Professional Documents
Culture Documents
Cy Complete PDF
Cy Complete PDF
UNIT-02
Characterization techniques
Introduction to spectroscopy, UV-Visible spectroscopy- Absorption laws, Instrumentation, formation
of absorption bands, Chromophore and auxochrome concept, application of UV-Visible spectroscopy;
IR spectroscopy - Principle, selection rules, spectral features of some classes of compounds,
important features of IR spectroscopy and application; Introduction to Thermal methods,
instrumentation and applications (TGA, DTA, DSC)
UNIT-04
Corrosion and its control
Introduction, Types of corrosion-chemical and electrochemical, Mechanisms of corrosion, factors
affecting corrosion and different protection methods for corrosion control.
UNIT-05
Lubricants
Introduction, Mechanisms of lubrication, Types of lubricants, properties and different methods for
testing of lubricant oils and greases.
Books and References
1. Spectrometric Identification of Organic Compounds by R. M. Silverstein, F. X.
Webseter, and D. Kiemle, John Wiley & Sons
2. Organic Spectroscopy by W. L. Kemp, Palgrave
3. Spectroscopy by D. L. Pavia, Cengage.
4. Engineering Chemistry by Jain & Jain, Dhanpat Rai Publishing Co.
5. A text Book of Engineering Chemistry by Shashi Chawla, Dhanpat Rai & Co.
6. Engineering Chemistry by S.Vairam and S. Ramesh, Wiley.
7. Nanotechnology, Principles and Practices by Sulabha K .Kulkarni, Capital
Publishing Company.
8. Introduction to Environmental Engineering by M. Davis, D. Cornwell, Mcgraw-hill
Spectroscopy
http://www.nanophoton.net/raman/raman-spectroscopy.html
What is spectroscopy ?
Spectroscopy is a scientific measurement technique. It measures light that is emitted,
absorbed, or scattered by materials and can be used to study, identify and quantify
those materials.
http://www.inphotonics.com/raman.htm
In other words, it is a science which studies how light interacts with matter.
Light and its properties
Wavelength
Distance between the two adjacent crests or troughs in a particular wave
Frequency
No. of waves passing through a point in one second.
Wavenumber
Reciprocal of wavelength and expressed terms of per cm
Total number of waves which can pass through a space of one cm.
Energy
Wavelength: Distance between any two crests or trough in a particular waves
1 Å = 10-8 cm
3800 Å 7600 Å
Frequency
No. of waves passing through a point in one second.
Energy
Wavenumber (cm)
Assignments
Exercise 2: If λ = 4000 Å then find the wavenumber (cm-1) and also convert into nm.
Exercise 2: Calculate the frequency and energy associated with radiation of λ = 400 nm
and λ = 760 nm.
Electromagnetic spectrum
http://loke.as.arizona.edu/~ckulesa/camp/spectroscopy_intro.html
Higher energy/frequency
Important thing is that "light" is a lot more than just the colored visible light that
we can see-Red, Orange, Yellow, Green, Blue, Indigo, Violet) color spectrum.
Relevant
Thereregions
are manyforother
this course:
forms of light which are not visible to the human
•Radio → nuclear spinspectroscopy
eye and in magneticisfield
extended to cover all these.
•Microwave → rotation
•Infrared
There→are
vibration
gamma rays, x-rays, ultraviolet (UV) radiation, infrared (IR)
•Ultraviolet → electronic
radiation, microwaves and radio waves!
The interaction of electromagnetic radiation with matter
One of the such example of X-ray interaction is XPS
where by measuring the binding energy of the core
Energy/frequency electrons, chemical/electronic states can be measured.
It is useful for studying the materials elemental
composition, charge state etc.
http://hyperphysics.phy-astr.gsu.edu/hbase/mod3.html#c1
Classification of spectroscopy………….
Most spectroscopic methods are based on the interaction of light
with atomic or molecular system
Absorption spectroscopy
measure the absorption of light….
This interaction might give rise to electronic excitations, (e.g. UV),
molecular vibrations (e.g. IR)
Emission spectroscopy
Where the substance first absorb and then radiates the energy for example:
fluorescence
Scattering spectroscopy
measures the amount of light that a substance scatter at certain wavelength..
One of the most useful applications of light scattering spectroscopy is →
Raman spectroscopy.
X-ray crystallography is a scattering process
Absorption spectroscopy
https://chem.libretexts.org
What is spectroscopy ?
Electromagnetic spectrum ?
Classification of spectroscopy ?
Absorption spectroscopy ?
