UNIT IV

FUNDAMENTAL SPECTROSCOPIC TECHNIQUES AND THERMAL ANALYSIS

4.1.1 The principle of spectroscopy

One form of electromagnetic radiations is allowed to interact with the atoms or
molecules and the emitted, or absorbed, or transmitted or scattered radiation is analyzed.
This is known as spectroscopy.

4.1.2 Differences between atomic and molecular spectra

Atomic spectra Molecular spectra

1 It is simple and line spectra It is complicated and band spectra

2 It is due to electronic transition – called It is due to vibration, rotation and

electronic spectra – appear in UV – electronic transitions– appear in IR
Visible region region

4.1.3 Lambert’s law

Lambert’s law is one of the photo-physical laws. It states, “when a beam of
monochromatic light is passed through a homogenous absorbing medium, the rate of decrease
 dl 
of it’s intensity with the thickness of the medium    is directly proportional to the
 d 
dI
intensity of the radiation. i.e., it is an exponential function.  I
d

Io k
Up on integration we get, log 
l 2.303 
t

Where Io  intensity of the incident radiation

It  intensity of the transmitted radiation

  length of the absorbing medium (thickness)

k  a constant called linear absorption coefficient
Io
log
Stands for absorbance. Hence the law may be stated “The amount of light
lt
absorbed is proportional to the thickness of the absorbing medium.”

4.1.4 Beer’s law

It is another photo – physical law applicable to solution. It brigs out the effect of
concentration on absorption. It states that “The amount of light absorbed by a solution is
proportional to the concentration of the solution” mathematically it is represented to
 Io k1
log  C
l t 2.303

C  Concentration ; k1  absorptivity constant

4.1.5 Beer – Lambert’s law

It is the combination of Lambert’s and Beer’s laws. It states “when a beam of
monochromatic light is passed through a solution of absorbing substance, the rate of decrease
 dI 
of intensity of radiation with the thickness of the medium    is directly proportional to
 dl 
the intensity of the radiation as well as the concentration of the solution.

dI
i.e.,   IC
dL

dI
  kIC where k  absorption coefficient (constant)
dL

dI
  kCd 
I
II t  
dI
Up on integration with the limits -   kC  d
II0 I  0

Io  intensity of the incident radiation & It  intensity of the transmitted radiation

The product kC is constant C  concentration of the solution

It
i.e.,  log  kCL k  the molar adsorption coefficient
l0

I0
i.e., log  kCL
lt

I0
i.e., 2.303 log  kCL
lt

I0 k
log  CL (This is a mathematical form of Beer – Lambert’s law)
l t 2.303

k
 ε , molar extinction coefficient or molar absorptivity or molar absorbance – It
2.303
is a constant for a particular solution.

Io
log  A , called absorbance or optical density (OD)
It
 A=CL L  length or thickness of the medium

Thus absorbance A is directly proportional to the concentration A  C as L is

constant for a particular solution and for constant thickness. When A is plotted against C, a
straight line is obtained.
A = 0, for a perfect transparent medium and A is infinity for perfect opaque medium.

Limitations of the law :

i) Beer – Lambert’s law is valid for dilute solutions Deviation
only; There is deviation when the concentration is

A
higher (> 0.01 M)
ii) The radiation should be purely monochromatic.
iii) There should not be much temperature variation.
iv) There should not be any structural change during C
dilution such as Cr2O72- CrO42-

Applications of Beer – Lambert’s law

i) To determine the concentration of a solution :-
A number of standard solutions are prepared, The

A
absorbance values (A) are determined for them by For unknown
means of spectrophotometer. Graph is drawn
connecting A & C. straight line is obtained. Then A is concentration
found out for unknown test solution. From the graph C
the corresponding concentration is found out.
ii) The concentration can also be determined using a single standard solution.
Astd = L Cstd and Aunknown = L Cunknown

A std Cstd

A unknown C unknown

A unknown  Cstd
C unknown   (calculate d)
A std

iii) This is the fundamental law for spectrophotometer and calorimetric

estimation.

4.1.6 Molar extinction coefficient Or molar absorptivity

Absorbance A = CL   absorption extinction coefficient.

A =  when C = 1 M and L = 1 cm. Hence absorbance coefficient is defined as

absorbance per unit concentration and unit length.
A A
ε   Unit of  is M-1 L cm-1 or M-1 dm3 cm-1
C  L C(m 1 ) Lcm
4.1.7 Transmittance of a solution
Transmittance (T) is defined as “the fraction of the incident light that is transmitted by
I
a given system” T  t
I0

It
Taking logarithm log T  log
I0

I0
i.e.,  log T  log A
It

i.e., A, (absorbance) = – log T (transmittance)

and also  C L = – log T

 – log T is called absorbance or optical density

I0
i.e., A  log  ε CL   log T
It

4.2 Ultra Violet – visible spectroscopy (UV-visible)

4.2.1 Principle
When a monochromatic beam of radiation is passed through a sample, a fraction of
radiation is absorbed bringing electronic transition; the rest is transmitted. Transmitted light
is recorded in terms of it’s absorbance ‘A’ which is 'plotted against it’s wavelength. The hike
in the curve indicates the region of absorption.
Region : Zero  800 nm.
A

