam of light with a

wavelength corresponding to any of the lines in the absorption spectrum.

Ø For example, gaseous sodium atoms are excited from E0 to E3p by

absorbing rays with a wavelength of 589 nm.

Ø Then, it is stopped by the back emission of the same wavelength beam in

a very short time, which is called fluorescence radiation.

Ø Here, the term resonance fluorescence is used if the wavelength of the

excitation beam is exactly equal to that of the emitted beam.

68
• The energy of the atom excited to the E2 level can fall to the E1 level by
colliding with other species in the environment and transferring non-radiative
energy.

• It is then also possible to settle into the E0 ground state with 589 nm photon
emission from the E1 level.

• It is even possible for an excited atom to come to ground state by heat transfer
by collisions, without emitting any rays.

b) Molecular fluorescence

• Fluorescence is a type of photoluminescence that involves the process of

excitation of atoms or molecules with an electromagnetic radiation.

• The return of the excited species to the ground state may occur by different
mechanisms.

69
 10-15 s

The band is
(less active) formed as it is
10-9 – 10-6 s transformed
λ1>λ5 or λ1<λ5 ? into a multitude
of vibrations.

Absorption, radiant relaxation and fluorescence processes of a molecule

70
• During collisions, the vibrational energy contained in the excited analyte
can be transferred to the solvent molecules in a cascading way.

• This vibrational deactivation or vibrational relaxation occurs as a result of

the collision of excited molecules with solvent molecules.

• This vibrational energy gained by the solvent manifests itself in the form of
a very small increase in ambient temperature.

• There may be a transition from the lowest vibrational energy level at an

electronic level to the highest vibrational energy level of a lower electronic
level.

• This type of non-radiative transition phenomenon is called internal

transformation.
71
• In fact, the relative number of fluorescent molecules is small.

• Some unique structural properties of a molecule should be able to slow

down the radiant relaxation processes and accelerate the fluorescence
process.

• Many molecules do not have these properties, and therefore their

nonradiative relaxation rates are much greater than that of radiant
relaxation.

• A band is also formed in fluorescence, as there is a conversion from the

molecular E1 electronic energy level to many vibrational states of E0.

• Molecular fluorescence bands have a longer wavelength (lower energy)

than the wavelength of the excitation beam.

• This situation between the wavelengths of the rays is called the Stokes
shift.
72
a) Propagation spectra (GENERAL CHEMISTRY Chapter 7)

• Newton (1850) said that sunlight is formed by the combination of

components of different colors and that light consists of very small
particles of light ejected from luminous objects.

• Maxwell stated that light propagates by electromagnetic waves (1864).

• Einstein explained the photoelectric phenomenon by stating that light has

a particle (photon) structure.

• Planck (1900) explained that light propagates in packets of energy

(quanta).

• When energy is transferred to a substance, a distinctive spread spectrum

is observed.

• For example, heated incandescent or red-hot iron exhibits a distinctive

shine. 73
• The fact that the sun or its heated solid has a continuous spectrum is
because it includes every wavelength in the visible region.

• The emission spectra of atoms in the gas phase do not show a distribution
of wavelengths ranging from red to purple.

• For example, in a discharge tube, electrons traveling from the negative

electrode to the positive electrode collide with the gas molecules in the
tube.

• These collisions cause the atoms to emit light.

• When these spread spectra are examined, bright lines appear in different
parts of the visible region.

• These line spectra are formed because matter emits light only at specific
wavelengths.

• In other words, each element has a unique spread spectrum. 74

 QUESTIONS and PROBLEMS

24-1 24-2 24-3 24-5 24-6 24-8 24-9

24-10 24-11 24-13 24-14 24-19 24-20 24-21

THIS PRESENTATION HAS BEEN PREPARED FROM THE FOLLOWING

TEXTBOOK

SKOOG / WEST HOLLER/CROUCH

9th Edition
75
1) Considering the wave property of electromagnetic rays, show schematically a wave propagating in space. Explain the
concepts of wavelength, amplitude, period, frequency and wavenumber of a wave in items.

2) Explain the absorption process of a parallel monochromatic beam of light as it passes through a medium. Define the
concepts of transmittance, percent transmittance and absorbance and write the relationship between them.

3) Can absorbance be found by measuring incident and transmitted beam intensities during the absorption process of a parallel
monochromatic beam of light passing through a medium? Explain the reasons for this in detail by drawing a figure.

4) Considering the light-matter interactions, what is meant by molecular absorption? What are the types of molecular
absorption? Briefly describe each.

5) What do electronic transition, vibration transition and rotational transition mean? Briefly describe. Draw an energy level
diagram showing these energy changes.

6) In practice, what is meant by deviations from Beer's Law? Indicate these deviations by grouping them in items. Explain the
reason for each in one sentence.

7) What does emission of electromagnetic rays mean? Three types of spectra emerge in an emission spectrum. State them and
explain the reason for each of them.

8) Briefly explain fluorescence and phosphorescence phenomena. Briefly explain how atomic fluorescence and molecular
fluorescence events occur in these processes, and show the energy changes in the events by drawing a figure.

9) What is the "Stokes shift" in molecular fluorescence and how does it occur? Please explain briefly.

76