UV-Visible spectroscopy
Unit-4 Learned so far
What is spectroscopy ?
Electromagnetic spectrum ?
Classification of spectroscopy ?
Absorption spectroscopy ?
UV-Visible spectroscopy-Characteristics
absorption band
Absorption spectrum
Generally valence electrons participate and form a strong bands, they do not absorb the norbmal UV-
radiation, mainly saturated hydrocarbons
This type of transition takes place in alkyl halide or saturated compounds containing one heteroatoms
(containing lone pair of electrons…non-bonding electrons)
Mainly unsaturated hydrocarbons, dienes, alkenes, alkynes, aromatic compounds etc having pi bonds.
This type of transition takes place in carbonyl compounds or compounds having non bonding electrons and
pi bonds
UV-Visible spectroscopy
UV-Visible spectroscopy
UV-Visible spectroscopy
Auxochromes
Unit-4 Learned so far
What is spectroscopy ?
Light and interaction with matter ?
Electromagnetic spectrum ?
Classification of spectroscopy ?
Absorption spectroscopy ?
255 nm 280 nm
Extend of conjugation
280 nm 203 nm
255 nm
280 nm
CH3-CH=CH2 or CH3-CH=CH-CH=CH-CH3
Which one will absorb at higher wavelength ?
Which one will absorb at higher wavelength ?
Red shift
Absorption shift: cis and trans isomers
Trans will absorb at higher wavelength as compared to the cis form due to more
effective π obital overlapping and coplanarity in the π system
Due to steric effect, cis structure will be twisted slightly out of plane and degree of
conjugation is slightly less than trans isomers resulting in greater energy for the
transition….higher wavelenth
Beer-Lambert’s absorption Law
Ultraviolet-visible spectroscopy (UV-Vis)
Interaction of molecules with UV and Vis lights.
Involves absorption of electromagnetic light from UV and Vis spectral region.
Absorbance results in promotion of electrons from ground state to higher energy states
Electronic transition
I It
T t %T x 100
Io Io Io
light intensity (I)
Io It
l
It cuvette
l Sample depth/concentration
A cl A log10 T
The equation is called the Beer-Lambert law.
is called the molar absorption coefficient
Absorbance
Concentration
Quantity of electromagnetic radiation absorbed by a substance is directly proportional
to the concentration of the substance and path length of the light through the solution.
Infrared (IR) spectroscopy
Molecules are not rigid or inflexible structures but can bend and stretch in many
different ways- Molecular vibration
Important points:
Range of IR electromagnetic radiation wavelength ?
UV-Visible radiation cause electronic excitation, whereas IR radiation induces
molecular vibrations which cause various bonds to stretch and bend
Main IR region of interest
2.5 μ to 15 μ
Infrared (IR) spectroscopy…….
Basic modes of vibration
for example (-CH2-)
Stretching
Symmetrical Asymmetrical
stretching stretching
Bending
http://www.dynamicscience.com.au
Particle Translation Rotation Vibration Total
type ftransftrans frotfrot fvibfvib ff
monatomic 3 0 0 (×2×2) 3
diatomic
3 2 1 (×2×2) 7
(linear)
triatomic
3 3 3 (×2×2) 12
(non-linear)
triatomic
3 2 4 (×2×2) 13
(linear)
Infrared (IR) spectroscopy…….
Principle of IR Spectroscopy
Absorption of IR radiations causes an excitation of molecule from a lower to higher
vibrational level.
IR absorption spectra or band is also accompanied with change in rotational energy
levels.
All the bonds in a molecule are not capable of absorbing IR radiation.
Only those bonds which are accompanied with change in dipole moment will
absorb radiation in IR region.
Change in dipole moment
O-H
N-H
C-Cl
Fundamental vibrations are called IR active which are accompanied with change in
dipole moment of the molecules.
Molecules with symmetrical alkenes and alkynes are not accompanied with change in
dipole moment and are IR inactive and do not absorb IR radiation
Symmetrical alkenes C-C
Symmetrical alkynes C=C
Or if molecule has centre of symmetry then vibrations are centrosymmetric and are
IR inactive molecules
Also the diatomic molecules such as Cl2, H2 , O2 , N2 (centrosymmetric molecules)
Selection rule: IR spectroscopy
IR spectroscopy………….
IR radiation is absorbed by the bonds of a molecule when the stretching and
bending of each bond yields a change in the dipole moment of the molecule.
When the electromagnetic radiation interacts with the changing dipole moment of
the bond, IR radiation is absorbed.