 

Block diagram of UV visible spectrometer

Beam
Sample cell Detector Recorder
splitter Ie It
1 2 3 4 5

Source of Monochromator
100 % Spectrum
Slit
light 3
A

Reference cell

 
Components and their function.
No 1 : Source of light : Tungsten filament lamp, H2 or
deuterium lamps are used to cover entire UV – Visible region
No 2 : It is a prism or a grating called Monochromator. It selects the desired wavelength,
cutting off others. It has two slits (entrance and exit).
No 3 : These are two transparent cells made up of quartz. One for keeping the sample
solution and another for solvent only.
No 4 Detector : After passing through the two cells, radiation enters the detector. It converts
the resulting light into equivalent current.
No 5 Recorder : Here the signal is received and recorded in terms of absorbance and
wavelength (A Vs ).
Functioning : A solution of analyte is taken in sample cell; And pure solvent is taken in
reference cell. Radiation from the source is passed into Monochromator where selection of
wavelength takes place. Then the radiation is split into two parts; one portion is passed
through the sample and another through reference cell. After passage through the cells, the
radiation is allowed to fall on the detector and then sent to the recorder, where the signal is
received and recorded. This is known as spectrum which is then interpreted.

4.2.2 Different types of electronic transition

 * >> n  * >   * > n  *

(1) (2) (3) (4)
Among these (1) appears at higher energy region; (2) is forbidden transition; hence
(3) and (4) are important. They occur in the region 200 – 450 nm.

Different types of electronic transitions possible in the following compounds

i) CH3OCH3 ii) CH3NH2 iii) CH3CH2OH
iv) CH3CH2CH3 v) CH3CHO
..
Solution : i) CH3OCH3 i.e., CH3 – .O. – CH3   * and n  *
..
ii) CH3NH2 i.e., CH3 – NH2 . .   * and n  *

iii) CH3-CH2-OH i.e., CH3 – CH2 – .O. – H   * and n  *

..
..
 iv) CH3-CH2-CH3 i.e., CH3 – CH2 – CH3 only   *

v) CH3 – CHO i.e., CH3 – CH = O  * ; n  *

  * ; n  *

4.2.3 Terms involved

i) Chromophore ii) Auxochrome
i) Chromophores : The groups or structures that absorbs radiation and gives colour to the
molecules, if present sufficiently are called chromophores. They contain multiple bonds in
their structure.

Example : C = C ; - C  C - ; C = N - ; - N = N - ; O = N  O (NO2) etc.,

They are capable of absorbing in the region 200 – 800 nm.
ii) Auxochrome : Some groups in the molecules do not absorb light by themselves but shift
the position of parental absorption to higher region (longer wavelength) and thereby make it
more colourful – They are called auxochrome. They are found to have lone pair of electrons
in them.
Example :. . – OH ;. . – NH2 . ;. – OR ; .. . –. Cl etc.,
.. .. ..
The shift is known as bathochromic shift (Red shift).
The groups that shift the absorption towards lower region are called hypsochromes and the
shift is called hypsochromic shift (low shift).

O 2N NO 2 OH

O 2N NO 2

Deep yellow dye

Yellow
NO 2

NO 2

Chromophore : – NO2 group

Auxochrome : – OH group

4.2.4. The applications of UV – Visible spectroscopy

i) To identify alkanes, alkynes and arenes (In quantitative analysis)
These compounds can be identified from the position of their spectrum.
 CH3 - CH3 CH2 = CH2

Only   *   *

(absorption at low max = 165 nm

Wavelengths – high   * and delocalization
energy region
max = 204 nm (low energy region
ii) To identify aldehyde and ketones
Aldehydes and ketones are functional isomers; They absorb at various positions from
which they can be identified.
CH3 CH2 CHO CH3 CO CH3

max = 165 nm

iii) To detect the presence of conjugation

Presence of conjugation shifts the position of absorption to higher region
CH2 =CH–CH2–CH=CH2 and CH2 =CH–CH=CH–CH3
(Non-conjugation or isolated) (Conjugated system)

 = 160 – 170 nm  = 217 nm

Similarly in ketones
CH2=CH–CH2–C=CH3 and CH3–CH=CH–C–CH3
O O

(Non-conjugated) (Conjugated system)

iv) To study the nature of shift and identify the position isomers

CH3 – CH = CH2 max = 180 (parent compound)

..
CH3 – CH = CH – Cl (absorption at higher region
C3H5Cl .. - bathochromic shift
Cl – CH2 – CH = CH2 (lower shift)

v) To study the influence of pH on absorption indicator

Phenolphthalein gives no colour in acid medium and gives pink colour in alkaline
medium. i.e., the alkali medium there is shift of absorption to higher region because of
delocalization of electrons.

vi) Detection of impurities

 Presence of impurities in organic compounds can be easily detected by UV – Visible
spectrometric method. Impure compounds will give high intense peak, but position will be
the same.

vii) In quantitative analysis

UV – absorption spectroscopy is also used in quantitative determination of
compounds. It is used in Beer’s law A = C L. where A  absorbance,   molar extinction
coefficient; C  concentration ; L  length of cell. For same cell and substance with
solvent,  and L are same.  A  C. Measuring Astd for unknown concentration

A Std CStd

A Un C Un

CUn can be evaluated. This can also be evaluated by graphical method.

viii) UV visible spectroscopy is also useful to determine the structure of organic compounds;
Compounds with similar structure will give similar spectrum. Thus structure of Isatin was
estimated as (1) and not (2)
(1) H (2)
N N

O OH

O O
ix) It is also useful in chemical kinetics, photometric titrations, molecular weight
determination etc.,

x) UV spectroscopy is also useful in inorganic estimation.