For example;
Molecules such as Cl2 are IR inactive because they have no dipoles and will not
absorb IR radiation and thus transparent to IR while HCl absorbs.
-Dipole moment arises due to non-uniform distributions of positive and negative charges
on the various atoms e.g. Hδ+- Clδ-
-occur when two atoms in a molecule have substantially different electronegativities.
If the molecule is symmetrical, e.g. N2, the band is not observed in the IR spectrum
http://www.dynamicscience.com.au
IR spectroscopy………….
IR absorption spectra
An infrared spectrometer analyses a compound by passing infrared radiation, over a
range of different frequencies, and measures the absorptions made by each type of
bond in the compound.
This produces a spectrum, normally a ‘plot’ of % transmittance against wavenumber.
cm-1
For example: O-H, N-H will form H bonding with other molecules
weakening the O-H and N-H bonds
+I and –I effect
For example:
CH3-CO-CH3 1715 cm-1
CH3-CO-CH2Cl 1725 cm-1
Features of some functional gropus
Impurities in a compound can be detected from the nature of the bands which
are no longer sharp or well defined.
CONH2 ???
RCOOR ??
RCOOH ??
How to find difference in IR spectra of CH3CH2CHO and CH3COCH3 ?
THERMAL
ANALYSIS TECHNIQUES
Block diagram: TGA
DIFFERENTIAL THERMAL ANALYSIS (DTA)
Block diagram: DTA
Characterization of polymers
Characterization of polymers
Differential Scanning Calorimetry (DSC)
What is corrosion ?
Why its happened ?
What is the mechanism ?
Types of corrosion ?
What are the factors influencing corrosion ?
How to control corrosion ?
Corrosion ??
Reason ?
Therefore the metals can be regarded as excited state than their ores. So they
have a tendency to revert back to combined state when exposed to environment
and the destruction and deterioration of the metal starts at surface.
Dry corrosion
Wet corrosion
Dry or Chemical corrosion
Direct chemical action of environment/atmospheric gases such as oxygen,
halogen, hydrogen sulphide, sulphur dioxide or anhydrous inorganic liquid
with metal surfaces in immediate proximity.
Oxidation corrosion
By direct action of oxygen at low or high temperatures on metals, usually in absence
of moisture. Alkali and alkaline-earth metals can be oxidized at relatively low
temperature. At high temperatures, almost all metals got oxidized (except Ag, Pt
etc.)
For oxidation to continue, either the metal must diffuse outwards or oxygen must
diffuse inwards through the scale to the underlying metal
Both transfer can occur but the outward diffusion of metal is more rapid than
the inward diffusion of oxygen, since the metal ions are usually smaller than
the oxide ion and hence have higher mobility
When the oxidation starts, a thin layer of oxide is formed on the
metal surface and the nature of this film decides further action
If the film is
Stable
A stable layer is fine-grained in structure and can get adhered tightly to the
parent metal surface. So it can be of impervious nature (inhibits penetration
of attacking oxygen to the underlying metal) and can behaves as protective
coating. E.g. Oxide films on Al, Sn, Pb, etc.
stable
protective coating
If the film is
Unstable
Oxide layer formed, decomposes back into the metal and oxygen
Consequently, oxidation corrosion is not possible in this case (e.g. Ag, Au,
Pt etc.)
Volatile
Oxide layer volatilizes as soon as it is formed, thereby leaving the
underlying metal surface exposed for further attack.
Porous
Having pores or cracks. In such cases, the atmospheric oxygen have
access to the underlying surface of the metals and thereby
corrosion continues unobstructed, till the entire metal is completely
converted to its oxide
Types of Corrosion
Majorly classified based on the way corrosion takes place due to the surrounding
Dry corrosion
Wet corrosion
Wet corrosion
OR
Electrochemical corrosion
Electrochemical set up
Wet Corrosion
It occurs:
Where a conducting liquid is in contact with metal or
When two dissimilar metals or alloys are either immersed or
dipped partially in a solution
The metallic ions (at anodic part) and non-metallic ions (formed at
cathodic part) diffuse towards each other through conducting medium
and form a corrosion product. The electrons set free at anode flow
through the metal and finally consumed in the cathodic reaction.