Example : Pb content in bone – ash. Ca in blood serum etc., can be estimated.

4.3 IR spectrascopy

4.3.1 Principle

IR spectra are other wise known as vibrational spectra shown by molecules, not by atoms. It
arises due to absorption of electromagnetic radiation at IR region (4000 – 400 cm-1) and
bringing variation in vibrational energy levels.
The IR spectrum is obtained as a plot of percentage transmission (%T) against wave
number  . The region is above 800 nm (wavelength) in electro-magnetic radiation.
%T

 
4.3.2 Conditions for a molecule to be IR active (OR) vibrational selection rule
i) When the molecule has permanent dipole moment, there should be change in dipole
moment during the vibration.

Example : (+)H – (-)Cl (+)H ----------- (-)Cl

Thus molecules like HCl, H2O, NH3, NO2, SO2 etc are IR active.
ii) In case there is no permanent dipole moment, the dipole moment should be created during
the mode of vibration. Example : CO2 has no dipole moment.; but it is IR active because
dipole moment () is created during one or two modes of vibration.

Molecules like H2, Cl2 and O2 are IR inactive – These molecules have neither permanent
dipole moment nor dipole moment is created during vibration.
CO2 has no permanent dipole moment. It has linear structure and hence (3 N – 5) four
nodes of vibrations. The symmetrical vibration O = C = O Or O = C = O
( = 0) is IR inactive. In the asymmetric vibration O = C = O  is created. IR active
There are two bending vibrations :

O=C=O O=C=O
%T

(in plane) (out of plane) 667 cm-1 2349 cm-1

 
But both are degenerate – IR active – absorb in the same region. As the result CO2
produces two dips – one for stretching and one for bending.
HCl, NH3 and H2O  IR active, they have permanent dipole moment
CO2  IR active. Though it does not have any dipole moment, it is induced
during vibration
H2, O2  IR inactive. Neither have dipole moment nor it is created.
Ne  It is in atomic state – atoms do not give IR spectra, because IR
spectrum is due to vibration.

4.3.3 Finger print and group frequency region

The region between 1400 – 700 cm-1 is called finger print region, because at this
region the band is rich and very intense and no two organic compounds will have identical IR
spectra in this region.
The region between 4000 – 1400 cm-1 is called group frequency region, because
many groups gives their characteristic signals at this region.

4.3.4 Instrumentation
Block diagram of double beam IR spectrometer

Beam
Sample cell Detector
1 splitter
2 4 6
3
Source of %T
Monochromator
7
Slit
light 
5 Recorder
Components Reference cell

1) Source of light : Nichrome wire filament or Nernst glower (oxides of Zn, Th, Cerium
etc.,) is made the source for production of IR radiation
2) Monochromator: It selects only the IR radiation, cutting off others.
3) Beam splitter : It splits the beam into two halves of equal intensity; one is allowed to pass
through the sample cell and other through the reference cell
4) Sample cell : It is transparent to IR radiation. It contains the sample solution
5) Reference cell : It is also made up of the same material as the sample cell. It contains the
pure solvent in which the sample is dissolved.
6) Detector: Here both the radiant beams from sample cell and reference cell are
recombining and produce oscillatory signal. (It is a photo conducting cell).
7) Recorder: Here the signal coming out of the detector is recorded in the form of peak
(dips) as % T Vs  .
Working : The sample solution is taken in sample cell and pure solvent in the reference cell.
Radiation beam from the source is passed through the monochromator; The useful radiation
is selected; the selected monochromatic beam is split into two halves; one half passed through
the reference cell and other through the sample cell; then the recombined beam is allowed to
pass through the detector and then to the recorder, where the spectrum is recorded. Then the
spectrum is interpreted.

4.3.5 Applications of IR spectrai) To identify functional groups :

a) Example : Carbonyl group : >C=O is called carbonyl group; It may be either in the form
of aldehyde or ketone.

C6H5 – C – H C6H5 – C – CH3 CH3 – C – CH3 C2H5 – C – C2H5

O O O O

All these compounds will give C=O absorption at 1700 cm-1; Thus carbonyl
compounds can be identified

b) If it is aldehyde it gives one more additional signal C-H near 2800 cm-1 (R – C – H)

O
 Similarly free – OH group (alcohol), hydrogen bonded OH group, C = C, C  C etc.,
have their own adsorption band.

ii) To identify the presence of H-bonding : For free OH group, OH = 3600 cm-1 ; If
hydrogen bond is present, it occurs at longer wavelength (3400 cm-1). They can be further
distinguished whether intermolecular or intra-molecular by dilution process.

iii) To study the progress (kinetics) of a chemical reaction : The conversion (oxidation) of
alcohols into aldehydes or ketones, can be followed by studying their IR spectrum at different
intervals of time Example : CH3CH2OH  CH3 CHO

OH  C=O
(near 3600 cm-1) (near 1750cm-1)
i.e., as the time proceeds, signal due to OH group disappears and the signal for >C=O
group appears at their respective region.

iv) To test the purity of sample : Pure sample gives sharp, well resolved band; When
impurity is mixed, it gives broad and poorly resolved band. Thus by comparison with
spectrum of pure sample, presence of impurity can be ascertained.

v) To identify cis – trans isomers : IR spectra is useful to identify cis – trans isomers.
H H

C C Cis 2-Butene

CH 3 CH 3
CH 3 HC CH CH 3
2-Butene CH 3 H

C C Trans 2-Butene
H CH 3

Generally cis isomer gives signal at higher region.

vi) IR spectrum is also useful to identify tautomers.

CH3 – CH2 – C – CH3 CH3 – CH = C – CH3

O OH
(keto form) (enol form)

C=O C=C and C-OH

From the position and intensity of the IR band, the predominating form at equilibrium
can be elucidated.
vii) Shape of molecules elucidated : From the number of peaks (three for each) the structure
of NO2 and H2O are established as non linear (angular).
O
O –N
H H O
4.4 Thermal Analysis

Thermal Analysis (TA) is a group of techniques that study the properties of materials
as they change with temperature.

Thermal analysis in practice thermal analysis gives properties like; enthalpy, thermal
capacity, mass changes and the coefficient of heat expansion. Solid state chemistry uses
thermal analysis for studying reactions in the solid state, thermal degradation reactions, phase
transitions and phase diagrams.
Techniques in which a physical (thermal) property of a substance is measured as a
function of temperature while the substance is subjected to a controlled temperature variation.

Types of Thermal analysis

Thermogravimetric analysis (TGA): mass Differential thermal analysis (DTA): temperature

difference Differential scanning calorimetry (DSC): heat difference Pressurized TGA
(PTGA): mass changes as function of pressure. Thermo mechanical analysis (TMA):
deformations and dimension Dilatometry (DIL): volume Evolved gas analysis (EGA):
gaseous decomposition products
Factors affecting the TG curve
1.heating rate 2. Sample size 3. particle size of sample 4. Packing Crucible shape 5.
Gas flow rate

More than a dozen of such thermal techniques are used. But only three techniques
are covered in this chapter
1) Thermogravimetry analysis (TGA)
2) Differential thermal analysis (DTA)
3) Differential scanning calorimetry (DSC)

4.4.1 Thermogravimetric Analysis (TGA)

The Thermogravimetric Analyzer (TGA) measures the change in weight of a sample

as tested through a temperature profile. The TGA can provide information about chemical
phenomena including chemisorptions, desolvation and dehydration, decomposition, and
solid-gas reactions such as oxidation or reduction.
The mass of a sample in a controlled atmosphere is recorded continuously as a
function of temperature (or time) as the temperature of the sample is increased.

Thermogravimetric Thermal Analysis (TGA) can be used for materials

characterization through analysis of characteristic decomposition patterns. It is an especially
useful technique for the study of thermoplastics, thermosets, elastomers, composites, plastic
films, fibers, adhesives, coatings, paints, and fuels. Thermogravimetry is useful in
determining the dynamic functional effect of temperature on the amount of volatile materials
leaving a specimen as the latter is heated progressively to higher temperatures.
Thermogravimetric Thermal Analysis (TGA) can be useful for process control, process
development, material evaluation, and for identification and quality control in specifications.

A Thermogravimetric Thermal Analysis (TGA) is performed by gradually raising the

temperature of a sample in a furnace as its weight is measured on an analytical balance that
remains outside of the furnace. In TGA, mass loss is observed if a thermal event involves loss
of a volatile component. The thermal stability of a material can be associated with the degree
and time rate of mass loss as a function of temperature. TGA curves can, therefore, be used as
a preliminary screen method in the evaluation of relative behavior of insulating materials of
the same generic family.
TGA thermogram:
- A plot of mass percent as a function of time or temperature.TGA measures the change
in weight of a sample as it is heated, cooled or held at constant (isothermal) temperature.

Instrumentation of TGA :
1) A sensitive analytical balance
Range : up to 100 mg.
Sample holder is in furnace. However, the rest of the balance must be thermally isolated
from the furnace.
2) Furnace
Temperature range: up to 1500oC.
3) Purge gas system
For prevention of oxidation:
N2, Ar, He, etc. For
oxidation: O2 orair.
4) Temperature control and a computer for data acquisition /display.

Thermobalance components. The balance beam is shown as A. The sample cup and
holder are B; C is a counterweight. D is a lamp and photodiodes, E is a magnetic coil,
 and F is a permanent magnet. The computer data-acquisition, data-processing, and
control systems are components G, H, and I. Component J is the printer and display unit.