Mechanism of Corrosion:
An Electrochemical Phenomenon
Flow of electron between anodic and cathodic areas
At Anodic area:
Dissolution of metal with liberation of electron (oxidation)
At Cathodic area:
Consumption of electron (reduction) either by
Evolution of hydrogen or
Absorption of oxygen
Absorption of oxygen
Eg. Rusting of iron in neutral aqueous solution of electrolyte (NaCl solution) in
presence of atmospheric oxygen
Surface of iron is coated with a thin film of iron oxide. If some cracks
developed, then anodic areas are created on the surface. Anodic areas are
small surface parts; while nearly the rest of the surface of the metal forms
large cathode
Fe2+ and OH- ions will diffuse and then combine to form the precipitate of
ferrous hydroxide. Smaller Fe2+ will diffuse more rapidly than larger OH-
ions. So corrosion occurs at the anode and rust deposited at or near the
cathode.
If enough oxygen is present, ferrous hydroxide will be oxidized to form
ferric hydroxide, which will form yellow rust
Zinc will dissolve at anodic areas and oxygen will take up electrons
at cathodic areas to form OH- ions.
Concentration Cell Corrosion
This type of corrosion is due to electrochemical attack on the metal surface,
exposed to an electrolyte of varying concentration or of varying aeration.
Differential aeration corrosion
(most common type of concentration cell corrosion)
When one part of metal is exposed to a different air concentration from the other
Crevice area has lack of oxygen (thus become anodic region and
corrosion takes there). The exposed area acts as cathode.
Eg. Buried pipelines passing from one type of soil to another suffer
corrosion due to differential aeration: like pipelines passing through
clay and then through sand. Since clay is less aerated than sand
hence corrosion starts.
Microbiological Corrosion
Due to metabolic activity under aerobic or anaerobic conditions
Caustic Embrittlement
Stress corrosion occurs in mild steels exposed to alkaline solution at
high temperature and stress (like in steam boilers)
Caustic embrittlement
Caustic embrittlement is the phenomenon in which the material of
a boiler becomes brittle due to the accumulation of caustic substances.
Humidity of air
Critical humidity: The relative humidity above which the
atmospheric corrosion rate of metal increases sharply. The value of
critical humidity depends on the physical characteristics of the
metal as well as the nature of the corrosion products.
5.2 Deactivation
Addition of chemicals capable of combining rapidly with oxygen in
aqueous solution (e.g. Na2SO3, hydrazine hydrate)
5.3 Dehumidification
Reduces the moisture content of air to such an extent that the
amount of water condensed on metal is too small to cause corrosion
(e.g. alumina, silica gel)
Hydrogen overvoltage is the potential difference that can be found between an electrode
and a reversible hydrogen electrode within a single solution. This is where hydrogen
(H2) undergoes formation from ions of hydrogen.
The key here is to elevate the hydrogen overvoltage in order to slow down or halt the
corrosion reaction. For instance, there are corrosion inhibitors that can make hydrogen
overvoltage increase and at the same time make dissolution current decrease as it
inhibits both cathodic and anodic processes.
The diffusion of H+ ions can be decreased by organic inhibitors
(amines, heterocyclic nitrogen compounds, substituted urea etc.),
which are capable of being adsorbed on the metal surface.
7. Protective Coatings
Coatings should prevent the penetration of corroding environment
to the material, which need to be protected
Coating must be chemically inert to the corroding environment
7.1 Anodic Coating
Coating metals are anodic w.r.t. the base metal (i.e. the metal to be
protected).
Eg. Coating of Zn on Fe
Eg. Coating of tin on iron sheet and the protection will be as long as
the surface of iron is completely covered. If the coating punctured,
then tin will act as cathode and exposed iron will act as anode. A
galvanic cell will be set up and an intense localized attack at the small
exposed part will occur, resulting severe pitting of the base metal.
Methods of application of metal coating
Hot dipping
For coating of low melting metals like Zn, Sn, Pb, Al etc on iron,
steel, copper etc., which have relatively higher melting points.
Immerse the base metal in a bath of molten coating metal
For good adhesion, the base metal surface must be very clean,
otherwise it cannot be properly wetted by the molten metal.
Procedure:
First clean the iron article by dilute H2SO4
Passed through a bath of zinc chloride flux and then pass through a
tank of molten tin and then through a series of rollers and finally
through palm oil, which protect the hot tin coated surface against
oxidation.
Metal Cladding
Dense, homogeneous layer of coating metal is bonded firmly and
permanently to the base metal on one or both sides.
Corrosion resisting metals (like Ni, Cu, Pb, Ag, Pt etc.) and alloys (like
stainless steel etc.) can be used as cladding materials.
Procedure
Thin sheets of coating metal and base metal are arranged in form of
sandwich
That sandwich then passed through rollers, under the action of heat
and pressure
Eg. Plate of duralumin is sandwiched between two layers of pure Al