PVC = polyvinyl chloride; PMMA = polymethyl-methacrylate; LDPE = low-density

polyethylene; PFE = polytetrafluoroethylene; Pl = aromatic polypyromelitimide.

Applications
TGA can provide information about physical phenomena, such as second- order
hase transitions, including vaporization, sublimation, absorption, adsorption, and
desorption. Likewise, TGA can provide information about chemical phenomena
including chemisorptions, desolvation (especially dehydration), decomposition, and
solid-gas reactions (e.g., oxidation or reduction).

Common applications of TGA are:

(1) Materials characterization through analysis of characteristic decomposition
patterns,
(2) Studies of degradation mechanisms and reaction kinetics,
(3) Determination of organic content in a sample, and determination of inorganic (e.g.
ash) content in a sample, which may be useful for corroborating predicted material
structures or simply used asa chemical analysis.
(4) TGA is commonly used to determine selected characteristics of materials that exhibit
either mass loss or gain due to decomposition, oxidation, or loss of volatiles (such as
moisture).
4.4.2 Differential Thermal Analysis

DTA, Basics The material under study and an inert reference are made to undergo identical
thermal cycles. Any temperature difference between sample and reference is recorded. In this
technique the heat flow to the sample and reference remain the same rather than the
temperature.

DTA, Basics The differential temperature is then plotted against time, or against
temperature (DTA curve or thermogram).
A technique in which the difference in temperatures between a substance and a
reference material is measured as a function of temperature while the substance and reference
material are subjected to a controlled temperature program.
In today’s market most manufactures no longer make a true DTA but rather have
incorporated this technology into a Thermogravimetric analysis (TGA), which provides both
mass loss and thermal information. With today’s advancements in software, even these
instruments are being replaced by true TGA-DSC instruments that can provide the
temperature and heat flow of the sample, simultaneously with mass loss.
DTA peaks result from both physical changes and chemical reactions induced by temperature
changes in the sample.
Physical processes that are endothermic include fusion, vaporization, sublimation,
absorption, and desorption. Adsorption and crystallization are generally exothermic.
Chemical reactions may also be exothermic or endothermic.
1. Endothermic reactions include dehydration, reduction in a gaseous atmosphere, and
decomposition.
2. Exothermic reactions include oxidation in air or oxygen, polymerization,
and catalytic reactions.

Instrumentation of DTA
-Furnace (to 1500oC)
-Thermocouples
-Purge gas system
TC = thermocouple.
Sample size: 1~20 mg Reference: inert materials (e.g., Al2O3 , SiC, glass, etc.)
Block diagram:

DTA thermogram
Applications - DTA
(1) In general, DTA is considered a qualitative technique.
(2) Although able to measure the temperatures at which various changes occur, DTA is
unable to measure the energy associated with each event.
(3) DTA is a widely used tool for studying and characterizing polymers or metals and
ceramic materials, etc.
(4) DTA is also widely used in the ceramics and metals industry
(5) The technique is capable of studying high temperature processes (up to 2400oC for
some units) and relatively large sample sizes (hundreds of milligrams).
(6) For such materials, DTA is used to study decomposition temperatures, phase
transitions, melting, and crystallization points, and thermal stability.
(7) A DTA curve can be used only as a finger print for identification purposes but
usually the applications of this method are the determination of phase diagrams,
heat change measurements and decomposition in various atmospheres.

(8) DTA is widely used in the pharmaceutical and food industries

(9) DTA may be used in cement chemistry, mineralogical research and in environmental
studies.

4.5 Flame photometry

When an atomized metal is introduced into a flame, it is electronically excited. On

return to the ground state, light of characteristic wavelength is given out. From the nature of
radiation (colour or ), the element is identified; From it’s intensity, it’s concentration is
estimated. Metals like Na, K, Li, Ca, etc are estimated by this method.

4.5.1 Principle of flame photometry

Flame photometry is otherwise called flame emission spectroscopy substance is

ignited by LPG and air under pressure to high temperature (1700 C). Electronic excitation of
atom or ions takes place. While the excited atom returns to the ground state, radiation,
characteristic of the element is given out. From the region of the wavelength (colour) the
element is identified. From the intensity of the radiation, concentration is determined.

Example : Na gives out yellow light at the region  = 580 nm

K gives out violet light at the region  = 766 nm

4.5.2 Functions of the components

Monochromator

cathode lamp
Flame (1700 –

Hollow
Power
Nebulizer 1900 C) Prism or filter
LPG

Sample introduction
Or grating disc

Flame
system
Air under 
pressure

Monochrometer
Concave Detector Display
Atomizer
(amplifier and
lens Rotating filter
recorder)
Detector
disc
NaCl solution Exhaust (exit)
Recorder/
Display

Block diagram of flame photometer

Instrumentations

Nebulizer : Air under pressure, LPG and solutions of test solutions are sent into this
component – mixed up well and sent to the burning chamber

Atomizer : Here the mixture burns at high temperature with characteristic flame (color). The
exhaust (H2O) is sent out through the exit

Concave lens : The radiation is made beam and sent into the filter

Monochromator : (otherwise called filter or prism or grater or rotating filter disc) Here only
the desired radiation alone is selected and others cut off. For example in the case of Na
yellow radiation with  = 580 nm is selected.

Detector : The selected radiation reaches this component. Here the intensity of the radiation
is recorded in terms of current. Hence it is called photo-cell

Recorder : The current from detector is amplified and recorded. This display is directly taken
as the intensity of the radiation given out.

4.5.3 Working or the important process (steps) that occur in the flame emission
spectroscopy

i) Evaporation of the solvent from the liquid sample

ii) Decomposition of the solid in to atoms and vaporization

iii) Thermal excitation and returning to ground state giving out light

The interferences come across in flame photometry

i) Spectral interference : This arises when two elements emit at particular wavelength.

ii) Ionic interference : It is due to ionization of certain atoms at high temperature.

iii) Anions interference : Some anions like oxalate, phosphate, sulphate etc., form stable
salts with cations and do not undergo dissociation and vaporization.

iii) Cation – cation - interference : It decreases the signal intensity

4.5.4 Estimation of Na

The instrument is warmed up for sometimes by passing mixture of air, water and LPG
in to the nebulizer and allowed to burn. The pressure of air and supply of LPG are adjusted
to produce non-luminous flame. The zero adjustment is made to display 00. (zero
absorption).

The rotating filter disc is rotated for Na.

A stock solution of NaCl solution is prepared. From it, a number of std. solutions
prepared by pipetting 1 ml, 2, ml, 3 ml, 4 ml, ….. and making up to 100 ml with distilled
water so that 1 ml  10 ppm. A sample of std. solution are fed in to the instrument and
ignited. For each sample the reading on the recorder (display) is noted.

C1 -------- A1
A
C2 -------- A2
Unknown
concentratio
C3 -------- A3 and so on. n
C
Finally, sample of unknown concentration Cun is fed into and corresponding Aun is
recorded. Then graph is drawn connectively A & C. From the graph, unknown concentration
is found out.

Steps involved :
High
NaCl NaCl NaCl Na + Cl
Solution Solid temperature
Vapour (g) (g)
Thermal
Return to excitation
ground
h+ Na state Na
Light normal excited
given out

Quantitative analysis of alkali or alkaline earth metals in flame photometry

These metals can be detected from the color of the flame that they produce.

Li  Scarlet red Na  Yellow K  Violet

Ca  Brick red Sr  Crimson red Cu  bluish green
4.5.5 Applications of flame photometry

i) It is useful for analysis of metals like Na, K, Ca, Fe etc., particularly in biological
fluids and tissues.
ii) Useful for analysis of soil, natural water, glasses, cement, petroleum products etc.,
iii) Useful in medicinal and agricultural analysis

4.5.6 Limitations of flame photometry

i) Liquid sample of analyte is to be prepared

ii) It is not applicable to all metals. Elements like C, H, halogens, inert gases etc., can
not be estimated
iii) It gives no information about the molecular form of the metal in the original
sample
 QUESTION BANK
PART - A

1. State and explain Lambert’s law

Lambert’s law is one of the photo-physical laws. It states, “when a beam of

monochromatic light is passed through a homogenous absorbing medium, the rate of decrease
 dl 
of it’s intensity with the thickness of the medium    is directly proportional to the
 d 
dI
intensity of the radiation. i.e., it is an exponential function.  I
d

2. State and explain Beer’s law

It is another photo – physical law applicable to solution. It brigs out the effect of
concentration on absorption. It states that “The amount of light absorbed by a solution is
proportional to the concentration of the solution” mathematically it is represented to

Io k1
log  C
l t 2.303

C  Concentration ; k1  absorptivity constant

3. State and derive Beer – Lambert’s law.

It is the combination of Lambert’s and Beer’s laws. It states “when a beam of

monochromatic light is passed through a solution of absorbing substance, the rate of decrease
 dI 
of intensity of radiation with the thickness of the medium    is directly proportional to
 dl 
the intensity of the radiation as well as the concentration of the solution.

dI
i.e.,   IC
dL

dI
  kIC where k  absorption coefficient (constant)
dL

dI
  kCd 
I

A=CL L  length or thickness of the medium

-
Thus absorbance A is directly proportional to the concentration A  C as L is
constant for a particular solution and for constant thickness. When A is plotted against C, a
straight line is obtained.
4. What are the limitations of Beer – Lambert’s law?

Limitations of the law :

 Beer – Lambert’s law is valid for dilute solutions only;

Deviation
There is deviation when the concentration is higher (>
0.01 M)

A
 The radiation should be purely monochromatic.
 There should not be much temperature variation.
 There should not be any structural change during dilution C
such as Cr2O72- CrO42-
5. What are applications of Beer – Lambert’s law

 To determine the concentration of a solution :- A

number of standard solutions are prepared, The

A
absorbance values (A) are determined for them by
For unknown
means of spectrophotometer. Graph is drawn
connecting A & C. straight line is obtained. Then A is concentration
found out for unknown test solution. From the graph C
the corresponding concentration is found out.
 The concentration can also be determined using a single standard solution.
Astd = L Cstd and Aunknown = L Cunknown

A std Cstd

A unknown C unknown

A unknown  Cstd
C unknown   (calculate d)
A std

 This is the fundamental law for spectrophotometer and calorimetric estimation.

6. What is molar extinction coefficient? Or molar absorptivity? What isit’sunit?

Absorbance A = CL   absorption extinction coefficient.

A =  when C = 1 M and L = 1 cm. Hence absorbance coefficient is defined as

absorbance per unit concentration and unit length.

A A
ε  Unit of  is M-1 L cm-1 or M-1 dm3 cm-1
C  L C(m 1 ) Lcm

7. What is transmittance of a solution? How is it related to absorbance?

Transmittance (T) is defined as “the fraction of the incident light that is transmitted by
I
a given system” T  t
I0
 It
Taking logarithm log T  log
I0

I0
i.e.,  log T  log A
It

i.e., A, (absorbance) = – log T (transmittance)

and also  C L = – log T

 – log T is called absorbance or optical density

I0
i.e., A  log  ε CL   log T
It

9. A solution shows a transmittance of 20 % when taken in a cell of 2.5 cm thickness.

Calculate it’s concentration. The molar extinction coefficient is 12000 dm3m-1cm-1

Solution : Given ;- It = 20 % That means if I0 = 100 ; It = 20

I0 100
A  log  εCL i.e., log  12000  C  2.5 M-1Lcm-1
It 20

C = 2.33 × 10-5 ML-1

10. What is flame photometry? Mention it’s uses

When an atomized metal is introduced into a flame, it is electronically excited. On

return to the ground state, light of characteristic wavelength is given out. From the nature of
radiation (colour or ), the element is identified; From it’s intensity, it’s concentration is
estimated. Metals like Na, K, Li, Ca, etc are estimated by this method.

11. Explain the principle involved in flame photometry

Flame photometry is otherwise called flame emission spectroscopy substance is

ignited by LPG and air under pressure to high temperature (1700 C). Electronic excitation of
atom or ions takes place. While the excited atom returns to the ground state, radiation,
characteristic of the element is given out. From the region of the wavelength (colour) the
element is identified. From the intensity of the radiation, concentration is determined.

Example : Na gives out yellow light at the region  = 580 nm

K gives out violet light at the region  = 766 nm

12. How can the alkali or alkaline earth metals can be detected quantitatively in flame
photometry?

These metals can be detected from the color of the flame that they produce.
 Li  Scarlet red Na  Yellow K  Violet
Ca  Brick red Sr  Crimson red Cu  bluish green

13. What are the important process (steps) that occur in the flame emission
spectroscopy

i) Evaporation of the solvent from the liquid sample

ii) Decomposition of the solid in to atoms and vaporization

iii) Thermal excitation and returning to ground state giving out light

14. Name the interferences that we come across in flame photometry

 Spectral interference : This arises when two elements emit at particular wavelength.

 Ionic interference : It is due to ionization of certain atoms at high temperature.

 Anions interference : Some anions like oxalate, phosphate, sulphate etc., form stable
salts with cations and do not undergo dissociation and vaporization.

 Cation – cation - interference : It decreases the signal intensity

15. What are the applications of flame photometry?

 It is useful for analysis of metals like Na, K, Ca, Fe etc., particularly in biological
fluids and tissues.
 Useful for analysis of soil, natural water, glasses, cement, petroleum products etc.,
 Useful in medicinal and agricultural analysis

16. What are the limitations of flame photometry?

 Liquid sample of analyte is to be prepared

 It is not applicable to all metals. Elements like C, H, halogens, inert gases etc., can
not be estimated
 It gives no information about the molecular form of the metal in the original
sample

17. What is spectroscopy? (Or) What is the principle of spectroscopic techniques?

One form of electromagnetic radiations is allowed to interact with the atoms or

molecules and the emitted, or absorbed, or transmitted or scattered radiation is analyzed.
This is known as spectroscopy.
18. Bring out two essential points of differences between atomic and molecular spectra

Atomic spectra Molecular spectra

1 It is simple and line spectra It is complicated and band spectra

2 It is due to electronic transition – called It is due to vibration, rotation and

electronic spectra – appear in UV – electronic transitions– appear in IR
Visible region region

19. What is the principle of UV – visible spectra? What is it’s region?

When a monochromatic beam of radiation is passed

through a sample, a fraction of radiation is absorbed bringing

A
electronic transition; the rest is transmitted. Transmitted light is
recorded in terms of it’s absorbance ‘A’ which is 'plotted
against it’s wavelength. The hike in the curve indicates the
 
region of absorption.

Region : Zero  800 nm.

20. What are the different types of electronic transition? Arrange them in order of their
(3) (4)
energy. (1) (2)

 * >> n  * >   * > n  *

Among these (1) appears at higher energy region; (2) is forbidden transition; hence
(3) and (4) are important. They occur in the region 200 – 450 nm.

21. What are the different types of electronic transitions possible in the following
compounds?

i) CH3OCH3 ii) CH3NH2 iii) CH3CH2OH

iv) CH3CH2CH3 v) CH3CHO

..
Solution : i) CH3OCH3 i.e., CH3 – .O. – CH3   * and n  *
..
ii) CH3NH2 i.e., CH3 – NH2 . .   * and n  *
..
iii) CH3-CH2-OH i.e., CH3 – CH2 – O – H   * and n  *
..
iv) CH3-CH2-CH3 i.e., CH3 – CH2 – .CH
. 3 only   *

v) CH3 – CHO i.e., CH3 – CH = O  * ; n  *

   * ; n  *

22. Explain the following terms, giving examples

i) Chromophore ii) Auxochrome

i) Chromophores : The groups or structures that absorbs radiation and gives colour to the
molecules, if present sufficiently are called chromophores. They contain multiple bonds in
their structure.

Example : C = C ; - C  C - ; C = N - ; - N = N - ; O = N  O (NO2) etc.,

They are capable of absorbing in the region 200 – 800 nm.

ii) Auxochrome : Some groups in the molecules do not absorb light by themselves but shift
the position of parental absorption to higher region (longer wavelength) and thereby make it
more colourful – They are called auxochrome. They are found to have lone pair of electrons
in them.

Example : – OH
. . ; – NH
. . 2 ; – OR
.. ; – Cl
. . . etc.,
.. .. .. .
The shift is known as bathochromic shift (Red shift).

The groups that shift the absorption towards lower region are called hypsochromes
and the shift is called hypsochromic shift (low shift).

O 2N NO 2 OH

O 2N NO 2

Deep yellow dye

Yellow
NO 2

NO 2

Chromophore : – NO2 group

Auxochrome : – OH group

23.List out the applications of UV – Visible spectroscopy

 To identify alkanes, alkynes and arenes (In quantitative analysis)

 To identify aldehyde and ketones

 To detect the presence of conjugation

  To study the nature of shift and identify the position isomers

 To study the influence of pH on absorption indicator

..
24. What are the sources of light used for visible and UV light in UV spectra?

. . filament lamp is used.

For visible light, Tungsten

For UV radiation, Hydrogen or Deuterium lamp is used.

25. Arrange the following in the increasing order of their UV absorption maxima. Give
reason.

i) CH2 = CH2 ii) CH2 = CH – CH = CH2

HC CH2
iii) CH2 = CH – CH2 – CH =CH2 iv)

Increasing order (i) ~ (iii) < (ii) < (iv) because of greater conjugation effect, the
energy gap between the levels becomes smaller.

26. Most absorption band in the visible – UV spectra are very broad. Give reasons (Or)
Molecular spectra are mostly band spectra – explain.

Most of the electronic transition is followed by vibrational and rotational transition.

Because of these larger number of transitions, it is broad. (or it is band type).

27. What is IR spectra due to?

IR spectra are other wise known as vibrational spectra

shown by molecules, not by atoms. It arises due to absorption
%T

of electromagnetic radiation at IR region (4000 – 400 cm-1) and

bringing variation in vibrational energy levels.

The IR spectrum is obtained as a plot of percentage transmission (%T) against wave

 
number  . The region is above 800 nm (wavelength) in electro-magnetic radiation.

28. What is the finger print and group frequency region? Why are they called so?

The region between 1400 – 700 cm-1 is called finger print region, because at this
region the band is rich and very intense and no two organic compounds will have identical IR
spectra in this region.

The region between 4000 – 1400 cm-1 is called group frequency region, because
many groups gives their characteristic signals at this region.

29. What are the conditions for a molecule to be IR active? (OR) state vibrational
selection rule
i) When the molecule has permanent dipole moment, there should be change in dipole
moment during the vibration.

Example : (+)H – (-)Cl (+)H ----------- (-)Cl

Thus molecules like HCl, H2O, NH3, NO2, SO2 etc are IR active.

ii) In case there is no permanent dipole moment, the dipole moment should be created during
the mode of vibration. Example : CO2 has no dipole moment.; but it is IR active because
dipole moment () is created during one or two modes of vibration.

30. Molecules like H2, Cl2 and O2 are IR inactive – Why?

These molecules have neither permanent dipole moment nor dipole moment is created
during vibration.

31. Identify the molecules which are IR active among the following – give reasons

CO2, H2, HCl, Cl2, NH3, Ne, O2 and H2O.

HCl, NH3 and H2O  IR active, they have permanent dipole moment

CO2  IR active. Though it does not have any dipole moment, it is induced during
vibration

H2, O2  IR inactive. Neither have dipole moment nor it is created.

Ne  It is in atomic state – atoms do not give IR spectra, because IR spectrum is due

to vibration.

32. Discuss the applications of IR spectra

i) To identify functional groups

ii) To identify the presence of H-bonding

iii) To study the progress (kinetics) of a chemical reaction

iv) To test the purity of sample

v) To identify cis – trans isomers

vi) IR spectrum is also useful to identify tautomers.

vii) Shape of molecules elucidated

 PART B

1. Sketch the block diagram of flame photometer and explain the functions of various
components (OR) Explain how sodium can be estimated by flame photometric method

2. Explain the block diagram of UV visible spectrometer and explain the various components
and their function.

3. Sketch the block diagram of double beam IR spectrometer – Explain the functioning of
various parts

4. Explain the block diagram of TGA and explain the various components and their function.

5. Sketching the block diagram of DTA and explain the various components and their
function.